JP2012174582A - Manufacturing method and manufacturing apparatus of wound type battery - Google Patents

Manufacturing method and manufacturing apparatus of wound type battery Download PDF

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JP2012174582A
JP2012174582A JP2011037011A JP2011037011A JP2012174582A JP 2012174582 A JP2012174582 A JP 2012174582A JP 2011037011 A JP2011037011 A JP 2011037011A JP 2011037011 A JP2011037011 A JP 2011037011A JP 2012174582 A JP2012174582 A JP 2012174582A
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electrode plate
softening agent
positive electrode
active material
flat
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JP5622048B2 (en
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Satoshi Fujita
聡 藤田
Takahiko Yamamoto
貴彦 山本
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Denso Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method and a manufacturing apparatus of a wound type battery capable of preventing trouble such as removal of an electrode active material layer and breakage of a collector from occurring even in a case of being bent by flat-pressing.SOLUTION: The manufacturing method of a wound type battery comprises a winding step of laminating and winding a positive electrode plate 10, a negative electrode plate 20 and a separator 30 (step S32), a flat-pressing step of flat-pressing a wound body formed in the winding step (step S34), and a softener impregnating step (step S30) of impregnating a softener into one or both electrode plates of the positive electrode plate 10 and the negative electrode plate 20. The electrode plate impregnated with softener is easily bent even if being bent by the flat-pressing, and thus the trouble such as removal of the electrode active material layer and breakage of the collector can be prevented from occurring.

Description

本発明は、少なくとも正極板，負極板，セパレータを備える捲回型電池を製造する製造方法および製造装置に関する。   The present invention relates to a manufacturing method and a manufacturing apparatus for manufacturing a wound battery including at least a positive electrode plate, a negative electrode plate, and a separator.

従来では、金属箔の内周側と外周側とで電極合剤のバインダ濃度を異ならせ、内周側のバインダ濃度が外周側のバインダ濃度より高くした非水電解液二次電池に関する技術の一例が開示されている（例えば特許文献１を参照）。   Conventionally, an example of a technique related to a non-aqueous electrolyte secondary battery in which the binder concentration of the electrode mixture is made different between the inner peripheral side and the outer peripheral side of the metal foil, and the binder concentration on the inner peripheral side is higher than the binder concentration on the outer peripheral side Is disclosed (see, for example, Patent Document 1).

また、電極の集電体の内側に塗布された電極合剤の塗布厚みが集電体の外側に塗布された電極合剤の塗布厚みより薄くした非水二次電池に関する技術の一例が開示されている（例えば特許文献２を参照）。   Also, an example of a technique related to a non-aqueous secondary battery in which the coating thickness of the electrode mixture applied to the inside of the electrode current collector is thinner than the coating thickness of the electrode mixture applied to the outside of the current collector is disclosed. (For example, refer to Patent Document 2).

さらに、正極集電体の最内周の端部には、いずれの面にも正極活物質が塗布されていない正極活物質非塗布部を設け、正極活物質非塗布部に隣接して捲き芯部の一周分が電極活物質の片面塗布部を有する捲回型電池に関する技術の一例が開示されている（例えば特許文献３を参照）。   Furthermore, a positive electrode active material non-applied portion on which no positive electrode active material is applied is provided on the innermost end portion of the positive electrode current collector, and the core is adjacent to the positive electrode active material non-applied portion. An example of a technique related to a wound battery in which a part of the part has a single-side coated part of an electrode active material is disclosed (see, for example, Patent Document 3).

そして、正極の電極合剤と心材との界面が、正極に曲げ応力を加えたときに剥離が起こる最弱部であって、捲回時に内側になる電極合剤層と心材との界面の剥離強度が外側の界面の剥離強度より小さくした非水電解液二次電池に関する技術の一例が開示されている（例えば特許文献４を参照）。   The interface between the electrode mixture of the positive electrode and the core material is the weakest part where peeling occurs when bending stress is applied to the positive electrode, and the interface between the electrode mixture layer and the core material that becomes inside when wound is peeled off An example of a technique related to a non-aqueous electrolyte secondary battery whose strength is smaller than the peel strength at the outer interface is disclosed (see, for example, Patent Document 4).

特許第３４２８１８４号公報Japanese Patent No. 3428184 特許第３４８９２８６号公報Japanese Patent No. 3489286 特許第３５０３９３５号公報Japanese Patent No. 3503935 特開２００８−０９１０５４号公報JP 2008-091054 A

しかし、特許文献１の技術を適用して内周側と外周側とで電極合剤のバインダ濃度を異ならせたり、特許文献２の技術を適用して内側と外側とで電極合剤の塗布厚みを異ならせても、扁平プレスによって屈曲される部位が所定の曲率半径よりも小さくなると、電極合剤や集電体等に不具合（例えば割れ，ヒビ等）が発生するという問題がある。   However, by applying the technique of Patent Document 1, the binder concentration of the electrode mixture is made different between the inner peripheral side and the outer peripheral side, or by applying the technique of Patent Document 2, the coating thickness of the electrode mixture on the inner side and the outer side. Even if they are different from each other, if the portion bent by the flat press becomes smaller than a predetermined radius of curvature, there is a problem that defects (for example, cracks, cracks, etc.) occur in the electrode mixture and the current collector.

また、特許文献３の技術を適用して、捲き芯部の一周分（最内周）について正極集電体に不具合が発生するのを防止できたとしても、二周目以降の外周側では扁平プレスによって正極集電体に不具合が発生するという問題がある。片面にのみ正極活物質を塗布する工程が必要になるので、正極活物質が塗布されていない部分の長さを管理するとともに、膜厚を均一にしなければならず、歩留まりが低下するという問題もある。   Moreover, even if it can prevent that a malfunction generate | occur | produces in a positive electrode electrical power collector about one round (innermost circumference) of a winding core part by applying the technique of patent document 3, it is flat on the outer peripheral side after the 2nd round. There is a problem that a problem occurs in the positive electrode current collector due to the press. Since the process of applying the positive electrode active material only on one side is required, the length of the portion where the positive electrode active material is not applied must be managed, the film thickness must be uniform, and the yield is also reduced. is there.

さらに、特許文献４の技術を適用して内側と外側とで剥離強度を異ならせても、扁平プレスによって屈曲される部位が所定の曲率半径よりも小さくなると、剥離が発生する可能性がある。剥離が発生すると、電極どうしが接触して蓄電力が低下したり、集電体に不具合が発生したりするという問題がある。   Furthermore, even if the technique of Patent Document 4 is applied and the peel strength is varied between the inside and the outside, peeling may occur if the portion bent by the flat press becomes smaller than a predetermined radius of curvature. When peeling occurs, there is a problem that the electrodes come into contact with each other and power storage is reduced, or a malfunction occurs in the current collector.

本発明はこのような点に鑑みてなしたものであり、扁平プレスによって屈曲しても、電極活物質層の剥離や集電体の切断等のような不具合の発生を防止できる捲回型電池の製造方法および製造装置を提供することを目的とする。   The present invention has been made in view of the above points, and is a wound battery that can prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector even when bent by a flat press. An object of the present invention is to provide a manufacturing method and a manufacturing apparatus.

上記課題を解決するためになされた請求項１に記載の発明は、それぞれが帯状の集電体上に電極活物質層を形成した正極板および負極板と、前記正極板と前記負極板との間に介在させる絶縁性のセパレータとを備える捲回型電池を製造する捲回型電池の製造方法において、前記正極板，前記負極板および前記セパレータを積層して捲回する捲回工程と、前記捲回工程によって形成される捲回体を扁平状に扁平プレスする扁平プレス工程と、前記捲回工程以前に行われ、前記正極板および前記負極板のうちで一方または双方の電極板に対し、軟化剤を含ませる軟化剤含蓄工程とを有することを特徴とする。   The invention according to claim 1, which has been made to solve the above-described problems, includes a positive electrode plate and a negative electrode plate each having an electrode active material layer formed on a strip-shaped current collector, and the positive electrode plate and the negative electrode plate. In a winding type battery manufacturing method for manufacturing a winding type battery comprising an insulating separator interposed therebetween, the winding step of laminating and winding the positive electrode plate, the negative electrode plate and the separator; and A flat pressing step for flatly pressing the wound body formed by the winding step, and performed before the winding step, one or both of the positive electrode plate and the negative electrode plate, And a softener storage step for containing the softener.

この構成によれば、軟化剤含蓄工程によって電極板に軟化剤を含ませると、当該軟化剤が含蓄された電極板は柔らかくなる。そのため、扁平プレス工程で扁平プレスを行って屈曲させても、電極板を容易に曲げることができる。したがって、電極活物質層の剥離や集電体の切断等のような不具合の発生を防止することができる。   According to this configuration, when the softener is included in the electrode plate in the softener storage step, the electrode plate containing the softener becomes soft. Therefore, the electrode plate can be bent easily even if it is bent by flat pressing in the flat pressing step. Therefore, it is possible to prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

なお、「集電体」は導電性の材料（物質を含む。以下同じである。）で帯状（長尺シート状）に形成されるが、板厚は任意である。「セパレータ」は正極板と負極板とが接触するのを防止する部材であって、例えば絶縁性の板材や固体電解質などを含む。「電極活物質層」は合剤層とも呼び、正極活物質層と負極活物質層とでは材料が異なる。正極活物質層は、例えばリチウムイオンなどの軽金属イオンを吸蔵・離脱することが可能な金属硫化物、金属酸化物または高分子化合物などの材料で構成される。負極活物質層は、例えばリチウム（Ｌｉ）やナトリウム（Ｎａ）などの軽金属、これらの軽金属を含む合金または軽金属を吸蔵・離脱することが可能な材料などで構成される。「短辺方向」は、集電体の長辺方向と交差する幅方向であって、かつ、面に沿う方向を意味する。「軟化剤」は、電極板（特に電極活物質層）を軟化させる材料（物質）であれば任意である。例えば、Ｎ−メチル−２−ピロリドン（ＮＭＰ）や、エタノール、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、イソプロパノール、水などが該当する。   Note that the “current collector” is formed of a conductive material (including a substance; the same applies hereinafter) in a band shape (long sheet shape), but the plate thickness is arbitrary. The “separator” is a member that prevents the positive electrode plate and the negative electrode plate from coming into contact with each other, and includes, for example, an insulating plate material or a solid electrolyte. The “electrode active material layer” is also called a mixture layer, and the positive electrode active material layer and the negative electrode active material layer are made of different materials. The positive electrode active material layer is made of a material such as a metal sulfide, a metal oxide, or a polymer compound capable of inserting and extracting light metal ions such as lithium ions. The negative electrode active material layer is made of, for example, a light metal such as lithium (Li) or sodium (Na), an alloy containing these light metals, or a material capable of inserting and extracting light metals. The “short-side direction” means a width direction that intersects the long-side direction of the current collector and a direction along the surface. The “softener” is optional as long as it is a material (substance) that softens the electrode plate (particularly the electrode active material layer). For example, N-methyl-2-pyrrolidone (NMP), ethanol, N, N-dimethylformamide (DMF), isopropanol, water and the like are applicable.

請求項２に記載の発明は、前記軟化剤含蓄工程は、前記軟化剤を滴下する滴下法、前記軟化剤を吹き付ける吹付法、軟化剤を塗布する塗布法、軟化剤を注入する注入法のうちでいずれかの方法で行うことを特徴とする。この構成によれば、軟化剤をより確実に電極板（特に電極活物質層）に含ませることができる。   The invention according to claim 2 is characterized in that the softening agent storing step includes a dropping method in which the softening agent is dropped, a spraying method in which the softening agent is sprayed, a coating method in which the softening agent is applied, and an injection method in which the softening agent is injected. The method is performed by any one of the methods. According to this configuration, the softener can be more reliably included in the electrode plate (particularly the electrode active material layer).

請求項３に記載の発明は、前記軟化剤含蓄工程は、前記電極板のうちで前記扁平プレス工程の扁平プレスによって得られる扁平体（すなわち扁平状の電極体）の屈曲部となる部位に対し、前記軟化剤を含ませることを特徴とする。電極活物質層の剥離や集電体の切断等のような不具合は、扁平プレスで屈曲させる曲率半径が小さくなる部位で発生し易い。この構成によれば、扁平体の屈曲部を含む部位に対して軟化剤を含ませるので、電極板を容易に曲げられるようになり、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。また、軟化剤を含ませる部位が限定されるので、必要な軟化剤が少なくて済み、コストを抑えることができる。   According to a third aspect of the present invention, in the softening agent-containing step, a portion of the electrode plate that becomes a bent portion of a flat body (that is, a flat electrode body) obtained by flat pressing in the flat pressing step. The softener is included. Problems such as peeling of the electrode active material layer and cutting of the current collector are likely to occur at a portion where the radius of curvature to be bent by the flat press is small. According to this configuration, since the softening agent is included in the portion including the bent portion of the flat body, the electrode plate can be easily bent, such as peeling of the electrode active material layer and cutting of the current collector. The occurrence of troubles can be prevented more reliably. Moreover, since the site | part to which a softener is included is limited, there are few required softeners and cost can be held down.

請求項４に記載の発明は、前記軟化剤含蓄工程は、前記扁平プレス工程で扁平プレスを行う際に前記軟化剤が全部乾燥しない時期に前記軟化剤を含ませることを特徴とする。この構成によれば、扁平プレスを行う際に軟化剤が全部乾燥していなければ、電極板（特に電極活物質層）の柔軟性が確保される。よって、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   The invention described in claim 4 is characterized in that the softening agent containing step includes the softening agent at a time when the softening agent is not completely dried when flat pressing is performed in the flat pressing step. According to this configuration, the flexibility of the electrode plate (particularly the electrode active material layer) is ensured if the softening agent is not completely dried during flat pressing. Therefore, it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

請求項５に記載の発明は、前記軟化剤含蓄工程は、前記軟化剤の含蓄量に対して、前記扁平プレス工程で扁平プレスを行う際に所定割合以上が残存する時期に前記軟化剤を含ませることを特徴とする。この構成によれば、扁平プレスを行う際に所定割合以上の軟化剤が残存すれば、電極板（特に電極活物質層）の柔軟性が確保される。よって、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。「所定割合」は電極板（特に電極活物質層）および軟化剤の各材料によって異なるので、用いる材料に適切な数値（例えば０．５％など）を設定する。   According to a fifth aspect of the present invention, the softening agent storage step includes the softening agent at a time when a predetermined ratio or more remains when flat pressing is performed in the flat pressing step with respect to the content of the softening agent. It is characterized by making it. According to this configuration, the flexibility of the electrode plate (particularly, the electrode active material layer) is ensured if a predetermined amount or more of the softening agent remains during flat pressing. Therefore, it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector. Since the “predetermined ratio” varies depending on each material of the electrode plate (particularly the electrode active material layer) and the softening agent, an appropriate numerical value (for example, 0.5%) is set for the material used.

請求項６に記載の発明は、前記軟化剤含蓄工程は、前記扁平体における所定の曲率半径以下となる部位に対応する前記電極板に対して前記軟化剤を含ませることを特徴とする。所定の曲率半径以下となる部位では、何ら措置を施さなければ電極活物質層の剥離や集電体の切断等のような不具合が発生する可能性がある。この構成によれば、所定の曲率半径以下となる部位に対応する電極板に対して軟化剤を含ませるので、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   The invention according to claim 6 is characterized in that the softening agent containing step includes the softening agent in the electrode plate corresponding to a portion of the flat body having a predetermined radius of curvature or less. If no measures are taken at a portion where the radius of curvature is equal to or less than a predetermined radius of curvature, problems such as peeling of the electrode active material layer and cutting of the current collector may occur. According to this configuration, since the softening agent is included in the electrode plate corresponding to the portion having a predetermined radius of curvature or less, the occurrence of problems such as peeling of the electrode active material layer or cutting of the current collector is further reduced. It can be surely prevented.

請求項７に記載の発明は、前記軟化剤含蓄工程は、前記扁平体における所定周回までの部位に対応する前記電極板に対して前記軟化剤を含ませることを特徴とする。所定周回（「捲数」とも呼ぶ。以下同じである。）までの部位では曲率半径が小さいため、何ら措置を施さなければ電極活物質層の剥離や集電体の切断等のような不具合が発生する可能性がある。この構成によれば、所定周回までの部位に対応する電極板に対して軟化剤を含ませるので、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。「所定周回」は集電体および電極活物質層の各厚さによって異なるが、例えば１〜３[回]である。   The invention described in claim 7 is characterized in that the softening agent storing step includes the softening agent in the electrode plate corresponding to a portion of the flat body up to a predetermined turn. Since the radius of curvature is small at a part up to a predetermined number of rounds (also called “the number of powers”, the same shall apply hereinafter), there are problems such as peeling of the electrode active material layer and cutting of the current collector if no measures are taken. May occur. According to this configuration, since the softening agent is included in the electrode plate corresponding to the part up to the predetermined turn, the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector can be prevented more reliably. can do. The “predetermined number of turns” varies depending on the thicknesses of the current collector and the electrode active material layer, but is, for example, 1 to 3 [times].

請求項８に記載の発明は、前記軟化剤含蓄工程は、前記扁平体の内周側から外周側に向かうにつれて、前記軟化剤の含蓄量を変化させることを特徴とする。捲きつけてゆく電極板は内周側から外周側に向かって、屈曲する部位の曲率半径が大きくなるので、何ら措置を施さなくても不具合が発生する割合は低下する。この構成によれば、扁平体の屈曲部を含む部位に対して含ませる軟化剤の含蓄量を変化させる（通常は少なくする）ので、軟化剤の必要量が少なくて済み、コストを抑えることができる。   The invention described in claim 8 is characterized in that in the softening agent storage step, the content of the softening agent is changed from the inner peripheral side to the outer peripheral side of the flat body. Since the radius of curvature of the bent portion of the electrode plate that is attracted increases from the inner peripheral side toward the outer peripheral side, the rate of occurrence of defects is reduced even if no measures are taken. According to this configuration, since the content of the softening agent to be included in the portion including the bent portion of the flat body is changed (usually reduced), the required amount of the softening agent can be reduced, and the cost can be reduced. it can.

請求項９に記載の発明は、前記軟化剤含蓄工程は、前記扁平体の周回数に基づいて、前記軟化剤の含蓄量を変化させることを特徴とする。この構成によれば、１周回目よりも２周回目に含ませる軟化剤の含蓄量を変化させ（通常は減らし）、２周回目よりも３周回目に含ませる軟化剤の含蓄量を変化させるなどのように周回数に応じて軟化剤の含蓄量を変化させる。よって軟化剤の必要量が少なくて済み、コストを抑えることができる。   The invention described in claim 9 is characterized in that the softener storage step changes the content of the softener based on the number of rounds of the flat body. According to this configuration, the content of the softening agent included in the second round than the first round is changed (usually reduced), and the content of the softening agent included in the third round is changed from the second round. The content of the softener is changed according to the number of laps. Therefore, the required amount of the softening agent is small, and the cost can be suppressed.

請求項１０に記載の発明は、前記軟化剤含蓄工程は、前記扁平体の曲率半径に基づいて、前記軟化剤の含蓄量を変化させることを特徴とする。この構成によれば、例えば曲率半径が大きくなるにつれて軟化剤の含蓄量を少なくする。こうすれば軟化剤の必要量が少なくて済み、コストを抑えることができる。   The invention described in claim 10 is characterized in that the softener storage step changes the content of the softener based on a curvature radius of the flat body. According to this configuration, for example, the content of the softening agent is decreased as the radius of curvature increases. In this way, the required amount of softening agent can be reduced, and the cost can be reduced.

請求項１１に記載の発明は、前記軟化剤含蓄工程は、前記電極活物質層を構成するバインダのＳＰ値との差が所定値範囲内となるＳＰ値を有する前記軟化剤を用いて、前記電極板に含ませることを特徴とする。この構成によれば、軟化剤のＳＰ（Solubility Parameter；溶解パラメーター）値はバインダのＳＰ値との差が所定値範囲内（例えば±１０以内）となる。ＳＰ値の差が小さいほど溶解度が大きくなることが経験的に知られているので、軟化剤が電極活物質層のバインダと溶解し易くなり、含蓄させ易い。したがって、軟化剤を含蓄させることが容易になるので、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   The invention according to claim 11 is characterized in that the softening agent storing step uses the softening agent having an SP value in which a difference from an SP value of a binder constituting the electrode active material layer is within a predetermined value range. It is included in an electrode plate. According to this configuration, the SP (Solubility Parameter) value of the softener is different from the SP value of the binder within a predetermined value range (for example, within ± 10). Since it is empirically known that the smaller the difference in SP value, the higher the solubility, the softener is easily dissolved with the binder of the electrode active material layer, and is easily contained. Therefore, it becomes easy to contain the softening agent, so that it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

請求項１２に記載の発明は、それぞれが帯状の集電体上に電極活物質層を形成した正極板および負極板と、前記正極板と前記負極板との間に介在させる絶縁性のセパレータとを備える捲回型電池を製造する捲回型電池の製造装置において、前記正極板，前記負極板および前記セパレータを積層して捲回する捲回手段と、前記捲回手段によって形成される捲回体を扁平状に扁平プレスする扁平プレス手段と、前記捲回手段以前に行われ、前記正極板および前記負極板のうちで一方または双方の電極板に対し、軟化剤を含ませる軟化剤含蓄手段とを有することを特徴とする。この構成によれば、請求項１に記載の発明と同様に、扁平プレス工程で扁平プレスを行って屈曲させても、電極板を容易に曲げることができる。したがって、電極活物質層の剥離や集電体の切断等のような不具合の発生を防止することができる。   The invention described in claim 12 includes a positive electrode plate and a negative electrode plate each having an electrode active material layer formed on a strip-shaped current collector, and an insulating separator interposed between the positive electrode plate and the negative electrode plate. In a winding type battery manufacturing apparatus for manufacturing a winding type battery comprising: a winding means for laminating and winding the positive electrode plate, the negative electrode plate and the separator; and a winding formed by the winding means Flat pressing means for flatly pressing the body, and softening agent storage means which is performed before the winding means and includes one or both of the positive electrode plate and the negative electrode plate. It is characterized by having. According to this configuration, similarly to the first aspect of the invention, the electrode plate can be easily bent even if it is bent by flat pressing in the flat pressing step. Therefore, it is possible to prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

電極板の構成例を模式的に示す側面図である。It is a side view which shows the structural example of an electrode plate typically. 捲回型電池の第１製造方法を示すチャート図である。It is a chart figure showing the 1st manufacturing method of a winding type battery. 軟化剤を含ませる部位を模式的に示す側面図である。It is a side view which shows typically the site | part which contains a softening agent. 軟化剤を含ませる部位を模式的に示す側面図である。It is a side view which shows typically the site | part which contains a softening agent. 捲回工程の一例を示す側面図である。It is a side view which shows an example of a winding process. 扁平プレス工程の一例を示す側面図である。It is a side view which shows an example of a flat press process. 捲回型電池の第２製造方法を示すチャート図である。It is a chart figure showing the 2nd manufacturing method of a winding type battery.

以下、本発明を実施するための形態について、図面に基づいて説明する。なお、各図は本発明を説明するために必要な要素を図示し、実際の全要素を図示してはいない。上下左右等の方向を言う場合には、図面の記載を基準とする。「材料」には物質を含む。単に「電極板」と言う場合には、正極板および負極板のうちで一方または双方を意味する。   Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. In addition, each figure shows the element required in order to demonstrate this invention, and does not show all the actual elements. When referring to directions such as up, down, left and right, the description in the drawings is used as a reference. “Material” includes substances. When it is simply referred to as “electrode plate”, it means one or both of a positive electrode plate and a negative electrode plate.

まず、捲回型電池の基礎となる電極板の構成例について、図１を参照しながら説明する。電極板の構成例を模式的に図１に示す。図１（Ａ）には捲回前の状態を側面図で示し、図１（Ｂ）には扁平プレス後の状態を側面図で示し、図１（Ｃ）には平面図で示す。   First, a configuration example of an electrode plate that is the basis of a wound battery will be described with reference to FIG. A configuration example of the electrode plate is schematically shown in FIG. 1A is a side view showing a state before winding, FIG. 1B is a side view showing a state after flat pressing, and FIG. 1C is a plan view.

捲回型電池の構成要素である電極体（後述する扁平体）は、帯状の電極板を捲回して渦巻き状にし、さらに扁平状にプレスすることで得られる。図１は、見易くするために屈曲部を中心とする一部分を示す。本形態にかかる捲回型電池の正極板と負極板とは、正負が異なるに過ぎない。よって正極板を代表して説明し、負極板については正極板と異なる内容を説明する。   An electrode body (a flat body to be described later) that is a constituent element of a wound battery is obtained by winding a band-shaped electrode plate into a spiral shape and further pressing it into a flat shape. FIG. 1 shows a portion centered on a bend for ease of viewing. The positive electrode plate and the negative electrode plate of the wound battery according to this embodiment are only different in positive and negative. Therefore, the positive electrode plate will be described as a representative, and the content different from the positive electrode plate will be described for the negative electrode plate.

図１（Ａ）に示す正極板１０は、帯状をなす正極集電体１２の面上に正極活物質層１１，１３が形成される。正極集電体１２は、導電性の材料（例えば金属や導電性プラスチック等）で帯状に形成される。厚さは製造する捲回型電池の仕様（例えば蓄電容量や外形寸法等）に合わせて設定され、例えば５〜３００[μｍ]程度である。負極板については、正極板１０と同じ厚さにしてもよく、異なる厚さにしてもよい。形状についても同様であり、例えば平板状，箔状，網状などが該当する。正極活物質層１１は捲回後の外周面側に形成され、正極活物質層１３は捲回後の内周面側に形成される。   In the positive electrode plate 10 shown in FIG. 1A, positive electrode active material layers 11 and 13 are formed on the surface of a positive electrode current collector 12 having a strip shape. The positive electrode current collector 12 is formed in a strip shape from a conductive material (for example, metal or conductive plastic). The thickness is set in accordance with the specifications of the wound battery to be manufactured (for example, storage capacity, outer dimensions, etc.), and is, for example, about 5 to 300 [μm]. The negative electrode plate may have the same thickness as the positive electrode plate 10 or a different thickness. The same applies to the shape, for example, a flat plate shape, a foil shape, a net shape, or the like. The positive electrode active material layer 11 is formed on the outer peripheral surface side after winding, and the positive electrode active material layer 13 is formed on the inner peripheral surface side after winding.

正極活物質層１１，１３は、例えばリチウムイオンなどの軽金属イオンを吸蔵・離脱することが可能な金属硫化物、金属酸化物または高分子化合物などの材料で構成される。なお図示しないが、負極板を構成する負極集電体の面上に形成される負極活物質層は、例えばリチウムやナトリウムなどの軽金属、これらの軽金属を含む合金または軽金属を吸蔵・離脱することが可能な材料などで構成される。   The positive electrode active material layers 11 and 13 are made of a material such as a metal sulfide, a metal oxide, or a polymer compound that can occlude / release light metal ions such as lithium ions. Although not shown, the negative electrode active material layer formed on the surface of the negative electrode current collector constituting the negative electrode plate can occlude / release light metals such as lithium and sodium, alloys containing these light metals, or light metals. Consists of possible materials.

扁平プレス後の屈曲部Ｂに対応する部位の正極板１０には、扁平プレスの際に曲げ易くするため、軟化剤を含ませる。具体的には、正極活物質層１１，１３に軟化剤を含ませる。負極板２０についても同様である。軟化剤を含ませる部位は、図１（Ａ）に斜線ハッチで示すように、扁平プレスによって得られる扁平体２００の屈曲部Ｂ（図１（Ｂ）を参照）を含む部位である。なお、外周面側の正極活物質層１３は、内周面側の正極活物質層１１よりも曲率半径が大きくなる。そのため、正極活物質層１３に含ませる軟化剤の含蓄量は、正極活物質層１１よりも少なくしてよい。   A softener is included in the positive electrode plate 10 corresponding to the bent portion B after the flat press in order to facilitate bending during the flat press. Specifically, a softener is included in the positive electrode active material layers 11 and 13. The same applies to the negative electrode plate 20. The site | part to which a softener is included is a site | part containing the bending part B (refer FIG. 1 (B)) of the flat body 200 obtained by flat press, as shown by the hatching hatching in FIG. 1 (A). The positive electrode active material layer 13 on the outer peripheral surface side has a larger radius of curvature than the positive electrode active material layer 11 on the inner peripheral surface side. Therefore, the content of the softener contained in the positive electrode active material layer 13 may be less than that of the positive electrode active material layer 11.

軟化剤は、正極活物質層１１，１３を軟化させる材料であれば任意である。すなわち、正極活物質層１１，１３の材料との関係で軟化剤が定まる。例えば、正極活物質層１１，１３のバインダ１０ａとしてポリフッ化ビニリデン（ＰＶＤＦ）を用いる場合には、Ｎ−メチル−２−ピロリドン（ＮＭＰ）や、エタノールなどが該当する（後述する表１，２を参照）。他の材料を用いる場合には、例えばＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、イソプロパノール、水などが該当する。   The softening agent is arbitrary as long as it is a material that softens the positive electrode active material layers 11 and 13. That is, the softening agent is determined depending on the material of the positive electrode active material layers 11 and 13. For example, when polyvinylidene fluoride (PVDF) is used as the binder 10a of the positive electrode active material layers 11 and 13, N-methyl-2-pyrrolidone (NMP), ethanol, and the like are applicable (see Tables 1 and 2 described later). reference). When other materials are used, for example, N, N-dimethylformamide (DMF), isopropanol, water and the like are applicable.

上述のように軟化剤を含ませた正極板１０および負極板２０の相互間に絶縁性のセパレータ３０を介在させて捲回し（図５を参照）、さらに扁平プレスすると（図６を参照）、図１（Ｂ）に示すような扁平体２００が形成される。軟化剤によって電極板（特に電極活物質層）は軟らかくなっているので、扁平プレスを行っても電極活物質層の剥離や集電体の切断等のような不具合が発生することはない。   When the insulating separator 30 is interposed between the positive electrode plate 10 and the negative electrode plate 20 containing the softening agent as described above (see FIG. 5), and further flat pressing (see FIG. 6), A flat body 200 as shown in FIG. 1B is formed. Since the electrode plate (especially the electrode active material layer) is softened by the softening agent, problems such as peeling of the electrode active material layer and cutting of the current collector do not occur even when flat pressing is performed.

帯状の正極板１０を平面的に見ると、図１（Ｃ）に示すような構造になる。電極板は、後述するスリット工程（図２に示すステップＳ１６，Ｓ２６）において、板幅を示す電極幅Ｗａで切断される。他に、板長（長辺方向の長さ）や板厚等で切断される場合もある。正極板１０には、図２（Ａ）の図面上側に示すように正極活物質層１１が形成されずに正極集電体１２が露出する部位、すなわち正極集電体１２のみの部位がある。当該正極集電体１２のみの部位は、後述する扁平プレス工程（図２に示すステップＳ３４）を行った後、正極集電体１２どうしを電気的に接続して正極とするために用いる。負極板２０の負極集電体２２についても同様である。なお、形成幅Ｗｃは正極集電体１２の面上に正極活物質層１１を形成する幅（幅方向の長さ）である。   When the belt-like positive electrode plate 10 is viewed in plan, the structure shown in FIG. The electrode plate is cut at an electrode width Wa indicating the plate width in a slit process (steps S16 and S26 shown in FIG. 2) described later. In addition, it may be cut by a plate length (length in the long side direction), a plate thickness, or the like. As shown in the upper side of FIG. 2A, the positive electrode plate 10 has a portion where the positive electrode current collector 12 is exposed without forming the positive electrode active material layer 11, that is, a portion of only the positive electrode current collector 12. The portion having only the positive electrode current collector 12 is used to electrically connect the positive electrode current collectors 12 to a positive electrode after performing a flat pressing process (step S34 shown in FIG. 2) described later. The same applies to the negative electrode current collector 22 of the negative electrode plate 20. The formation width Wc is a width (length in the width direction) for forming the positive electrode active material layer 11 on the surface of the positive electrode current collector 12.

図１（Ｃ）に斜線ハッチで示すように、軟化剤を含ませる部位は扁平プレスによって得られる扁平体２００の屈曲部Ｂを含む部位であって、正極活物質層１１（反対面の正極活物質層１３）がある部位である。なお、集電体を軟化させる材料が軟化剤に含まれている場合には、露出する部位の正極集電体１２にも含ませるのが望ましい。   As shown by the hatched hatching in FIG. 1C, the part containing the softening agent is a part including the bent portion B of the flat body 200 obtained by flat pressing, and the positive electrode active material layer 11 (the positive electrode active material on the opposite surface). This is where the material layer 13) is. In addition, when the material which softens a collector is contained in the softening agent, it is desirable to include also in the positive electrode collector 12 of the exposed part.

次に、正極板１０，負極板２０，セパレータ３０などを積層して捲回型電池を製造する工程について、チャート図で示す図２を参照しながら説明する。図２に示す製造方法は、正極板１０を形成する第１工程と、負極板２０を形成する第２工程と、形成された正極板１０および負極板２０とともにセパレータ３０を積層して捲回および扁平プレスを行う第３工程とに大きく分けられる。以下では第１工程から第３工程の順番に説明するが、第１工程と第２工程は順不同で行ってよい。   Next, a process of manufacturing a wound battery by stacking the positive electrode plate 10, the negative electrode plate 20, the separator 30 and the like will be described with reference to FIG. The manufacturing method shown in FIG. 2 includes a first step of forming the positive electrode plate 10, a second step of forming the negative electrode plate 20, winding the separator 30 together with the formed positive electrode plate 10 and negative electrode plate 20, This can be broadly divided into the third step of flat pressing. In the following, description will be given in the order from the first step to the third step, but the first step and the second step may be performed in any order.

（第１工程）正極板１０の形成工程
まず、正極集電体１２上に形成する正極活物質層１１，１３の混練物を作製する混練工程を行う〔ステップＳ１０〕。混練物は、バインダ１０ａ、正極活物質１０ｂ、導電材１０ｃ、溶媒１０ｄなどを混ぜ合わせて液状またはペースト状にした物である。 (First Step) Formation Step of Positive Electrode Plate 10 First, a kneading step is performed to produce a kneaded product of the positive electrode active material layers 11 and 13 formed on the positive electrode current collector 12 [Step S10]. The kneaded product is a product obtained by mixing a binder 10a, a positive electrode active material 10b, a conductive material 10c, a solvent 10d, and the like into a liquid or paste form.

バインダ１０ａは、任意の結着剤を用いることができる。例えば、ポリフッ化ビニリデン（ＰＶＤＦ）や、ポリフッ化ビニリデンの変性体、ポリテトラフルオロエチレン（ＰＴＦＥ）、アクリレート単位を有するゴム粒子結着剤などが該当する。なお、反応性官能基を導入したアクリレートモノマーや、アクリレートオリゴマーなどを混入してもよい。   Any binder can be used for the binder 10a. For example, polyvinylidene fluoride (PVDF), a modified body of polyvinylidene fluoride, polytetrafluoroethylene (PTFE), a rubber particle binder having an acrylate unit, and the like are applicable. In addition, you may mix the acrylate monomer which introduce | transduced the reactive functional group, an acrylate oligomer, etc.

正極活物質１０ｂは、例えばリチウムイオンなどの軽金属イオンを吸蔵・離脱することが可能な物質で構成される。具体的には、金属硫化物、金属酸化物または高分子化合物などが該当する。金属硫化物や金属酸化物には、例えば硫化チタン（ＴｉＳ2）、硫化モリブデン（ＭｏＳ2）、セレン化ニオブ（ＮｂＳｅ2）または酸化バナジウム（Ｖ2Ｏ5）などのリチウムを含有しないものが挙げられる。金属酸化物には、上記したリチウムを含有しない物質のほか、ＬｉxＭＯyなどで表されるリチウム複合酸化物が挙げられる。なお、Ｍαは、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、マンガン（Ｍｎ）などの遷移金属である。ＭβやＭγは、鉄（Ｆｅ）、亜鉛（Ｚｎ）、クロム（Ｃｒ）、Ａｌ、Ｍｎ、Ｃｏ、Ｎｉ、Ｔｉのうちで一以上の金属元素、あるいはリン（Ｐ）やホウ素（Ｂ）などの非金属元素である。組成式の添字について、ｘは０．０５≦ｘ≦２．０、ｙは２≦ｙ≦４の範囲内でそれぞれ設定するのが望ましい。 The positive electrode active material 10b is made of a material capable of inserting and extracting light metal ions such as lithium ions. Specifically, metal sulfides, metal oxides, polymer compounds, and the like are applicable. Examples of metal sulfides and metal oxides include those that do not contain lithium, such as titanium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), niobium selenide (NbSe 2 ), or vanadium oxide (V 2 O 5 ). It is done. Examples of the metal oxide include lithium composite oxides represented by Li x MO y in addition to the above-described substances not containing lithium. Note that Mα is a transition metal such as cobalt (Co), nickel (Ni), or manganese (Mn). Mβ and Mγ are one or more metal elements among iron (Fe), zinc (Zn), chromium (Cr), Al, Mn, Co, Ni and Ti, or phosphorus (P) and boron (B). It is a nonmetallic element. As for the subscripts of the composition formula, it is desirable to set x within a range of 0.05 ≦ x ≦ 2.0 and y within a range of 2 ≦ y ≦ 4.

正極活物質１０ｂは、特に高電圧・高エネルギー密度の確保およびサイクル特性を向上させるため、リチウム・コバルト複合酸化物やリチウム・ニッケル酸化物などのリチウム複合酸化物を用いるのが望ましい。上述した金属硫化物や金属酸化物などのうちで二種以上組み合わせて用いてもよい。正極活物質１０ｂに用いる材料は、電池の種類や用途等に応じて任意に選択可能である。   As the positive electrode active material 10b, it is desirable to use a lithium composite oxide such as lithium / cobalt composite oxide or lithium / nickel oxide in order to ensure high voltage and high energy density and improve cycle characteristics. Two or more of the metal sulfides and metal oxides described above may be used in combination. The material used for the positive electrode active material 10b can be arbitrarily selected according to the type and use of the battery.

導電材１０ｃは、例えばカーボンブラックなどのような導電性の材料を用いる。カーボンブラックは、ＢＥＴ法による比表面積が３０[ｍ2／ｇ]以上の高比表面積のものを用いるのが望ましい。 For the conductive material 10c, for example, a conductive material such as carbon black is used. It is desirable to use carbon black having a high specific surface area of 30 [m 2 / g] or more by a BET method.

溶媒１０ｄは、混練に適したものを用いる。例えば、１，２−ジメトキシエタン、１，２−ジエトキシエタン、プロピレンカーボネート、ブチレンカーボネート、エチレンカーボネート、γ−ブチロラクトン、テトラヒドロフラン、１，３−ジオキソラン、ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネートなどの単独溶媒や、これらの溶媒のうちで二種以上を選択して混合させた混合溶媒などが該当する。   A solvent suitable for kneading is used as the solvent 10d. For example, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene carbonate, butylene carbonate, ethylene carbonate, γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, etc. A solvent, a mixed solvent in which two or more of these solvents are selected and mixed, and the like are applicable.

ステップＳ１０で作製した混練物を正極集電体１２上に正極活物質層１１，１３として形成する塗工・乾燥工程を行う〔ステップＳ１２〕。具体的には、混練物を正極集電体１２上に塗工した後、所定温度下で乾燥させて固形化する。塗工は、例えば塗装，塗りつけ，吹きつけ等が該当する。正極活物質層１１，１３は、乾燥後に所定厚さ（例えば１００〜３００[μｍ]）となるように塗工量を調整する。正極集電体１２の厚さは、例えば１０〜２０[μｍ]程度である。こうして帯状の正極板１０が形成される。   A coating / drying process is performed in which the kneaded material prepared in step S10 is formed as the positive electrode active material layers 11 and 13 on the positive electrode current collector 12 [step S12]. Specifically, after the kneaded material is coated on the positive electrode current collector 12, it is dried at a predetermined temperature to be solidified. Examples of the coating include painting, painting, spraying, and the like. The coating amount of the positive electrode active material layers 11 and 13 is adjusted so as to have a predetermined thickness (for example, 100 to 300 [μm]) after drying. The thickness of the positive electrode current collector 12 is, for example, about 10 to 20 [μm]. In this way, a strip-like positive electrode plate 10 is formed.

その後、プレス機（例えばローラ等）によって正極板１０をプレスするプレス工程〔ステップＳ１４〕と、スリット加工機によって正極板１０を所定形状（板長，板厚，板幅等）に切断するスリット工程〔ステップＳ１６〕とを順不同で行う。こうして、捲回可能な正極板１０が形成される。   Thereafter, a pressing step (step S14) of pressing the positive electrode plate 10 with a press machine (for example, a roller) and a slitting step of cutting the positive electrode plate 10 into a predetermined shape (plate length, plate thickness, plate width, etc.) with a slitting machine. [Step S16] is performed in any order. In this way, the positive electrode plate 10 which can be wound is formed.

（第２工程）負極板２０の形成工程
負極集電体２２に形成する負極活物質層２１，２３の混練物を作製する混練工程を行う〔ステップＳ２０〕。混練物は、バインダ２０ａ、負極活物質２０ｂ、分散材２０ｃ、溶媒２０ｄなどを混練した物である。 (2nd process) Formation process of the negative electrode plate 20 The kneading | mixing process which produces the kneaded material of the negative electrode active material layers 21 and 23 formed in the negative electrode collector 22 is performed [step S20]. The kneaded product is a product obtained by kneading the binder 20a, the negative electrode active material 20b, the dispersion material 20c, the solvent 20d, and the like.

バインダ２０ａは、バインダ１０ａと同様に任意の結着剤を用いることができる。例えば、ポリフッ化ビニリデン（ＰＶＤＦ）や、その変性体などが該当する。なお、リチウムイオン受入れ性を向上させるため、スチレン−ブタジエン共重合体ゴム粒子（ＳＢＲ）およびその変性体に対し、カルボキシメチルセルロース（ＣＭＣ）をはじめとするセルロース系樹脂等を併用したり、少量添加したりするのが望ましい。   The binder 20a can use arbitrary binders similarly to the binder 10a. For example, polyvinylidene fluoride (PVDF) or a modified product thereof is applicable. In order to improve the lithium ion acceptability, styrene-butadiene copolymer rubber particles (SBR) and modified products thereof may be used in combination with cellulose resins such as carboxymethyl cellulose (CMC) or in small amounts. Is desirable.

負極活物質２０ｂは、軽金属、当該軽金属を含む合金、当該合金や軽金属自体を吸蔵・離脱することが可能な材料などで構成される。軽金属は、例えばリチウム（Ｌｉ）やナトリウム（Ｎａ）などが該当する。軽金属を吸蔵・離脱することが可能な材料は、例えば炭素材料、珪素（Ｓｉ）、珪素化合物、金属酸化物または高分子化合物などが該当する。炭素材料は、例えば熱分解炭素類、コークス類、黒鉛類、ガラス状炭素類、有機高分子化合物焼成体、炭素繊維または活性炭などが該当する。コークス類には、例えばピッチコークス，ニードルコークス，石油コークスなどを含む。ガラス状炭素類には、難黒鉛化炭素材料などを含む。有機高分子化合物焼成体は、不活性ガス気流中または真空中において高分子化合物（例えばフェノール樹脂やフラン樹脂など）を高温（例えば約５００℃以上）で焼成して炭素化された物質である。珪素化合物は、例えばＣａＳｉ2やＣｏＳｉ2などが該当する。金属酸化物は、例えば酸化スズ（ＳｎＯ2）などが該当する。高分子化合物は、例えばポリアセチレンやポリピロールなどが該当する。負極活物質２０ｂとして用いる材料は、電池の種類や用途等に応じて任意に選択可能である。 The negative electrode active material 20b is composed of a light metal, an alloy containing the light metal, a material capable of inserting and extracting the alloy and the light metal itself, and the like. Examples of the light metal include lithium (Li) and sodium (Na). Examples of the material capable of inserting and extracting light metals include carbon materials, silicon (Si), silicon compounds, metal oxides, and polymer compounds. Examples of the carbon material include pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers, and activated carbon. Examples of the coke include pitch coke, needle coke, and petroleum coke. Glassy carbons include non-graphitizable carbon materials. The organic polymer compound fired body is a carbonized substance obtained by firing a polymer compound (for example, phenol resin or furan resin) at a high temperature (for example, about 500 ° C. or more) in an inert gas stream or in a vacuum. Examples of the silicon compound include CaSi 2 and CoSi 2 . An example of the metal oxide is tin oxide (SnO 2 ). Examples of the polymer compound include polyacetylene and polypyrrole. The material used as the negative electrode active material 20b can be arbitrarily selected according to the type and application of the battery.

分散材２０ｃは任意であり、例えばＮ−メチル−２−ピロリドン等を用いる。溶媒２０ｄは、溶媒１０ｄと同様に混練に適したものを用いる。溶媒１０ｄと同じ材料でもよく、異なる材料でもよい。   The dispersing material 20c is arbitrary, and for example, N-methyl-2-pyrrolidone or the like is used. As the solvent 20d, a solvent suitable for kneading is used similarly to the solvent 10d. The same material as the solvent 10d may be used, or a different material may be used.

絶縁性のセパレータ３０は、高分子材料（特に多孔質のもの）などから形成できる。セパレータ３０の厚さは、例えば１０〜３０[μｍ]の範囲である。高分子材料は、例えばポリプロピレン、ポリエチレン、ポリメチルペンテンなどが該当する。さらには、これらの高分子材料から形成した不織布や、延伸多孔質化したフィルムなどを用いてもよい。   The insulating separator 30 can be formed from a polymer material (particularly porous). The thickness of the separator 30 is, for example, in the range of 10 to 30 [μm]. Examples of the polymer material include polypropylene, polyethylene, and polymethylpentene. Furthermore, you may use the nonwoven fabric formed from these polymeric materials, the film | membrane which made the stretch porous, etc.

ステップＳ１２と同様にして、ステップＳ２０で作製した混練物を負極集電体２０ｅ上に負極活物質層２１，２３として形成する塗工・乾燥工程を行う〔ステップＳ２２〕。具体的には、混練物を負極集電体２０ｅ上に塗工した後、所定温度下で乾燥させて固形化する。負極活物質層２１，２３は、乾燥後に所定厚さ（例えば１００〜２００[μｍ]）となるように塗工量を調整する。負極集電体２０ｅの厚さは、例えば１０〜２０[μｍ]程度である。こうして帯状の負極板２０が形成される。   In the same manner as in step S12, a coating / drying process for forming the kneaded material prepared in step S20 as the negative electrode active material layers 21 and 23 on the negative electrode current collector 20e is performed [step S22]. Specifically, after the kneaded material is coated on the negative electrode current collector 20e, it is dried and solidified at a predetermined temperature. The coating amount of the negative electrode active material layers 21 and 23 is adjusted so as to have a predetermined thickness (for example, 100 to 200 [μm]) after drying. The thickness of the negative electrode current collector 20e is, for example, about 10 to 20 [μm]. In this way, a strip-like negative electrode plate 20 is formed.

その後、ステップＳ１２と同様にして負極板２０をプレスするプレス工程〔ステップＳ２４〕と、ステップＳ１６と同様にして負極板２０を所定形状（板長，板厚，板幅等）に切断するスリット工程〔ステップＳ２６〕とを順不同で行う。こうして、捲回可能な負極板２０が形成される。   Thereafter, a pressing step [step S24] for pressing the negative electrode plate 20 in the same manner as in step S12, and a slit step for cutting the negative electrode plate 20 into a predetermined shape (plate length, plate thickness, plate width, etc.) in the same manner as in step S16. [Step S26] is performed in any order. In this way, the negative electrode plate 20 that can be wound is formed.

（第３工程）捲回および扁平プレス
正極板１０および負極板２０が形成された後に行われた後、扁平体２００の屈曲部Ｂに対応する正極板１０および負極板２０のうちで一方または双方に対して軟化剤を含ませる軟化剤含蓄工程を行う〔ステップＳ３０〕。 (Third Step) Winding and Flat Pressing After the positive electrode plate 10 and the negative electrode plate 20 are formed, one or both of the positive electrode plate 10 and the negative electrode plate 20 corresponding to the bent portion B of the flat body 200 A softener storage step of containing a softener is performed [Step S30].

図５には、滴下機（軟化剤含蓄手段４２）から軟化剤４２ａを滴下し、電極板（特に電極活物質層）に含ませる例を示す。その他、噴射機による軟化剤４２ａの吹き付け、塗布機による軟化剤４２ａの塗布、注入機による軟化剤４２ａの注入などで行ってもよい。滴下機，噴射機，塗布機，注入機などは、いずれも軟化剤含蓄手段４２に相当する。軟化剤を含ませる他の方法を適用してもよい。例えば、スリットダイ塗工法、スクリーン塗工法、カーテン塗工法、ナイフ塗工法、グラビア塗工法、静電スプレー法等が該当する。   FIG. 5 shows an example in which the softening agent 42a is dropped from a dropping machine (softening agent-containing means 42) and is included in an electrode plate (particularly an electrode active material layer). In addition, the softening agent 42a may be sprayed with an injector, the softening agent 42a may be applied with an applicator, or the softening agent 42a may be injected with an injector. The dripping machine, the jetting machine, the coating machine, the pouring machine, etc. all correspond to the softener storage means 42. Other methods of including a softener may be applied. For example, a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, an electrostatic spray method, and the like are applicable.

軟化剤４２ａを含ませる時期は、早過ぎると軟化剤４２ａが乾燥してしまい、逆に遅すぎると電極板を十分に軟化させられない。そのため、後述するステップＳ３６の扁平プレス工程において扁平プレスを行う際に軟化剤４２ａが全部乾燥しないことや、軟化剤４２ａの含蓄量に対して扁平プレスを行う際に所定割合以上が残存することなどの条件を満たす時期に行うのが望ましい。所定割合は、電極板や軟化剤４２ａに用いる材料に応じて適切な数値（例えば０．５％など）を設定する。   When the softening agent 42a is included too early, the softening agent 42a dries out. Conversely, when it is too late, the electrode plate cannot be sufficiently softened. Therefore, when the flat press is performed in the flat press step of step S36 described later, the softener 42a is not completely dried, or when a flat press is performed with respect to the content of the softener 42a, a predetermined ratio or more remains. It is desirable to do this when the conditions are met. The predetermined ratio is set to an appropriate numerical value (for example, 0.5%) according to the material used for the electrode plate and the softening agent 42a.

軟化剤を含ませる部位の設定例について、図３，図４を参照しながら説明する。軟化剤を含ませる部位は、後述する扁平プレス工程によって形成される扁平体２００の屈曲部Ｂとなる部位（図３，図４を参照）の範囲内に設定するのが望ましい。軟化剤を含ませる量（含蓄量）が多くなるにつれて、後述する浸透時間（表１，２を参照）を長く確保する必要がある。そのため、電極板を確実に軟化でき、かつ、浸透時間が短くなるように、含蓄量を試験等で適正化するのが望ましい。   An example of setting a site to contain the softener will be described with reference to FIGS. It is desirable to set the site | part to which a softener is included in the range of the site | part (refer FIG. 3, FIG. 4) used as the bending part B of the flat body 200 formed by the flat press process mentioned later. As the amount (content) of the softener is increased, it is necessary to ensure a longer permeation time (see Tables 1 and 2) described later. For this reason, it is desirable to optimize the content by testing or the like so that the electrode plate can be reliably softened and the permeation time is shortened.

図３には、所定周回や曲率半径に基づいて軟化剤の含蓄量を変化させる例を示す。設定する範囲の一例を斜線ハッチで示す。図３（Ａ）には、扁平体２００における所定周回までであって、かつ、屈曲部Ｂに対応する電極板の部位Ａ１を示す。図３（Ｂ）には、扁平体２００における所定の曲率半径Ｒｘ（例えば０〜６００[μｍ]）以下であって、かつ、屈曲部Ｂに対応する電極板の部位Ａ２を示す。   FIG. 3 shows an example in which the content of the softening agent is changed based on the predetermined number of turns and the radius of curvature. An example of the setting range is indicated by hatching. FIG. 3A shows a part A1 of the electrode plate up to a predetermined turn in the flat body 200 and corresponding to the bent portion B. FIG. FIG. 3B shows a portion A2 of the electrode plate that is equal to or less than a predetermined curvature radius Rx (for example, 0 to 600 [μm]) in the flat body 200 and corresponds to the bent portion B.

所定周回は、集電体および電極活物質層の各厚さによって異なるが、例えば１〜３[回]である。この場合、周回数に応じて軟化剤４２ａの含蓄量を変化させるのが望ましい。例えば、１周回目よりも２周回目に含ませる軟化剤４２ａの含蓄量を減らし、２周回目よりも３周回目に含ませる軟化剤４２ａの含蓄量を減らすなどである。   The predetermined number of rounds varies depending on the thicknesses of the current collector and the electrode active material layer, but is, for example, 1 to 3 [times]. In this case, it is desirable to change the content of the softener 42a according to the number of turns. For example, the content of the softening agent 42a to be included in the second round than the first round is reduced, and the content of the softening agent 42a to be included in the third round than the second round is reduced.

図４には、曲率半径に基づいて軟化剤の含蓄量を変化させる例を示す。図４（Ａ）では、設定しようとする周回（斜線ハッチで示す位置）の正極板１０に対して、扁平体２００の屈曲部Ｂにかかる曲率半径に基づいて変化させる。曲率と曲率半径とは逆数の関係にあるので、曲率が大きくなれば曲率半径は小さくなり、曲率が小さくなれば曲率半径は大きくなる。そこで、軟化剤を含ませる位置の曲率に基づいて含蓄量を設定する。例えば、屈曲部Ｂの中心点Ｐｒから電極板の位置までの半径Ｒ１，Ｒ２，Ｒ３，…（すなわち曲率半径）を求め、さらに曲率半径の比率に応じて含蓄量を設定する。式で表すと、例えば「Ｄａ：Ｄｂ：Ｄｃ＝１／Ｒ１：１／Ｒ２：１／Ｒ３」である。   FIG. 4 shows an example in which the content of the softening agent is changed based on the radius of curvature. In FIG. 4A, the positive electrode plate 10 of the circumference to be set (position indicated by hatched hatching) is changed based on the radius of curvature applied to the bent portion B of the flat body 200. Since the curvature and the radius of curvature are inversely related, the curvature radius decreases as the curvature increases, and the curvature radius increases as the curvature decreases. Therefore, the content is set based on the curvature of the position where the softener is included. For example, radii R1, R2, R3,... (Namely, a curvature radius) from the center point Pr of the bent portion B to the position of the electrode plate are obtained, and the content is set according to the ratio of the curvature radii. For example, “Da: Db: Dc = 1 / R1: 1 / R2: 1 / R3”.

図４（Ｂ）には、屈曲部Ｂの中心点Ｐｒから放射状に伸ばした仮想線Ｌ１，Ｌ２，Ｌ３，…と正極板１０とが交差する位置の正極板１０に対し、軟化剤を含ませる例を示す。すなわち、仮想線Ｌ１と正極板１０とが交差する位置Ｐ１ａ，Ｐ１ｂ，Ｐ１ｃ，…や、仮想線Ｌ２と正極板１０とが交差する位置Ｐ２ａ，Ｐ２ｂ，Ｐ２ｃ，…、仮想線Ｌ３と正極板１０とが交差する位置Ｐ３ａ，Ｐ３ｂ，Ｐ３ｃ，…などに対応して、上述したように曲率半径の比率に応じて含蓄量を設定する。この場合の含蓄量は、必ずしも厳密である必要はなく、階段状に変化させてもよい。   In FIG. 4B, a softener is included in the positive electrode plate 10 at a position where the imaginary lines L1, L2, L3,... Radially extending from the center point Pr of the bent portion B and the positive electrode plate 10 intersect. An example is shown. That is, positions P1a, P1b, P1c,... Where virtual line L1 and positive electrode plate 10 intersect, positions P2a, P2b, P2c,... Where virtual line L2 and positive electrode plate 10 intersect, virtual line L3 and positive electrode plate 10 In correspondence with the positions P3a, P3b, P3c,..., Etc., the storage amount is set according to the ratio of the curvature radii as described above. The content in this case is not necessarily strict, and may be changed stepwise.

図２に戻って、正極板１０，負極板２０，セパレータ３０などを積層して渦巻き状に捲回する捲回工程を行い〔ステップＳ３４〕、当該捲回工程によって形成される捲回体１００を扁平状にプレスする扁平プレス工程を行う〔ステップＳ３６〕。扁平プレス後は、図１（Ｂ）に示すような扁平体２００が形成される。   Returning to FIG. 2, a winding process is performed in which the positive electrode plate 10, the negative electrode plate 20, the separator 30, and the like are stacked and wound in a spiral shape [Step S <b> 34], and the wound body 100 formed by the winding process is obtained. A flat pressing step of flatly pressing is performed [Step S36]. After flat pressing, a flat body 200 as shown in FIG. 1B is formed.

ステップＳ３４では、図５に示すように、正極板１０，負極板２０，セパレータ３０などを積層して、捲回手段４０に捲回する。捲回手段４０は、例えば円柱状や円筒状のローラ等が該当し、所定方向（例えば矢印Ｄ１方向）に回転して捲き取る。   In step S34, as shown in FIG. 5, the positive electrode plate 10, the negative electrode plate 20, the separator 30 and the like are stacked and wound on the winding means 40. The winding means 40 corresponds to, for example, a columnar or cylindrical roller and rotates in a predetermined direction (for example, the direction of the arrow D1).

ステップＳ３６では、図６に示すように平面台４４（平面の作業台）上に固定した捲回体１００に対して、扁平プレス手段４６を矢印Ｄ２方向に移動させて扁平プレスする。扁平プレス手段４６は、平面状のプレス面４６ａを有するプレス機などが該当する。   In step S36, as shown in FIG. 6, the flat pressing means 46 is moved flat in the direction of the arrow D2 with respect to the wound body 100 fixed on the flat table 44 (planar work table). The flat press means 46 corresponds to a press machine having a flat press surface 46a.

捲回体１００を扁平プレスして扁平体２００を得る際に不具合（具体的には電極の破断）が発生するか否かについて、軟化剤４２ａの割合やＳＰ値差などの試験条件を変えて試験した。まず、試験条件を以下に示す。   Whether or not a defect (specifically, electrode breakage) occurs when the wound body 100 is flat-pressed to obtain the flat body 200 is changed by changing the test conditions such as the ratio of the softening agent 42a and the SP value difference. Tested. First, test conditions are shown below.

（試験条件）
正極板１０は、正極活物質１０ｂにリン酸鉄リチウム（ＬｉＦｅＰＯ4）を用い、導電材１０ｃにデンカブラックを用い、バインダ１０ａにポリフッ化ビニリデン（ＰＶＤＦ）を用いた。混合比率をＬｉＦｅＰＯ4：デンカブラック：ＰＶＤＦ＝９０：５：５としてスラリーを作製し、作製したスラリーを塗布、乾燥、プレス、スリットすることで正極板１０を作製した。この作製形状は、電極幅Ｗａ＝４０[mm]、形成幅Ｗｃ＝３４[mm]、板長＝１．４[ｍ]、全板厚＝２０５[μｍ]、正極集電体１２の厚さ＝１５[μｍ]、密度＝１．９[g/cm3]である。 (Test conditions)
The positive electrode plate 10, using the lithium iron phosphate (LiFePO 4) as a positive electrode active material 10b, using Denka black conductive material 10c, with polyvinylidene fluoride (PVDF) as the binder 10a. A slurry was prepared with a mixing ratio of LiFePO 4 : denka black: PVDF = 90: 5: 5, and the prepared slurry was applied, dried, pressed, and slitted to produce a positive electrode plate 10. The production shape is as follows: electrode width Wa = 40 [mm], formation width Wc = 34 [mm], plate length = 1.4 [m], total plate thickness = 205 [μm], thickness of positive electrode current collector 12 = 15 [μm], density = 1.9 [g / cm 3 ].

負極板２０は、負極活物質２０ｂにメソカーボンマイクロビーズ（大阪ガスケミカル株式会社製「ＭＣＭＢ−２５−２８」、平均粒子径２５[μｍ]）を用い、分散材２０ｃにカルボキシメチルセルロース（ＣＭＣ）を用い、スチレンブタジエンゴム（ＳＢＲ）を用いた。混合比率を負極活物質：ＣＭＣ：ＳＢＲ＝９４：３：３としてスラリーを作製し、作製したスラリーを塗布、乾燥、プレス、スリットすることで負極板２０を作製した。この作製形状は、電極幅Ｗａ＝４２[mm]、形成幅Ｗｃ＝３７[mm]、板長＝１．５[ｍ]、全板厚＝１５０[μｍ]、負極集電体２２の厚さ＝１０[μｍ]、密度＝１．３４[g/cm3]である。 The negative electrode plate 20 uses mesocarbon microbeads (“MCMB-25-28” manufactured by Osaka Gas Chemical Co., Ltd., average particle size 25 [μm]) as the negative electrode active material 20b, and carboxymethyl cellulose (CMC) as the dispersion material 20c. Styrene butadiene rubber (SBR) was used. A slurry was prepared with a mixing ratio of the negative electrode active material: CMC: SBR = 94: 3: 3, and the prepared slurry was applied, dried, pressed, and slit to prepare the negative electrode plate 20. The production shape is as follows: electrode width Wa = 42 [mm], formation width Wc = 37 [mm], plate length = 1.5 [m], total plate thickness = 150 [μm], thickness of negative electrode current collector 22 = 10 [μm], density = 1.34 [g / cm 3 ].

図５に示すように軟化剤含蓄手段４２から軟化剤４２ａを正極板１０および負極板２０に滴下した。滴下して軟化剤を含ませる範囲は、扁平プレスによって屈曲される部位を中心として５[mm]の範囲である。軟化剤４２ａの材料は、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、エタノール、水を設定した。電極板に軟化剤４２ａと滴下してから扁平プレスを行うまでの浸透時間は、１分間、５分間、１０分間を設定した。   As shown in FIG. 5, the softener 42 a was dropped from the softener storage means 42 onto the positive electrode plate 10 and the negative electrode plate 20. The range in which the softening agent is added by dripping is a range of 5 [mm] centering on the portion bent by the flat press. The material of the softening agent 42a was set to N-methyl-2-pyrrolidone (NMP), ethanol, and water. The permeation time from when the softening agent 42a was dropped onto the electrode plate until flat pressing was set to 1 minute, 5 minutes, and 10 minutes.

軟化剤４２ａを含ませた後、正極板１０，負極板２０，セパレータ３０などを積層して、図５に示すように捲回手段４０に捲回し、図６に示すように扁平プレス手段４６で扁平プレスを行った。なお、セパレータ３０はポリエチレンで作製し、電極幅Ｗａ＝４３[mm]、板厚＝２０[μｍ]とした。試験結果を下記の表１と表２とに分けて示す。すなわち、表１には試験番号が「１」〜「１０」を示し、表２には試験番号が「１１」〜「１９」を示す。不具合の欄には、電極破断が発生すれば「有」を示し、発生しなければ「無」を示す。結果の欄には、電極破断が全く発生しなければ「○」を示し、最内周にのみ電極破断が発生すれば「△」を示し、２周回以降にも電極破断が発生すれば「×」を示す。   After the softening agent 42a is included, the positive electrode plate 10, the negative electrode plate 20, the separator 30 and the like are laminated, wound on the winding means 40 as shown in FIG. 5, and flattened pressing means 46 as shown in FIG. A flat press was performed. The separator 30 was made of polyethylene and had an electrode width Wa = 43 [mm] and a plate thickness = 20 [μm]. The test results are shown separately in Table 1 and Table 2 below. That is, Table 1 shows test numbers “1” to “10”, and Table 2 shows test numbers “11” to “19”. In the column of defect, “exist” is indicated if an electrode break occurs, and “none” is indicated if no electrode break occurs. In the result column, “○” is shown if no electrode breakage occurs, “△” is shown if electrode breakage occurs only in the innermost circumference, and “×” is shown if electrode breakage occurs after two rounds. Is shown.

Figure 2012174582
Figure 2012174582

Figure 2012174582
Figure 2012174582

上記の結果表から明らかなように、軟化剤４２ａと電極活物質層のバインダ１０ａ，２０ａとにかかるＳＰ値差が小さくなるほど電極破断が発生しにくくなる。特に所定値範囲内（±１０以内）で電極破断が発生しにくい。また、浸透時間が長くなるにつれて、電極破断が発生しにくくなる。   As apparent from the above result table, the smaller the SP value difference between the softening agent 42a and the binders 10a and 20a of the electrode active material layer, the less likely the electrode breaks. In particular, electrode breakage hardly occurs within a predetermined value range (within ± 10). Further, as the permeation time becomes longer, electrode breakage is less likely to occur.

上述した実施の形態によれば、以下に示す各効果を得ることができる。まず請求項１，１２に対応し、正極板１０，負極板２０およびセパレータ３０を積層して捲回する捲回手段４０（捲回工程）と、捲回手段４０によって形成される捲回体１００を扁平状に扁平プレスする扁平プレス手段４６（扁平プレス工程）と、正極板１０および負極板２０のうちで一方または双方の電極板に対して軟化剤４２ａを含ませる軟化剤含蓄手段４２（軟化剤含蓄工程）とを有する構成とした（図２を参照）。この構成によれば、扁平プレスを行って屈曲させても、軟化剤４２ａを含んだ電極板は容易に曲げられるので、電極活物質層の剥離や集電体の切断等のような不具合の発生を防止することができる。   According to the embodiment described above, the following effects can be obtained. First, corresponding to claims 1 and 12, a winding means 40 (winding process) for laminating and winding the positive electrode plate 10, the negative electrode plate 20 and the separator 30, and a wound body 100 formed by the winding means 40. Flat pressing means 46 (flat pressing process) for flatly pressing the material, and softener storage means 42 (softening) for including one or both of the positive electrode plate 10 and the negative electrode plate 20 with the softening agent 42a. Agent storage step) (see FIG. 2). According to this configuration, the electrode plate containing the softening agent 42a can be easily bent even if it is bent by a flat press, so that problems such as peeling of the electrode active material layer and cutting of the current collector occur. Can be prevented.

請求項２に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、軟化剤４２ａを滴下する滴下法、軟化剤４２ａを吹き付ける吹付法、軟化剤４２ａを塗布する塗布法、軟化剤４２ａを注入する注入法のうちでいずれかの方法で行う構成とした（図２のステップＳ３０を参照）。この構成によれば、軟化剤４２ａをより確実に電極板（特に電極活物質層）に含ませることができる。   Corresponding to claim 2, the softener storage means 42 (softener storage step) includes a dropping method in which the softener 42a is dropped, a spraying method in which the softener 42a is sprayed, a coating method in which the softener 42a is applied, and a softener 42a. One of the injection methods to be injected is used (see step S30 in FIG. 2). According to this configuration, the softening agent 42a can be more reliably included in the electrode plate (particularly the electrode active material layer).

請求項３に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、電極板のうちで扁平プレスによって得られる扁平体２００の屈曲部Ｂとなる部位に対し、軟化剤４２ａを含ませる構成とした（図１，図３を参照）。この構成によれば、扁平体２００の屈曲部Ｂを含む部位に対して軟化剤４２ａを含ませるので、電極板を容易に曲げられるようになり、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。また、軟化剤４２ａを含ませる部位が限定されるので、必要な軟化剤４２ａが少なくて済み、コストを抑えることができる。   Corresponding to claim 3, the softener-containing means 42 (softener-containing process) includes a softener 42a in the portion of the electrode plate that becomes the bent portion B of the flat body 200 obtained by flat pressing. (See FIGS. 1 and 3). According to this configuration, since the softening agent 42a is included in the portion including the bent portion B of the flat body 200, the electrode plate can be easily bent, and the electrode active material layer is peeled off and the current collector is cut. The occurrence of problems such as these can be prevented more reliably. Moreover, since the site | part to which the softening agent 42a is included is limited, the required softening agent 42a can be reduced and cost can be held down.

請求項４に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、扁平プレスを行う際に軟化剤４２ａが全部乾燥しない時期に軟化剤４２ａを含ませる構成とした（図２のステップＳ３０を参照）。この構成によれば、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   Corresponding to claim 4, the softener storage means 42 (softener storage step) is configured to include the softener 42a when the softener 42a is not completely dried when performing flat pressing (step S30 in FIG. 2). See). According to this configuration, it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

請求項５に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、軟化剤４２ａの含蓄量に対して、扁平プレス工程で扁平プレスを行う際に所定割合以上が残存する時期に軟化剤４２ａを含ませる構成とした（図２のステップＳ３０を参照）。この構成によれば、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   Corresponding to claim 5, the softener storage means 42 (softener storage step) is a softener at a time when a predetermined ratio or more remains when flat pressing is performed in the flat pressing step with respect to the content of the softening agent 42a. 42a is included (see step S30 in FIG. 2). According to this configuration, it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

請求項６に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、扁平体２００における所定の曲率半径以下となる部位に対応する電極板に対して軟化剤４２ａを含ませる構成とした（図３（Ｂ）を参照）。この構成によれば、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   Corresponding to claim 6, the softener storage means 42 (softener storage step) is configured to include the softener 42a in the electrode plate corresponding to the portion of the flat body 200 having a predetermined radius of curvature or less ( (See FIG. 3B). According to this configuration, it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

請求項７に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、扁平体２００における所定周回までの部位に対応する電極板に対して軟化剤４２ａを含ませる構成とした（図３（Ａ）を参照）。この構成によれば、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   Corresponding to claim 7, the softening agent storing means 42 (softening agent storing step) is configured to include the softening agent 42a in the electrode plate corresponding to the portion of the flat body 200 up to the predetermined turn (FIG. 3 ( See A)). According to this configuration, it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

請求項８に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、扁平体２００の内周側から外周側に向かうにつれて、軟化剤４２ａの含蓄量を変化させる構成とした（図４を参照）。この構成によれば、軟化剤４２ａの必要量が少なくて済み、コストを抑えることができる。   Corresponding to claim 8, the softener storage means 42 (softener storage step) is configured to change the content of the softener 42a from the inner peripheral side of the flat body 200 toward the outer peripheral side (see FIG. 4). reference). According to this configuration, the required amount of the softening agent 42a is small, and the cost can be suppressed.

請求項９に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、扁平体２００の周回数に基づいて、軟化剤４２ａの含蓄量を変化させる構成とした（図２のステップＳ３０，図３（Ａ）を参照）。この構成によれば、よって軟化剤４２ａの必要量が少なくて済み、コストを抑えることができる。   Corresponding to claim 9, the softener storage means 42 (softener storage step) is configured to change the content of the softener 42a based on the number of rounds of the flat body 200 (step S30 in FIG. 2, FIG. 3 (A)). According to this configuration, the required amount of the softening agent 42a can be reduced, and the cost can be reduced.

請求項１０に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、扁平体２００の曲率半径に基づいて、軟化剤４２ａの含蓄量を変化させる構成とした（図２のステップＳ３０，図３（Ｂ）を参照）。この構成によれば、軟化剤４２ａの必要量が少なくて済み、コストを抑えることができる。   Corresponding to claim 10, the softener storage means 42 (softener storage step) is configured to change the content of the softener 42a based on the radius of curvature of the flat body 200 (step S30 in FIG. 2, FIG. 3 (B)). According to this configuration, the required amount of the softening agent 42a is small, and the cost can be suppressed.

請求項１１に対応し、軟化剤含蓄手段４２（軟化剤含蓄工程）は、電極活物質層を構成するバインダ１０ａ，２０ａのＳＰ値との差が所定値範囲内となるＳＰ値を有する軟化剤４２ａを用いて、電極板に含ませる構成とした（図２のステップＳ３０を参照）。この構成によれば、軟化剤４２ａを含蓄させることが容易になるので、電極活物質層の剥離や集電体の切断等のような不具合の発生をより確実に防止することができる。   Corresponding to claim 11, the softener storage means 42 (softener storage step) is a softener having an SP value in which the difference between the SP values of the binders 10a and 20a constituting the electrode active material layer is within a predetermined value range. It was set as the structure included in an electrode plate using 42a (refer step S30 of FIG. 2). According to this configuration, it becomes easy to contain the softening agent 42a, and thus it is possible to more reliably prevent the occurrence of problems such as peeling of the electrode active material layer and cutting of the current collector.

〔他の実施の形態〕
以上では本発明を実施するための形態について説明したが、本発明は当該形態に何ら限定されるものではない。言い換えれば、本発明の要旨を逸脱しない範囲内において、種々なる形態で実施することもできる。例えば、次に示す各形態を実現してもよい。 [Other Embodiments]
Although the form for implementing this invention was demonstrated above, this invention is not limited to the said form at all. In other words, various forms can be implemented without departing from the scope of the present invention. For example, the following forms may be realized.

上述した実施の形態では、集電体（正極集電体１２や負極集電体２２）の両面に電極活物質層（正極活物質層１１，１３や負極活物質層２１，２３）を形成した電極板を適用した（図１等を参照）。この形態に代えて、集電体の片面にのみ電極活物質層を形成した電極板を適用することもできる。電極活物質層の形成面が相違するに過ぎないので、上述した実施の形態と同様の作用効果を得ることができる。   In the embodiment described above, the electrode active material layers (the positive electrode active material layers 11 and 13 and the negative electrode active material layers 21 and 23) are formed on both surfaces of the current collector (the positive electrode current collector 12 and the negative electrode current collector 22). An electrode plate was applied (see FIG. 1 etc.). It can replace with this form and can also apply the electrode plate which formed the electrode active material layer only in the single side | surface of a collector. Since only the formation surface of the electrode active material layer is different, it is possible to obtain the same effect as the above-described embodiment.

上述した実施の形態では、バインダ１０ａ，正極活物質１０ｂ，導電材１０ｃ，溶媒１０ｄを混練した混練物を正極集電体１２上に正極活物質層１１，１３として形成する構成とした（図２，図１１のステップＳ１２，Ｓ２２に示す塗工・乾燥工程を参照）。この形態に代えて、バインダ１０ａ，正極活物質１０ｂ，導電材１０ｃ，溶媒１０ｄを正極集電体１２上に並行して（あるいは前後して順番に）塗工することで、正極集電体１２上に直接的に正極活物質層１１，１３として形成する構成としてもよい。負極集電体２２上に負極活物質層２１，２３として形成する場合も同様である。この形態によれば、混練工程が不要になるので、電極板の形成に要する時間を短縮することができる。   In the above-described embodiment, the kneaded material obtained by kneading the binder 10a, the positive electrode active material 10b, the conductive material 10c, and the solvent 10d is formed as the positive electrode active material layers 11 and 13 on the positive electrode current collector 12 (FIG. 2). , See the coating / drying process shown in steps S12 and S22 of FIG. 11). Instead of this form, the positive electrode current collector 12 is formed by coating the binder 10a, the positive electrode active material 10b, the conductive material 10c, and the solvent 10d in parallel (or in order, before and after) on the positive electrode current collector 12. It is good also as a structure directly formed as the positive electrode active material layers 11 and 13 on it. The same applies when the negative electrode active material layers 21 and 23 are formed on the negative electrode current collector 22. According to this embodiment, since the kneading step is unnecessary, the time required for forming the electrode plate can be shortened.

上述した実施の形態では、正極板１０および負極板２０についてそれぞれスリット工程（ステップＳ１６，Ｓ２６）を行った後、軟化剤４２ａを含ませる軟化剤含蓄工程（ステップＳ３０）を行う構成とした（図２を参照）。この形態に代えて、スリット工程よりも前に軟化剤含蓄工程を行う構成としてもよい。例えば図７に示すように、正極板１０の形成ではプレス工程（ステップＳ１４）の後に行う構成としてもよく、負極板２０の形成では塗工・乾燥工程（ステップＳ２２）の後に行う構成としてもよい。いずれの構成も、扁平プレスを行う際に軟化剤４２ａが全部乾燥しないことや、軟化剤４２ａの含蓄量に対して扁平プレスを行う際に所定割合以上が残存することなどの条件を満たせばよい。また、正極板１０および負極板２０のうち一方または双方に適用可能である。この構成であっても、上述した実施の形態と同様の作用効果を得ることができる。   In the above-described embodiment, the positive electrode plate 10 and the negative electrode plate 20 are each subjected to the slit process (steps S16 and S26), and then the softener containing process (step S30) including the softener 42a is performed (FIG. 2). Instead of this form, a softener storage step may be performed prior to the slitting step. For example, as shown in FIG. 7, the positive electrode plate 10 may be formed after the pressing step (step S14), and the negative electrode plate 20 may be formed after the coating / drying step (step S22). . In any configuration, it is only necessary to satisfy the conditions such that the softening agent 42a is not completely dried when the flat pressing is performed, or that a predetermined ratio or more remains when the flat pressing is performed with respect to the content of the softening agent 42a. . Further, the present invention can be applied to one or both of the positive electrode plate 10 and the negative electrode plate 20. Even with this configuration, it is possible to obtain the same effects as the above-described embodiment.

１０ 正極板（電極板）
１０ａ，２０ａ バインダ（結着剤）
１０ｂ 正極活物質（電極活物質）
１０ｃ 導電材
１０ｄ，２０ｄ 溶媒
１１，１３ 正極活物質層（電極活物質層）
１２ 正極集電体（集電体）
２０ 負極板（電極板）
２０ｂ 負極活物質（電極活物質）
２０ｃ 分散材
２１，２３ 負極活物質層（電極活物質層）
２２ 負極集電体（集電体）
３０ セパレータ
４０ 捲回手段
４２ 軟化剤含蓄手段
４２ａ 軟化剤
４６ 扁平プレス手段
１００ 捲回体
２００ 扁平体 10 Positive plate (electrode plate)
10a, 20a Binder (binder)
10b Positive electrode active material (electrode active material)
10c Conductive material 10d, 20d Solvent 11, 13 Positive electrode active material layer (electrode active material layer)
12 Positive current collector (current collector)
20 Negative electrode plate (electrode plate)
20b Negative electrode active material (electrode active material)
20c Dispersant 21, 23 Negative electrode active material layer (electrode active material layer)
22 Negative electrode current collector (current collector)
30 Separator 40 Winding means 42 Softener containing means 42a Softener 46 Flat pressing means 100 Winding body 200 Flat body

Claims (12)

それぞれが帯状の集電体上に電極活物質層を形成した正極板および負極板と、前記正極板と前記負極板との間に介在させる絶縁性のセパレータとを備える捲回型電池を製造する捲回型電池の製造方法において、
前記正極板，前記負極板および前記セパレータを積層して捲回する捲回工程と、
前記捲回工程によって形成される捲回体を扁平状に扁平プレスする扁平プレス工程と、
前記捲回工程以前に行われ、前記正極板および前記負極板のうちで一方または双方の電極板に対し、軟化剤を含ませる軟化剤含蓄工程と、
を有することを特徴とする捲回型電池の製造方法。 A wound battery comprising a positive electrode plate and a negative electrode plate each having an electrode active material layer formed on a strip-shaped current collector, and an insulating separator interposed between the positive electrode plate and the negative electrode plate is manufactured. In the manufacturing method of the wound battery,
A winding step of laminating and winding the positive electrode plate, the negative electrode plate and the separator;
A flat pressing step of flatly pressing the wound body formed by the winding step;
A softening agent containing step, which is performed before the winding step, and contains a softening agent for one or both of the positive electrode plate and the negative electrode plate;
A method for producing a wound battery, comprising: 前記軟化剤含蓄工程は、前記軟化剤を滴下する滴下法、前記軟化剤を吹き付ける吹付法、軟化剤を塗布する塗布法、軟化剤を注入する注入法のうちでいずれかの方法で行うことを特徴とする請求項１に記載の捲回型電池の製造方法。   The softening agent containing step is performed by any one of a dropping method for dropping the softening agent, a spraying method for spraying the softening agent, a coating method for applying the softening agent, and an injection method for injecting the softening agent. The method of manufacturing a wound battery according to claim 1. 前記軟化剤含蓄工程は、前記電極板のうちで前記電極板のうちで前記扁平プレス工程の扁平プレスによって得られる扁平体の屈曲部を含む部位に対し、前記軟化剤を含ませることを特徴とする請求項１または２に記載の捲回型電池の製造方法。   The softening agent containing step includes the softening agent in a portion of the electrode plate that includes a bent portion of a flat body obtained by flat pressing in the flat pressing step in the electrode plate. A method for manufacturing a wound battery according to claim 1 or 2. 前記軟化剤含蓄工程は、前記扁平プレス工程で扁平プレスを行う際に前記軟化剤が全部乾燥しない時期に前記軟化剤を含ませることを特徴とする請求項１から３のいずれか一項に記載の捲回型電池の製造方法。   The softening agent-containing step includes the softening agent at a time when the softening agent is not completely dried when flat pressing is performed in the flat pressing step. A method for manufacturing a wound battery. 前記軟化剤含蓄工程は、前記軟化剤の含蓄量に対して、前記扁平プレス工程で扁平プレスを行う際に所定割合以上が残存する時期に前記軟化剤を含ませることを特徴とする請求項４に記載の捲回型電池の製造方法。   5. The softening agent containing step includes the softening agent at a time when a predetermined ratio or more remains when flat pressing is performed in the flat pressing step with respect to the content of the softening agent. A method for producing the wound battery according to claim 1. 前記軟化剤含蓄工程は、前記扁平体における所定の曲率半径以下となる部位に対応する前記電極板に対して前記軟化剤を含ませることを特徴とする請求項１から５のいずれか一項に記載の捲回型電池の製造方法。   The softening agent containing step includes the softening agent in the electrode plate corresponding to a portion having a predetermined radius of curvature or less in the flat body. The manufacturing method of the winding type battery of description. 前記軟化剤含蓄工程は、前記扁平体における所定周回までの部位に対応する前記電極板に対して前記軟化剤を含ませることを特徴とする請求項１から５のいずれか一項に記載の捲回型電池の製造方法。   The said softener storage process makes the said softener be included with respect to the said electrode plate corresponding to the site | part to the predetermined circumference | surroundings in the said flat body, The scissors as described in any one of Claim 1 to 5 characterized by the above-mentioned. A method of manufacturing a rechargeable battery. 前記軟化剤含蓄工程は、前記扁平体の内周側から外周側に向かうにつれて、前記軟化剤の含蓄量を変化させることを特徴とする請求項１から７のいずれか一項に記載の捲回型電池の製造方法。   The winding according to any one of claims 1 to 7, wherein the softening agent content changing step changes the content of the softening agent as it goes from the inner circumference side to the outer circumference side of the flat body. Type battery manufacturing method. 前記軟化剤含蓄工程は、前記扁平体の周回数に基づいて、前記軟化剤の含蓄量を変化させることを特徴とする請求項８に記載の捲回型電池の製造方法。   The method for manufacturing a wound battery according to claim 8, wherein the softening agent storage step changes the storage amount of the softening agent based on the number of rounds of the flat body. 前記軟化剤含蓄工程は、前記扁平体の曲率半径に基づいて、前記軟化剤の含蓄量を変化させることを特徴とする請求項８に記載の捲回型電池の製造方法。   The method for manufacturing a wound battery according to claim 8, wherein the softening agent storing step changes a storing amount of the softening agent based on a curvature radius of the flat body. 前記軟化剤含蓄工程は、前記電極活物質層を構成するバインダのＳＰ値との差が所定値範囲内となるＳＰ値を有する前記軟化剤を用いて、前記電極板に含ませることを特徴とする請求項１から１０のいずれか一項に記載の捲回型電池の製造方法。   The softening agent containing step includes the electrode plate using the softening agent having an SP value in which a difference from an SP value of a binder constituting the electrode active material layer is within a predetermined value range. The method for manufacturing a wound battery according to any one of claims 1 to 10. それぞれが帯状の集電体上に電極活物質層を形成した正極板および負極板と、前記正極板と前記負極板との間に介在させる絶縁性のセパレータとを備える捲回型電池を製造する捲回型電池の製造装置において、
前記正極板，前記負極板および前記セパレータを積層して捲回する捲回手段と、
前記捲回手段によって形成される捲回体を扁平状に扁平プレスする扁平プレス手段と、
前記捲回手段以前に行われ、前記正極板および前記負極板のうちで一方または双方の電極板に対し、軟化剤を含ませる軟化剤含蓄手段と、
を有することを特徴とする捲回型電池の製造装置。 A wound battery comprising a positive electrode plate and a negative electrode plate each having an electrode active material layer formed on a strip-shaped current collector, and an insulating separator interposed between the positive electrode plate and the negative electrode plate is manufactured. In a wound battery manufacturing device,
Winding means for laminating and winding the positive electrode plate, the negative electrode plate and the separator;
Flat pressing means for flatly pressing the wound body formed by the winding means;
Softening agent storage means that is performed before the winding means, and contains a softening agent for one or both of the positive electrode plate and the negative electrode plate;
An apparatus for manufacturing a wound battery, comprising:
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