JP6020929B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary battery Download PDFInfo
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- JP6020929B2 JP6020929B2 JP2013186531A JP2013186531A JP6020929B2 JP 6020929 B2 JP6020929 B2 JP 6020929B2 JP 2013186531 A JP2013186531 A JP 2013186531A JP 2013186531 A JP2013186531 A JP 2013186531A JP 6020929 B2 JP6020929 B2 JP 6020929B2
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、非水電解液二次電池に関する。詳しくは、扁平形状の捲回電極体を備える非水電解液二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery. Specifically, the present invention relates to a non-aqueous electrolyte secondary battery including a flat wound electrode body.
リチウムイオン二次電池、ニッケル水素電池等の非水電解液二次電池は、近年、携帯電子機器や輸送機器の電源として広く用いられている。特に軽量で高エネルギー密度が得られるリチウムイオン二次電池は、車両駆動用の高出力電源として好適に利用されている。 In recent years, nonaqueous electrolyte secondary batteries such as lithium ion secondary batteries and nickel metal hydride batteries have been widely used as power sources for portable electronic devices and transportation devices. In particular, a lithium ion secondary battery that is lightweight and has a high energy density is suitably used as a high-output power source for driving a vehicle.
このような非水電解液二次電池は、典型的には、正極シートおよび負極シートがセパレータシートを介して積層された形態の電極体と、非水電解液とを備える。上記セパレータシートは、正負極間を電気的に絶縁する機能に加え、非水電解液を保持する機能や、シャットダウン機能（すなわち電池内の温度が上昇して一定の温度（典型的には軟化点）に達すると軟化し、電荷担体の伝導パスを遮断する機能）を兼ねる。さらに、セパレータシートには所定レベルの形状保持性（耐熱性）をも要求される。すなわち、例えば過充電等によって電池内の温度が上昇し、セパレータシートに熱収縮が生じた場合であっても、内部短絡を的確に防止することが求められる。かかる要求に応える手段として、例えば特許文献１には、電池内温度が上昇した際のＴＤ方向（セパレータシートを製膜する際の機械方向（巻き取り方向）に直交する方向。すなわち巾方向。）の最大収縮率を規定したセパレータシートが開示されている。
Such a non-aqueous electrolyte secondary battery typically includes an electrode body in which a positive electrode sheet and a negative electrode sheet are laminated via a separator sheet, and a non-aqueous electrolyte. In addition to the function of electrically insulating the positive and negative electrodes, the separator sheet has a function of holding a non-aqueous electrolyte and a shutdown function (that is, a constant temperature (typically a softening point as the temperature in the battery rises). ), It softens and reaches the function of blocking the conduction path of the charge carrier. Further, the separator sheet is required to have a predetermined level of shape retention (heat resistance). That is, for example, even when the temperature in the battery rises due to overcharging or the like and thermal contraction occurs in the separator sheet, it is required to prevent internal short circuit accurately. As means for meeting such demands, for example,
しかしながら、セパレータシートは、電池内温度が上昇した際、ＴＤ方向だけでなくＭＤ方向（セパレータシートを製膜する際の機械方向（巻き取り方向）。すなわち長手方向。）にも熱収縮し得る。このため、例えばＭＤ方向の熱収縮率が大きい場合には、セパレータシートが熱収縮や破断を生じ、内部短絡することがあり得る。本発明者らの検討によれば、かかる問題は、扁平形状の捲回電極体を備える非水電解液二次電池であって、例えば車載用途に用いられるもののように高容量タイプの電池で生じ易い傾向にあった。
本発明は、かかる事情に鑑みてなされたものであり、その目的は、扁平形状の捲回電極体を備える非水電解液二次電池であって、セパレータシートの破断が生じ難く、過充電耐性に優れた非水電解液二次電池を提供することである。
However, when the temperature in the battery rises, the separator sheet can be thermally shrunk not only in the TD direction but also in the MD direction (the machine direction (winding direction) when forming the separator sheet), that is, the longitudinal direction). For this reason, for example, when the thermal contraction rate in the MD direction is large, the separator sheet may undergo thermal contraction or breakage, and internal short circuit may occur. According to the study by the present inventors, such a problem is caused in a high-capacity type battery such as a non-aqueous electrolyte secondary battery including a flat wound electrode body, for example, used in an in-vehicle application. It tended to be easy.
The present invention has been made in view of such circumstances, and an object thereof is a non-aqueous electrolyte secondary battery including a flat wound electrode body, which is unlikely to break the separator sheet and is resistant to overcharge. An excellent nonaqueous electrolyte secondary battery is provided.
ところで、車載用の電池では、高容量化のために電極体の捲回数（捲回量）が他の用途に比べて相対的に多くなっている。かかる捲回電極体を備えた電池は、過充電等によって電池内（捲回電極体内）の温度が上昇した際に放熱しにくい。このため捲回電極体内の温度は、例えば図１に示すように内周（中央）部分で最も高くなり、外周に向かうにつれて低下する傾向にある。 By the way, in the battery for vehicle mounting, the number of times of winding (winding amount) of the electrode body is relatively larger than that of other applications in order to increase the capacity. A battery including such a wound electrode body is unlikely to dissipate heat when the temperature in the battery (in the wound electrode body) rises due to overcharging or the like. For this reason, for example, as shown in FIG. 1, the temperature inside the wound electrode body is highest at the inner periphery (center) portion and tends to decrease as it goes toward the outer periphery.
また、扁平形状の捲回電極体は、例えば図２に示すように、捲回軸に直交する方向において、両端のＲ部と該２つのＲ部に挟まれた平坦部とから構成されている。そして、車載用の電池は、典型的には上記扁平形状の捲回電極体の平坦部が拘束された状態で使用される。すなわち、捲回電極体には、拘束されている部分（平坦部）と、拘束されていない部分（平坦部の両側に位置する半円形状のＲ部）とが存在することになる。かかる捲回電極体を備えた電池の温度が上昇した場合、上記拘束されている部分では熱収縮が抑制される一方で、未拘束の部分では熱収縮が生じ得る。
図１には、捲回電極体の捲回数（ターン）に対するπＲ／（２Ｌ＋πＲ）の関係を示している。なお、図１の「Ｒ」および「Ｌ」は図２中の符号と対応しており、「Ｒ」は捲回電極体の平坦部の平均厚み（ｍｍ）を、「Ｌ」は捲回軸に直交する方向における平坦部の長さ（ｍｍ）を、それぞれ示している。すなわち、「πＲ／（２Ｌ＋πＲ）」は、捲回電極体全体に対する未拘束部分の割合を示している。図１に示すように、未拘束部分の割合は捲回電極体の外周に向かうにつれて増加するため、外周方向に向かって熱収縮する部分が多くなる傾向にある。
Further, as shown in FIG. 2, for example, the flat wound electrode body is composed of R portions at both ends and flat portions sandwiched between the two R portions in a direction orthogonal to the winding axis. . In-vehicle batteries are typically used in a state where the flat portion of the flat wound electrode body is constrained. That is, the wound electrode body has a constrained portion (flat portion) and a non-constrained portion (semicircular R portions located on both sides of the flat portion). When the temperature of a battery provided with such a wound electrode body rises, heat shrinkage can be suppressed in the constrained portion, while heat shrinkage can occur in the unconstrained portion.
FIG. 1 shows the relationship of πR / (2L + πR) to the number of turns (turns) of the wound electrode body. Note that “R” and “L” in FIG. 1 correspond to the reference numerals in FIG. 2, “R” is the average thickness (mm) of the flat portion of the wound electrode body, and “L” is the wound axis. The length (mm) of the flat part in the direction orthogonal to is shown, respectively. That is, “πR / (2L + πR)” indicates the ratio of the unconstrained portion to the entire wound electrode body. As shown in FIG. 1, since the ratio of the unconstrained portion increases as it goes toward the outer periphery of the wound electrode body, there is a tendency that the portion that thermally contracts toward the outer peripheral direction increases.
本発明者らの検討によれば、このような捲回電極体を備えた電池が過充電状態となり電池内の温度が上昇すると、上記放熱性と未拘束部分の割合とのバランスから、所定の領域でセパレータシートの破断が多く発生し得る。具体的には、図１に示すように、捲回電極体の全捲回数をｎとしたときに、その１／３ｎ〜２／３ｎの捲回数領域（例えば、全捲回数が３０ターンの場合には１０〜２０ターンの範囲内）において、セパレータシートの耐電圧性が著しく低下することがわかった。
そこで、本発明者らは、かかる耐電圧性の低下を改善することによってセパレータシートの破断を防止し、電池の過充電耐性を向上させることを考えた。そして、鋭意検討を重ねた結果、上記課題を解決し得る手段を見出し、本発明を完成させた。
According to the study by the present inventors, when a battery having such a wound electrode body is overcharged and the temperature in the battery rises, a predetermined amount is obtained from the balance between the heat dissipation and the ratio of the unconstrained portion. Many breaks of the separator sheet can occur in the region. Specifically, as shown in FIG. 1, when the total number of times of winding of the wound electrode body is n, the number of times of winding of 1 / 3n to 2 / 3n (for example, when the total number of times of winding is 30 turns) In the range of 10 to 20 turns), it was found that the voltage resistance of the separator sheet was significantly reduced.
Therefore, the present inventors have considered to improve the overcharge resistance of the battery by preventing breakage of the separator sheet by improving such a decrease in voltage resistance. As a result of intensive studies, a means capable of solving the above problems has been found and the present invention has been completed.
本発明によって、長尺状の正極シートと長尺状の負極シートとが長尺状のセパレータシートを介して長手方向に重ね合わされ形成された扁平形状の捲回電極体と、非水電解液と、を備える非水電解液二次電池が提供される。上記捲回電極体は、捲回軸に直交する方向において、両端のＲ部と、該２つのＲ部に挟まれた平坦部とから構成されている。そして、以下の条件をすべて満たしている。
（１）上記捲回電極体の捲回軸方向の長さは、１１０〜２００ｍｍである。
（２）上記捲回電極体は、上記捲回軸に直交する方向における上記平坦部の長さをＬ（ｍｍ）とし、上記セパレータシートの積層数をｍとしたときに、０．１≦（Ｌ／ｍ）≦１を満たしている。
（３）上記正極シートの平均厚みは、４０〜１００μｍである。
（４）上記負極シートの平均厚みは、５０〜１５０μｍである。
（５）上記セパレータシートの平均厚みは、１５〜３０μｍである。
（６）上記セパレータシートは、１５０℃で加熱したときの上記捲回軸に直交する方向（ＭＤ方向）の熱収縮率ａ（％）と上記捲回軸方向（ＴＤ方向）の熱収縮率をｂ（％）とが、１≦ａ≦３０および０．５≦ｂ≦１０ならびに１≦ａｂ≦１５０を満たしている。
According to the present invention, a flat wound electrode body formed by overlapping a long positive electrode sheet and a long negative electrode sheet in the longitudinal direction via a long separator sheet, a non-aqueous electrolyte, A non-aqueous electrolyte secondary battery is provided. The wound electrode body includes an R portion at both ends and a flat portion sandwiched between the two R portions in a direction orthogonal to the winding axis. And all the following conditions are satisfied.
(1) The length of the wound electrode body in the winding axis direction is 110 to 200 mm.
(2) When the length of the flat portion in the direction orthogonal to the winding axis is L (mm) and the number of stacked separator sheets is m, the wound electrode body is 0.1 ≦ ( L / m) ≦ 1 is satisfied.
(3) The average thickness of the positive electrode sheet is 40 to 100 μm.
(4) The average thickness of the negative electrode sheet is 50 to 150 μm.
(5) The average thickness of the separator sheet is 15 to 30 μm.
(6) The separator sheet has a heat shrinkage rate a (%) in a direction orthogonal to the winding axis (MD direction) and a heat shrinkage rate in the winding axis direction (TD direction) when heated at 150 ° C. b (%) satisfies 1 ≦ a ≦ 30 and 0.5 ≦ b ≦ 10 and 1 ≦ ab ≦ 150.
上記Ｌ／ｍは放熱性を示すパラメータであり、すなわちＬ／ｍが大きいほど放熱性に優れる電池と言え、該電池の耐電圧性が高いと考えられる。本発明者らの検討によれば、Ｌ／ｍが０．１より小さい場合は放熱性が低いため、電池内の温度上昇が速く、耐電圧性が低下するため好ましくない。また、Ｌ／ｍが1より大きい場合は、放熱性に優れる一方で電池容量が小さくなったり電池の機械的強度が低下したりする虞がある。捲回電極体の性状が、０．１≦（Ｌ／ｍ）≦１を満たす場合、電池特性を満足しつつ、且つ、放熱性の優れた電池を実現することができる。
また、セパレータシートの熱収縮率の積ａｂが１より小さい場合はセパレータシートの熱収縮が小さいため、充電による電極の膨張を抑えられずに局所的に反応を生じ、耐電圧性が低下する虞がある。一方、ａｂが１５０より大きい場合は、セパレータシートの熱収縮が大きすぎるため、セパレータシートの一部に収縮応力が偏り、そこからセパレータシートの破断が発生し、短絡する虞がある。セパレータシートの性状が１≦ａｂ≦１５０を満たす場合、優れた耐電圧性を実現することができる。
したがって、ここに開示される構成によれば、捲回電極体の放熱性を高め、且つセパレータシートに適度な熱収縮性を付与することによって、電極体の形状保持や内部短絡の抑制を行うことができ、過充電時に高い耐電圧性を実現できる。
The above L / m is a parameter indicating heat dissipation, that is, it can be said that the larger the L / m, the better the heat dissipation, and the voltage resistance of the battery is considered high. According to the study by the present inventors, when L / m is smaller than 0.1, the heat dissipation is low, so the temperature rise in the battery is fast and the withstand voltage is lowered, which is not preferable. On the other hand, when L / m is larger than 1, there is a possibility that the battery capacity may be reduced or the mechanical strength of the battery may be reduced while being excellent in heat dissipation. When the properties of the wound electrode body satisfy 0.1 ≦ (L / m) ≦ 1, it is possible to realize a battery with excellent heat dissipation while satisfying battery characteristics.
In addition, when the product ab of the thermal contraction rate of the separator sheet is smaller than 1, the thermal contraction of the separator sheet is small, and therefore, the expansion of the electrode due to charging cannot be suppressed and a local reaction occurs, and the withstand voltage may be reduced. There is. On the other hand, if ab is larger than 150, the thermal contraction of the separator sheet is too large, and the contraction stress is biased in a part of the separator sheet, and the separator sheet breaks from there, and there is a possibility of short circuit. When the properties of the separator sheet satisfy 1 ≦ ab ≦ 150, excellent voltage resistance can be realized.
Therefore, according to the configuration disclosed herein, the shape of the electrode body is maintained and internal short-circuit is suppressed by increasing the heat dissipation of the wound electrode body and imparting appropriate heat shrinkability to the separator sheet. And withstand high voltage during overcharge.
なお、上記平坦部の長さＬは、捲回軸に直交する方向における捲回電極体の全長から捲回電極体の平坦部の平均厚みＲを差し引くことによって求めることができる。また、セパレータシートの積層数ｍは、セパレータシートを１ターン捲回すると捲回軸中心からみて手前側と背面側に計２回積層されることから、典型的には、２×セパレータシートの使用枚数（枚）×捲回数（ターン）で求めることができる。また、セパレータシートの積層数ｍは、通常は１つの捲回電極体に２枚のセパレータシートが使用されることから、４×捲回数（ターン）で求めることができる。また、上記平均厚みは、一般的なノギスや厚さ測定機等を用いて数箇所（典型的には５箇所以上、例えば１０箇所）の厚みを計測した結果を算術平均することにより求めることができる。 The length L of the flat portion can be obtained by subtracting the average thickness R of the flat portion of the wound electrode body from the total length of the wound electrode body in the direction orthogonal to the winding axis. In addition, the number m of separator sheets is typically 2 times because the separator sheet is wound twice on the front side and the back side as viewed from the center of the winding axis when the separator sheet is wound one turn. It can be obtained by the number of sheets (sheets) x the number of spears (turns). Further, the number m of separator sheets stacked can be obtained by 4 × number of turns (turns) since usually two separator sheets are used for one wound electrode body. The average thickness can be obtained by arithmetically averaging the results of measuring the thickness at several locations (typically 5 locations or more, for example, 10 locations) using a general caliper or a thickness measuring instrument. it can.
セパレータシートの捲回軸に直交する方向（ＭＤ方向）の熱収縮率ａは、例えば以下のようにして測定することができる。即ち、先ず試験片として、長辺がＴＤ方向、短辺がＭＤ方向と一致するようセパレータシートを長方形状に切り出す。ここでは、後述する測定部（正方形状）の１辺が凡そ２〜１０ｃｍになるように切り出すとよい。次に、該試験片の測定部を正方形状に残して、両短辺部をテープ等で固定する。なお、試験片の固定はガラス板等の板の上でも良いし、板なしで直接恒温槽の壁面等に固定してもよい。例えばガラス板を使用する場合には、ＨＲＬ面が板側になるようにして固定するとよい。その状態で試験片を１５０℃に温度調節した恒温槽に入れ、１０分〜１時間程度保持した後、該試験片を取り出して室温まで放冷する。その後、加熱前後のＭＤ方向の長さから、熱収縮率ａを算出することができる。なお、熱収縮率ａは、加熱後、ＭＤ方向で最も収縮した箇所を測定して算出しても良いし、または、加熱前にＭＤ方向と平行に、かつ正方形の重心を通るように、正方形の一辺より短い線を加筆しておきその長さの収縮量から算出してもよい。
また、セパレータシートの捲回軸方向（ＴＤ方向）の熱収縮率ｂは、例えば以下のようにして測定することができる。即ち、先ず試験片として、長辺がＭＤ方向、短辺がＴＤ方向と一致するようセパレータシートを長方形状に切り出す。その後、上記ＭＤ方向の熱収縮率ａと同様に、加熱前後のＴＤ方向の長さから熱収縮率ｂを算出することができる。
The thermal contraction rate a in the direction orthogonal to the winding axis of the separator sheet (MD direction) can be measured, for example, as follows. That is, first, as a test piece, the separator sheet is cut into a rectangular shape so that the long side coincides with the TD direction and the short side coincides with the MD direction. Here, it is good to cut out so that one side of the measurement part (square shape) mentioned later may become about 2-10 cm. Next, the measurement part of the test piece is left in a square shape, and both short sides are fixed with a tape or the like. The test piece may be fixed on a plate such as a glass plate, or may be fixed directly on the wall surface of the thermostatic chamber without a plate. For example, when a glass plate is used, the glass plate may be fixed so that the HRL surface is on the plate side. In this state, the test piece is placed in a thermostat whose temperature is adjusted to 150 ° C. and held for about 10 minutes to 1 hour, and then the test piece is taken out and allowed to cool to room temperature. Thereafter, the thermal contraction rate a can be calculated from the length in the MD direction before and after heating. The heat shrinkage ratio a may be calculated by measuring the most contracted portion in the MD direction after heating, or a square so as to pass through the center of gravity of the square in parallel with the MD direction before heating. A line shorter than one side may be added and calculated from the contraction amount of the length.
Moreover, the thermal contraction rate b of the separator sheet in the winding axis direction (TD direction) can be measured, for example, as follows. That is, first, as a test piece, the separator sheet is cut into a rectangular shape so that the long side coincides with the MD direction and the short side coincides with the TD direction. Thereafter, similarly to the MD thermal contraction rate a, the thermal contraction rate b can be calculated from the length in the TD direction before and after heating.
以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄（例えば、本発明を特徴付けない構成要素や電池の一般的な製造プロセス）は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。 Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than matters specifically mentioned in the present specification and necessary for carrying out the present invention (for example, general manufacturing processes of components and batteries not characterizing the present invention) It can be grasped as a design matter of those skilled in the art based on the prior art. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.
ここに開示される非水電解液二次電池は、長尺状の正極シートと長尺状の負極シートとが長尺状のセパレータシートを介して長手方向に重ね合わされ形成された捲回電極体と、非水電解液とを備える。以下、各構成要素について順に説明する。 The non-aqueous electrolyte secondary battery disclosed herein is a wound electrode body formed by laminating a long positive electrode sheet and a long negative electrode sheet in the longitudinal direction via a long separator sheet. And a non-aqueous electrolyte. Hereinafter, each component will be described in order.
ここに開示される非水電解液二次電池の捲回電極体は、扁平形状を有している。捲回電極体の捲回軸方向（すなわち幅方向）の長さは１１０〜２００ｍｍとすることができる。図２に、かかる捲回電極体の捲回軸に直交する断面を模式的に示す。図２に示すように、扁平形状の捲回電極体１は、正極シート２と負極シート４とセパレータシート６とを備える。また、捲回電極体は、捲回軸に直交する断面において略角丸長方形状を有しており、両端のＲ部と、該２つのＲ部に挟まれた（中央側に位置する）平坦部とから構成されている。かかる扁平形状の捲回電極体は、例えば、長尺状の正極シート、長尺状のセパレータシート、長尺状の負極シート、長尺状のセパレータシートの順に重ね合わせて長手方向に捲回し、側面方向から押しつぶして拉げさせることによって作製し得る。
The wound electrode body of the non-aqueous electrolyte secondary battery disclosed herein has a flat shape. The length of the wound electrode body in the winding axis direction (that is, the width direction) can be 110 to 200 mm. FIG. 2 schematically shows a cross section orthogonal to the winding axis of the wound electrode body. As shown in FIG. 2, the flat
ここに開示される技術では、捲回軸に直交する方向における平坦部の長さをＬ（ｍｍ）とし、セパレータシートの積層数をｍとしたときに、０．１≦（Ｌ／ｍ）≦１を満たす。これにより、正常作動時の電池性能が良好で、且つ過充電耐性の高い非水電解液二次電池を提供することができる。平坦部の長さＬは、通常２５〜６０ｍｍ程度とすることが好ましい。また、セパレータシートの積層数ｍは、通常４０以上の整数であり、６０〜２５０程度とすることが好ましい。 In the technique disclosed herein, when the length of the flat portion in the direction orthogonal to the winding axis is L (mm) and the number of separator sheets stacked is m, 0.1 ≦ (L / m) ≦ 1 is satisfied. As a result, it is possible to provide a non-aqueous electrolyte secondary battery having good battery performance during normal operation and high overcharge resistance. In general, the length L of the flat portion is preferably about 25 to 60 mm. Moreover, the lamination | stacking number m of a separator sheet is an integer of 40 or more normally, and it is preferable to set it as about 60-250.
ここに開示される非水電解液二次電池の正極シートは、平均厚みが４０〜１００μｍである。かかる正極シートは、典型的には正極集電体と、該正極集電体上に形成された正極活物質層とを備える。正極活物質層は、少なくとも正極活物質を備える。正極集電体の単位面積当たり設けられる正極活物質層の質量（目付量）は、例えば９．８〜１５．２ｍｇ／ｃｍ２とすることができる。正極活物質層の平均厚みは、例えば３０〜９０μｍ程度とすることができる。正極活物質層の密度は、例えば１．８〜２．４ｇ／ｃｍ３とすることができる。 The positive electrode sheet of the non-aqueous electrolyte secondary battery disclosed herein has an average thickness of 40 to 100 μm. Such a positive electrode sheet typically includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector. The positive electrode active material layer includes at least a positive electrode active material. The mass (weight per unit area) of the positive electrode active material layer provided per unit area of the positive electrode current collector can be, for example, 9.8 to 15.2 mg / cm 2 . The average thickness of the positive electrode active material layer can be, for example, about 30 to 90 μm. The density of the positive electrode active material layer can be set to, for example, 1.8 to 2.4 g / cm 3 .
正極集電体としては、導電性の良好な金属（例えばアルミニウム、ニッケル、チタン、ステンレス鋼等）からなる導電性部材を採用し得る。正極集電体の平均厚みは、通常１０〜２０μｍ程度である。正極活物質としては、層状系、スピネル系等のリチウム複合金属酸化物（例えば、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉＯ２、ＬｉＣｏＯ２、ＬｉＦｅＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉ０．５Ｍｎ１．５Ｏ４，ＬｉＣｒＭｎＯ４、ＬｉＦｅＰＯ４等）を好適に採用し得る。正極活物質層にはまた、活物質以外の成分を含ませることもできる。そのような任意の成分としては、導電材やバインダ等が挙げられる。導電材としては、カーボンブラック（例えば、アセチレンブラックやケッチェンブラック）等の炭素材料を好ましく採用し得る。バインダとしては、ポリフッ化ビニリデン（ＰＶｄＦ）やポリエチレンオキサイド（ＰＥＯ）等のポリマー材料を好ましく採用し得る。 As the positive electrode current collector, a conductive member made of a metal having good conductivity (for example, aluminum, nickel, titanium, stainless steel, etc.) can be employed. The average thickness of the positive electrode current collector is usually about 10 to 20 μm. Examples of the positive electrode active material include lithium composite metal oxides such as layered and spinel (for example, LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNiO 2 , LiCoO 2 , LiFeO 2 , LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiCrMnO 4 , LiFePO 4, etc.) can be suitably employed. The positive electrode active material layer can also contain components other than the active material. Examples of such optional components include conductive materials and binders. As the conductive material, a carbon material such as carbon black (for example, acetylene black or ketjen black) can be preferably used. As the binder, polymer materials such as polyvinylidene fluoride (PVdF) and polyethylene oxide (PEO) can be preferably used.
ここに開示される非水電解液二次電池の負極シートは、平均厚みが５０〜１５０μｍである。かかる負極シートは、典型的には負極集電体と、該負極集電体上に形成された負極活物質層とを備える。負極活物質層は、少なくとも負極活物質を備える。負極集電体の単位面積当たり設けられる負極活物質層の質量（目付量）は、例えば４．８〜１０．２ｍｇ／ｃｍ２とすることができる。負極活物質層の平均厚みは、例えば４５〜１４５μｍ程度とすることができる。負極活物質層の密度は、例えば０．８〜１．４ｇ／ｃｍ３とすることができる。 The negative electrode sheet of the non-aqueous electrolyte secondary battery disclosed herein has an average thickness of 50 to 150 μm. Such a negative electrode sheet typically includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector. The negative electrode active material layer includes at least a negative electrode active material. The mass (weight per unit area) of the negative electrode active material layer provided per unit area of the negative electrode current collector can be, for example, 4.8 to 10.2 mg / cm 2 . The average thickness of the negative electrode active material layer can be, for example, about 45 to 145 μm. The density of the negative electrode active material layer can be set to, for example, 0.8 to 1.4 g / cm 3 .
負極集電体としては、導電性の良好な金属（例えば、銅、ニッケル、チタン、ステンレス鋼等）からなる導電性部材を採用し得る。負極集電体の平均厚みは、通常５〜２０μｍ程度である。負極活物質としては、黒鉛（グラファイト）、難黒鉛化炭素（ハードカーボン）、易黒鉛化炭素（ソフトカーボン）等の炭素材料を好適に用いることができ、なかでも非晶質炭素被覆黒鉛を好ましく採用し得る。負極活物質層にはまた、活物質以外の成分を含ませることもできる。そのような任意の成分としては、バインダや増粘剤等が挙げられる。バインダとしては、例えば、スチレンブタジエンゴム（ＳＢＲ）、ポリフッ化ビニリデン（ＰＶｄＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等のポリマー材料を好ましく採用し得る。増粘剤としては、例えば、カルボキシメチルセルロース（ＣＭＣ）やメチルセルロース（ＭＣ）等を好ましく採用し得る。 As the negative electrode current collector, a conductive member made of a metal having good conductivity (for example, copper, nickel, titanium, stainless steel, etc.) can be employed. The average thickness of the negative electrode current collector is usually about 5 to 20 μm. As the negative electrode active material, carbon materials such as graphite (graphite), non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon) and the like can be suitably used, and amorphous carbon-coated graphite is particularly preferable. Can be adopted. The negative electrode active material layer can also contain components other than the active material. Examples of such optional components include binders and thickeners. As the binder, for example, a polymer material such as styrene butadiene rubber (SBR), polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE) or the like can be preferably used. As the thickener, for example, carboxymethylcellulose (CMC), methylcellulose (MC) and the like can be preferably used.
ここに開示される非水電解液二次電池のセパレータシートは、平均厚みが１５〜３０μｍである。これにより、高い熱的安定性や機械的強度（形状安定性）と優れたイオン透過性とを兼ね備える。かかるセパレータシートは、典型的には、基材と、該基材上に形成された耐熱層（Heat Resistance Layer：ＨＲＬ）とを備える。基材の平均厚みは通常５〜２５μｍ程度とすることが好ましい。また、耐熱層は、無機フィラーを主体として構成され、典型的にはさらにバインダと増粘剤とを含み、高い耐熱性と絶縁性（非導電性性）とを備える。耐熱層の平均厚みは通常１〜１０μｍ程度とすることが好ましい。このようなセパレータシートは、無機フィラーとバインダと増粘剤とを含む耐熱層形成用スラリー（ペースト、インクを包含する。）を基材上に付与（典型的には塗布）することで作製し得る。なお、上述の通り、１つの捲回電極体には通常２枚のセパレータシートが使用される。 The separator sheet of the non-aqueous electrolyte secondary battery disclosed herein has an average thickness of 15 to 30 μm. Thereby, it has high thermal stability, mechanical strength (shape stability), and excellent ion permeability. Such a separator sheet typically includes a base material and a heat resistance layer (HRL) formed on the base material. The average thickness of the substrate is usually preferably about 5 to 25 μm. The heat-resistant layer is mainly composed of an inorganic filler, and typically includes a binder and a thickener, and has high heat resistance and insulation (non-conductive). The average thickness of the heat-resistant layer is usually preferably about 1 to 10 μm. Such a separator sheet is prepared by applying (typically applying) a slurry for forming a heat-resistant layer (including paste and ink) containing an inorganic filler, a binder, and a thickener. obtain. As described above, usually two separator sheets are used for one wound electrode body.
基材としては、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン系樹脂から成る多孔質樹脂シートを好適に採用し得る。かかる基材は単層構造であってもよく、あるいは材質や性状（厚みや空孔率等）の異なる２種以上の多孔質樹脂シートが積層された構造であってもよい。好適例として、ポリエチレン（ＰＥ）層の両面にポリプロピレン（ＰＰ）層が積層された三層構造のセパレータシートが挙げられる。
耐熱層に含まれる無機フィラーとしてはアルミナ（酸化アルミニウム：Ａｌ２Ｏ３）、アルミナ水和物（例えばベーマイト（Ａｌ２Ｏ３・Ｈ２Ｏ））、マグネシア（酸化マグネシウム：ＭｇＯ）、シリカ（酸化ケイ素：ＳｉＯ２）、チタニア（二酸化チタン：ＴｉＯ２）、ジルコニア（二酸化ジルコニウム：ＺｒＯ２）等を好適に用いることができ、なかでもアルミナやベーマイトを好ましく採用し得る。バインダとしては、例えば、アクリル系バインダ、スチレンブタジエンゴム（ＳＢＲ）、ポリオレフィン系バインダ、ポリテトラフルオロエチレン（ＰＴＦＥ）等のポリマー材料や、ポリ−Ｎ−ビニルアセトアミド（ＰＮＶＡ）等のアミドポリマー材料を好ましく採用し得る。増粘剤としては、例えば、カルボキシメチルセルロース（ＣＭＣ）、メチルセルロース（ＭＣ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等を好ましく採用し得る。
As the substrate, a porous resin sheet made of a polyolefin resin such as polyethylene (PE) or polypropylene (PP) can be suitably employed. Such a substrate may have a single layer structure, or may have a structure in which two or more porous resin sheets having different materials and properties (thickness, porosity, etc.) are laminated. A preferable example is a separator sheet having a three-layer structure in which a polypropylene (PP) layer is laminated on both sides of a polyethylene (PE) layer.
As the inorganic filler contained in the heat-resistant layer, alumina (aluminum oxide: Al 2 O 3 ), alumina hydrate (for example, boehmite (Al 2 O 3 .H 2 O)), magnesia (magnesium oxide: MgO), silica (oxidation) Silicon: SiO 2 ), titania (titanium dioxide: TiO 2 ), zirconia (zirconium dioxide: ZrO 2 ) and the like can be suitably used, and among these, alumina and boehmite can be preferably employed. As the binder, for example, an acrylic binder, a polymer material such as styrene butadiene rubber (SBR), a polyolefin binder, polytetrafluoroethylene (PTFE), or an amide polymer material such as poly-N-vinylacetamide (PNVA) is preferable. Can be adopted. As the thickener, for example, carboxymethylcellulose (CMC), methylcellulose (MC), N-methyl-2-pyrrolidone (NMP) and the like can be preferably used.
ここに開示される技術では、１５０℃で加熱したときの捲回軸に直交する方向（ＭＤ方向）の熱収縮率ａ（％）と上記捲回軸方向（ＴＤ方向）の熱収縮率をｂ（％）とが、１≦ａｂ≦１５０を満たすセパレータシートを用いる。これにより、セパレータシートに好適な熱収縮率が備わり、過充電耐性の高い非水電解液二次電池を提供することができる。捲回軸に直交する方向（ＭＤ方向）の熱収縮率ａは、通常１〜３０％であり、２〜２０％程度とすることが好ましい。捲回軸方向（ＴＤ方向）の熱収縮率ｂは、通常０．５〜１０％であり、０．５〜４％程度とすることが好ましい。なお、ａ，ｂは、例えば耐熱層形成用スラリーの固形分率や、基材上への付与条件、乾燥温度等によって調整することができる。 In the technique disclosed herein, the heat shrinkage rate a (%) in the direction orthogonal to the winding axis (MD direction) when heated at 150 ° C. and the heat shrinkage rate in the winding axis direction (TD direction) are expressed as b. (%) Uses a separator sheet satisfying 1 ≦ ab ≦ 150. As a result, a non-aqueous electrolyte secondary battery having a heat shrinkage ratio suitable for the separator sheet and having high overcharge resistance can be provided. The thermal shrinkage rate a in the direction orthogonal to the winding axis (MD direction) is usually 1 to 30%, preferably about 2 to 20%. The thermal contraction rate b in the winding axis direction (TD direction) is usually 0.5 to 10%, preferably about 0.5 to 4%. In addition, a and b can be adjusted with the solid content rate of the slurry for heat-resistant layer formation, the provision conditions on a base material, a drying temperature, etc., for example.
ここに開示される非水電解液二次電池の非水電解液は、典型的には非水溶媒中に支持塩を含有する。
非水溶媒としては、カーボネート類、エステル類、エーテル類、ニトリル類、スルホン類、ラクトン類等の非プロトン性溶媒を好適に用いることができる。なかでも、カーボネート類、例えば、エチレンカーボネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）等を好ましく採用し得る。支持塩としては、リチウム塩、ナトリウム塩、マグネシウム塩等を好適に用いることができ、なかでもＬｉＰＦ６を好ましく採用し得る。非水電解液中の支持塩の濃度は、０．７ｍｏｌ／Ｌ〜１．３ｍｏｌ／Ｌの範囲内となるよう調製することが好ましい。
The non-aqueous electrolyte solution of the non-aqueous electrolyte secondary battery disclosed herein typically contains a supporting salt in a non-aqueous solvent.
As the non-aqueous solvent, aprotic solvents such as carbonates, esters, ethers, nitriles, sulfones, and lactones can be suitably used. Of these, carbonates such as ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) can be preferably used. As the supporting salt, a lithium salt, a sodium salt, a magnesium salt, or the like can be suitably used, and among them, LiPF 6 can be preferably used. It is preferable to prepare so that the density | concentration of the supporting salt in a non-aqueous electrolyte may be in the range of 0.7 mol / L-1.3 mol / L.
非水電解液には、上記非水溶媒および支持塩に加えて各種添加剤を含み得る。該添加剤としては、例えばビニレンカーボネート（ＶＣ）、ビニルエチレンカーボネート（ＶＥＣ）、フルオロエチレンカーボネート（ＦＥＣ）、リオリチウムビス（オキサラト）ボレート（Ｌｉ［Ｂ（Ｃ２Ｏ４）２］）、エチレンサルファイト（ＥＳ）、プロパンサルトン（ＰＳ）、リチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）、ジフルオロリン酸リチウム（ＬｉＰＯ２Ｆ２）等を好適に用いることができ、なかでもＬｉ［Ｂ（Ｃ２Ｏ４）２やＬｉＰＯ２Ｆ２を好ましく採用し得る。非水電解液中の添加剤の濃度は、添加剤の限界溶解量を１００％としたときに、５〜９０％程度とすることが好ましい。例えば、Ｌｉ［Ｂ（Ｃ２Ｏ４）２］やＬｉＰＯ２Ｆ２であれば、それぞれ０．０１〜０．２ｍｏｌ／Ｌの範囲内となるように調整することが好ましい。 The non-aqueous electrolyte may contain various additives in addition to the non-aqueous solvent and the supporting salt. Examples of the additive include vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), liolithium bis (oxalato) borate (Li [B (C 2 O 4 ) 2 ]), ethylene sal Phyto (ES), propane sultone (PS), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium difluorophosphate (LiPO 2 F 2 ) and the like can be suitably used, and in particular, Li [B (C 2 O 4 ) 2 or LiPO 2 F 2 can be preferably employed. The concentration of the additive in the non-aqueous electrolyte is preferably about 5 to 90% when the limit dissolution amount of the additive is 100%. E.g., Li if [B (C 2 O 4) 2] and LiPO 2 F 2, respectively is preferably adjusted to be within the scope of 0.01~0.2mol / L.
ここで開示される非水電解液二次電池は各種用途に利用可能であるが、高い電池性能と信頼性（過充電耐性）とを兼ね備えていることを特徴とする。従って、かかる特徴を活かして、例えば車両用の動力源（駆動電源）として好適に利用し得る。 The non-aqueous electrolyte secondary battery disclosed herein can be used for various applications, but is characterized by having both high battery performance and reliability (overcharge resistance). Therefore, taking advantage of this feature, it can be suitably used as a power source (drive power source) for vehicles, for example.
以下、本発明に関するいくつかの実施例を説明するが、本発明をかかる具体例に示すものに限定することを意図したものではない。 Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to the specific examples.
＜Ｉ．捲回電極体の放熱性（Ｌ／ｍ）の検討＞
まず、耐熱層を形成するための耐熱層形成用の組成物を調製した。具体的には、無機フィラーとアクリル系バインダとを、質量比率が９５：５となるように秤量し、超音波分散機（Ｍテクニック株式会社製のクレアミックス）を用いてイオン交換水と混合し、固形分率が４５％のスラリー状の組成物を調製した。なお、混練時間は、予備分散（１５０００ｒｐｍ）が５分、本分散（２００００ｒｐｍ）が１５分とした。次に、上記組成物を基材（ここでは、表１に示す種類、厚みおよび熱収縮率の多孔質樹脂シート）の片面にグラビアコート法で塗布して、６０℃で乾燥することにより、５μｍの耐熱層を形成した。塗布には、線数：♯１００本／ｉｎｃｈ、インキ保有量：１９．５ｍｌ／ｃｍ２のグラビアロールを用い、条件は、塗布速度を３ｍ／分、グラビアロール速度を３．８ｍ／分、速比（グラビア速度／塗布速度比）を１．２７とした。これにより、基材の片面に耐熱層を備えたセパレータシート（実施例１〜３および比較例１，２）を作製した。
<I. Examination of heat dissipation (L / m) of wound electrode body>
First, a composition for forming a heat-resistant layer for forming a heat-resistant layer was prepared. Specifically, the inorganic filler and the acrylic binder are weighed so that the mass ratio is 95: 5, and mixed with ion-exchanged water using an ultrasonic disperser (Cleamix manufactured by M Technique Co., Ltd.). A slurry-like composition having a solid content of 45% was prepared. The kneading time was 5 minutes for preliminary dispersion (15000 rpm) and 15 minutes for main dispersion (20000 rpm). Next, the above composition is applied to one side of a base material (here, a porous resin sheet of the type, thickness and heat shrinkage shown in Table 1) by a gravure coating method, and dried at 60 ° C. to obtain 5 μm. A heat-resistant layer was formed. For the application, a gravure roll having a line number of # 100 lines / inch and an ink holding amount of 19.5 ml / cm 2 was used. The conditions were a coating speed of 3 m / min and a gravure roll speed of 3.8 m / min. The ratio (gravure speed / coating speed ratio) was 1.27. This produced the separator sheet (Examples 1-3 and Comparative Examples 1 and 2) which provided the heat-resistant layer on the single side | surface of the base material.
正極活物質としてのＬｉ[Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３]Ｏ２粉末（ＬＮＣＭ）と、導電材としてのアセチレンブラック（ＡＢ）と、バインダとしてのポリフッ化ビニリデン（ＰＶｄＦ）とを、ＬＮＣＭ：ＡＢ：ＰＶｄＦ＝９４：３：３の質量比率でＮ−メチルピロリドン（ＮＭＰ）と混合し、スラリー状組成物（正極活物質スラリー）を調製した。この組成物を、平均厚み１５μｍの長尺状アルミニウム箔（正極集電体）の両面に帯状に塗布して乾燥、プレスすることにより、正極シート（総厚み６５μｍ）を得た。 Li [Ni 0.33 Co 0.33 Mn 0.33 ] O 2 powder (LNCM) as a positive electrode active material, acetylene black (AB) as a conductive material, and polyvinylidene fluoride (PVdF) as a binder , LNCM: AB: PVdF = 94: 3: 3 was mixed with N-methylpyrrolidone (NMP) at a mass ratio to prepare a slurry composition (positive electrode active material slurry). This composition was applied to both sides of a long aluminum foil (positive electrode current collector) having an average thickness of 15 μm in a strip shape, dried and pressed to obtain a positive electrode sheet (total thickness 65 μm).
負極活物質としての非晶質炭素被覆黒鉛（Ｃ）と、バインダとしてのスチレンブタジエンゴム（ＳＢＲ）と、増粘剤としてのカルボキシメチルセルロース（ＣＭＣ）とを、Ｃ：ＳＢＲ：ＣＭＣ＝９８：１：１の質量比率でイオン交換水と混合して、スラリー状組成物（負極活物質スラリー）を調製した。このスラリーを、平均厚み１０μｍの長尺状銅箔（負極集電体）の両面に帯状に塗布して乾燥、プレスすることにより、負極シート（総厚み７５μｍ）を得た。 Amorphous carbon-coated graphite (C) as a negative electrode active material, styrene butadiene rubber (SBR) as a binder, and carboxymethyl cellulose (CMC) as a thickener, C: SBR: CMC = 98: 1: A slurry composition (negative electrode active material slurry) was prepared by mixing with ion exchange water at a mass ratio of 1. The slurry was applied in a strip shape on both sides of a long copper foil (negative electrode current collector) having an average thickness of 10 μm, dried and pressed to obtain a negative electrode sheet (total thickness 75 μm).
正極シートと負極シートとをセパレータシートを介して長手方向に重ね合わせ、扁平形状に捲回して、表１に示す平坦部の長さＬと積層数ｍとを満たす捲回電極体（実施例１，２および比較例１〜３）を作製した。この電極体を、それぞれ電池ケース内に収容し、開口部から非水電解液を注入した。非水電解液としては、エチレンカーボネート（ＥＣ）とエチルメチルカーボネート（ＥＭＣ）とジメチルカーボネート（ＤＭＣ）とをＥＣ：ＥＭＣ：ＤＭＣ＝３：４：３の体積比で含む混合溶媒に、支持塩としてのＬｉＰＦ６を１．１ｍｏｌ／Ｌの濃度で溶解させたものを用いた。これにより、実施例１，２および比較例１〜３に係る非水電解液二次電池（リチウムイオン二次電池）を構築した。 A positive electrode sheet and a negative electrode sheet are stacked in a longitudinal direction through a separator sheet, wound into a flat shape, and a wound electrode body that satisfies the flat portion length L and the number m of layers shown in Table 1 (Example 1) , 2 and Comparative Examples 1-3) were prepared. Each of these electrode bodies was housed in a battery case, and a nonaqueous electrolyte was injected from the opening. As a non-aqueous electrolyte, a mixed solvent containing ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of EC: EMC: DMC = 3: 4: 3 is used as a supporting salt. In which LiPF 6 was dissolved at a concentration of 1.1 mol / L was used. Thus, non-aqueous electrolyte secondary batteries (lithium ion secondary batteries) according to Examples 1 and 2 and Comparative Examples 1 to 3 were constructed.
上記作製した電池について、２５℃の温度環境下で過充電時の耐電圧性を評価した。具体的には、各電池の外表面に熱電対を張り付けた後、１０Ｃの定電流で電池を強制的に充電し続け、電流遮断を生じさせた。次に、電流遮断直後とその１分後の電池温度（外表面温度）を測定した。そして、次式：温度上昇率（％）＝〔（１分後の電池温度）−（電流遮断直後の電池温度）〕／（電流遮断直後の電池温度）×１００から温度上昇率を求め、過充電時の耐電圧性を比較した。温度上昇率は、値が小さいほど耐電圧性の高いことを表していると言える。結果を、表１の「温度上昇率」の欄に示す。 About the produced battery, the withstand voltage property at the time of overcharge was evaluated under the temperature environment of 25 degreeC. Specifically, after a thermocouple was attached to the outer surface of each battery, the battery was forcibly charged with a constant current of 10 C to cause current interruption. Next, the battery temperature (outer surface temperature) immediately after the current interruption and 1 minute after that was measured. Then, the temperature increase rate is calculated from the following formula: temperature increase rate (%) = [(battery temperature after 1 minute) − (battery temperature immediately after current interruption)] / (battery temperature immediately after current interruption) × 100. The voltage resistance during charging was compared. It can be said that the temperature increase rate indicates that the smaller the value, the higher the voltage resistance. The results are shown in the column of “temperature increase rate” in Table 1.
表１に示すように、比較例１，２に比べ、実施例１〜３では温度上昇率が２０％以下と低く抑えられていた。このことから、０．１≦（Ｌ／ｍ）≦１とすることで耐電圧性を高めることができ、過充電耐性に優れた電池を実現できることがわかった。 As shown in Table 1, compared with Comparative Examples 1 and 2, in Examples 1 to 3, the temperature increase rate was suppressed to 20% or less. From this, it was found that by setting 0.1 ≦ (L / m) ≦ 1, it is possible to improve the voltage resistance and to realize a battery with excellent overcharge resistance.
＜ＩＩ．セパレータシートの熱収縮率の検討＞
上記Ｉ．と同様に、表２に示す構成の非水電解液二次電池（実施例４〜１０および比較例５〜８）を構築し、過充電時の温度上昇率を測定した。結果を表２の「温度上昇率」の欄に示す。
<II. Examination of thermal shrinkage of separator sheet>
I. above. Similarly, non-aqueous electrolyte secondary batteries (Examples 4 to 10 and Comparative Examples 5 to 8) having the configuration shown in Table 2 were constructed, and the temperature increase rate during overcharge was measured. The results are shown in the column of “Temperature rise rate” in Table 2.
表２に示すように、比較例３〜５に比べ、実施例４〜１０では温度上昇率が２０％以下と低く抑えられていた。このことから、セパレータシートのＭＤ方向の熱収縮率ａが１〜３０％の範囲であり、ＴＤ方向の熱収縮率ｂが０．５〜１０％の範囲であり、且つ、ａとｂの積（ａｂ）が１〜１５０の範囲である場合、耐電圧性を高めることができ、過充電耐性に優れた電池を実現できることがわかった。 As shown in Table 2, compared with Comparative Examples 3-5, in Examples 4-10, the rate of temperature increase was suppressed to 20% or less. From this, the thermal contraction rate a in the MD direction of the separator sheet is in the range of 1 to 30%, the thermal contraction rate b in the TD direction is in the range of 0.5 to 10%, and the product of a and b It has been found that when (ab) is in the range of 1 to 150, the withstand voltage can be increased, and a battery having excellent overcharge resistance can be realized.
＜ＩＩＩ．正極シート、負極シート、セパレータシートの厚みの検討＞
上記Ｉ．と同様に、表３に示す構成の非水電解液二次電池（実施例１１〜２１および比較例９〜１５）を構築し、過充電時の温度上昇率を測定した。結果を表３の「温度上昇率」の欄に示す。
<III. Examination of thickness of positive electrode sheet, negative electrode sheet, separator sheet>
I. above. Similarly, non-aqueous electrolyte secondary batteries (Examples 11 to 21 and Comparative Examples 9 to 15) configured as shown in Table 3 were constructed, and the rate of temperature increase during overcharging was measured. The result is shown in the column of “temperature rise rate” in Table 3.
表３に示すように、比較例９〜１５に比べ、実施例１１〜２１では温度上昇率が２０％以下と低く抑えられていた。このことから、正極シートの厚みが４０〜１００μｍであり、負極シートの厚みが５０〜１５０μｍであり、セパレータシートの厚みが１５〜３０μｍであり、捲回電極体の捲回軸方向の長さ（幅方向の厚み）が２００ｍｍ以下の範囲にある場合、本発明の効果を好適に発揮し得ることがわかった。なお、車載用途の電池の場合、捲回電極体の捲回軸方向の長さが１１０ｍｍより小さいと、活物質の量が少なくなり、電池容量が不足する虞がある。換言すれば、高容量の電池では捲回電極体の捲回軸方向の長さを１１０〜２００ｍｍとすることで電池容量と過充電耐性とを両立することができる。 As shown in Table 3, compared with Comparative Examples 9-15, in Examples 11-21, the temperature increase rate was suppressed to 20% or less. From this, the thickness of the positive electrode sheet is 40 to 100 μm, the thickness of the negative electrode sheet is 50 to 150 μm, the thickness of the separator sheet is 15 to 30 μm, and the length of the wound electrode body in the winding axis direction ( It has been found that when the thickness in the width direction is in the range of 200 mm or less, the effects of the present invention can be suitably exhibited. In the case of a battery for in-vehicle use, if the length of the wound electrode body in the winding axis direction is smaller than 110 mm, the amount of the active material is decreased, and the battery capacity may be insufficient. In other words, in a high-capacity battery, both the battery capacity and the overcharge resistance can be achieved by setting the length of the wound electrode body in the winding axis direction to 110 to 200 mm.
これらの評価結果から明らかなように、ここで開示される技術によれば、信頼性や過充電耐性に優れた非水電解液二次電池を提供することができる。 As is clear from these evaluation results, according to the technology disclosed herein, a non-aqueous electrolyte secondary battery excellent in reliability and overcharge resistance can be provided.
以上、本発明を詳細に説明したが、上記実施形態および実施例は例示にすぎず、ここで開示される発明には上述の具体例を様々に変形、変更したものが含まれる。 As mentioned above, although this invention was demonstrated in detail, the said embodiment and Example are only illustrations and what changed and changed the above-mentioned specific example is contained in the invention disclosed here.
１ 捲回電極体
２ 正極シート
４ 負極シート
６ セパレータシート
1
Claims (1)
前記捲回電極体は、捲回軸に直交する方向において、両端のＲ部と、該２つのＲ部に挟まれた平坦部と、から構成されており、
ここで、前記捲回電極体の捲回軸方向の長さは１１０〜２００ｍｍであり、且つ、前記捲回軸に直交する方向における前記平坦部の長さをＬ（ｍｍ）とし、前記セパレータシートの積層数をｍとしたときに、０．１≦（Ｌ／ｍ）≦１を満たし、
前記正極シートの平均厚みは４０〜１００μｍであり、
前記負極シートの平均厚みは５０〜１５０μｍであり、
前記セパレータシートは、平均厚みが１５〜３０μｍであり、且つ、１５０℃で加熱したときの前記捲回軸に直交する方向（ＭＤ方向）の熱収縮率ａ（％）と前記捲回軸方向（ＴＤ方向）の熱収縮率をｂ（％）とが、以下：
１≦ａ≦３０、
０．５≦ｂ≦１０、
１≦ａｂ≦１５０、を満たす、非水電解液二次電池。 A non-aqueous electrolyte comprising: a flat wound electrode body formed by overlapping a long positive electrode sheet and a long negative electrode sheet in a longitudinal direction with a long separator sheet interposed therebetween; and a non-aqueous electrolyte. A water electrolyte secondary battery,
The wound electrode body is composed of R portions at both ends in a direction perpendicular to the winding axis, and a flat portion sandwiched between the two R portions,
Here, the length of the wound electrode body in the winding axis direction is 110 to 200 mm, and the length of the flat portion in the direction orthogonal to the winding axis is L (mm), and the separator sheet When the number of stacked layers is m, 0.1 ≦ (L / m) ≦ 1 is satisfied,
The positive electrode sheet has an average thickness of 40 to 100 μm,
The negative electrode sheet has an average thickness of 50 to 150 μm,
The separator sheet has an average thickness of 15 to 30 μm and a heat shrinkage rate a (%) in the direction perpendicular to the winding axis (MD direction) when heated at 150 ° C. and the winding axis direction ( The thermal contraction rate in the TD direction is b (%),
1 ≦ a ≦ 30,
0.5 ≦ b ≦ 10,
A nonaqueous electrolyte secondary battery satisfying 1 ≦ ab ≦ 150.
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