JP6049520B2 - Lithium ion secondary battery separator manufacturing apparatus and manufacturing method - Google Patents
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- 238000003860 storage Methods 0.000 description 4
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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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
Description
本発明は、リチウムイオン二次電池用セパレータの製造装置および製造方法に関する。 The present invention relates to a manufacturing apparatus and a manufacturing method of a separator for a lithium ion secondary battery.
リチウムイオン二次電池（以下、「電池」と略記することがある）は、高いエネルギー密度を有することから、携帯機には、電気自動車、電気貯蔵システム等に用いる蓄電デバイスとして注目されている。しかし、リチウムイオン二次電池には、内部に可燃性の電解液や負極を用いることから、内部短絡等が引き金となって発火する等の危険性がある。とりわけ、セパレータの小さな穿孔から始まり、「短絡」−「短絡電流による発熱」−「セパレータの収縮による穿孔の拡大」−「短絡電流の増大」のサイクルを繰り返して急激に短絡電流が増大する事象（熱暴走）は、特に危険な事象として知られている。 Lithium ion secondary batteries (hereinafter may be abbreviated as “batteries”) have a high energy density, and thus have attracted attention as portable storage devices as electric storage devices used in electric vehicles, electric storage systems, and the like. However, since a lithium ion secondary battery uses a flammable electrolyte solution or a negative electrode inside, there is a risk that an internal short circuit or the like triggers ignition. In particular, an event in which the short-circuit current suddenly increases by repeating the cycle of “short circuit” − “heat generation due to short-circuit current” − “expansion of perforation due to contraction of separator” − “increase in short-circuit current” starting from small perforations of the separator ( Thermal runaway) is known as a particularly dangerous event.
リチウムイオン二次電池セパレータ（以下、「セパレータ」と略記することがある）としては、ポリエチレン、ポリプロピレン等のポリオレフィンからなる多孔質フィルムが広く用いられている。しかし、これら多孔質フィルムからなるセパレータは高温下で収縮しやすく、熱暴走防止という観点から好ましいとは言えない。高温下での収縮を抑制するために、多孔質フィルムの表面に耐熱性粒子を主体とする塗工層を設けたセパレータが提案されているが、熱収縮を好ましい水準まで抑制できるには至っていない。 As lithium ion secondary battery separators (hereinafter sometimes abbreviated as “separators”), porous films made of polyolefins such as polyethylene and polypropylene are widely used. However, separators made of these porous films tend to shrink at high temperatures and are not preferable from the viewpoint of preventing thermal runaway. In order to suppress shrinkage at high temperatures, a separator having a coating layer mainly composed of heat-resistant particles on the surface of a porous film has been proposed, but thermal shrinkage has not been suppressed to a desirable level. .
高温下での収縮が少ないセパレータとして、耐熱性の良好な不織布基材に、耐熱性粒子を含む層（例えば、特許文献１参照）を形成してなるセパレータが提案されている。このようなセパレータは、不織布基材に耐熱性粒子を含む塗工液を付与後、乾燥させることによって連続的に製造される。しかし、不織布基材の目の開きは、一般に塗工層を構成する耐熱性粒子の粒子径よりも大きいため、塗工液が不織布基材を通り抜けて塗工面の反対側にまで回りこみやすく、塗布液を付与後、乾燥させるまでの間の搬送ロールに塗工液がランダムに転写し、さらには搬送ロールに付着した塗工液やその乾固物が不織布基材に再付着する等が繰り返されることによって、不織布基材の面内において、塗工量のムラが生じやすいという問題があった。 As a separator with low shrinkage at high temperatures, a separator formed by forming a layer containing heat-resistant particles (for example, see Patent Document 1) on a non-woven fabric base material having good heat resistance has been proposed. Such a separator is continuously produced by applying a coating liquid containing heat-resistant particles to a nonwoven fabric substrate and then drying it. However, since the opening of the nonwoven fabric substrate is generally larger than the particle size of the heat-resistant particles constituting the coating layer, the coating liquid easily passes through the nonwoven fabric substrate to the opposite side of the coating surface, After applying the coating liquid, the coating liquid is randomly transferred to the transport roll until it is dried, and the coating liquid adhering to the transport roll and its dried solid are reattached to the nonwoven fabric substrate. As a result, there is a problem that unevenness of the coating amount is likely to occur within the surface of the nonwoven fabric substrate.
一般に、不織布基材に耐熱性粒子を含む層を形成してなるセパレータにおいては、塗工量が少なくなると内部抵抗が低くなり、塗工量が多くなると自己放電が起こりにくくなる。自己放電は、不織布基材の面内で最も塗工量が少ない部分に支配される。そのため、塗工量ムラがある場合、最も塗工量の少ない部分でも自己放電が十分に抑制されるように、全体の塗工量を増加させる必要がある。その結果、内部抵抗の上昇は避けられなくなる。したがって、内部抵抗と自己放電を最も良好な水準で両立するためには、面内での塗工量分布が均一であることが必要である。しかし、不織布基材に耐熱性粒子を含む層を形成してなるセパレータにおいて、従来の技術で製造されたものは、塗工量の面内均一性が十分な水準に達しておらず、内部抵抗と自己放電の両立度合いにも限界があった。 In general, in a separator formed by forming a layer containing heat-resistant particles on a nonwoven fabric base material, the internal resistance decreases when the coating amount decreases, and self-discharge hardly occurs when the coating amount increases. Self-discharge is governed by the portion with the smallest coating amount within the surface of the nonwoven fabric substrate. Therefore, when there is uneven coating amount, it is necessary to increase the entire coating amount so that self-discharge can be sufficiently suppressed even in the portion with the smallest coating amount. As a result, an increase in internal resistance is inevitable. Therefore, in order to achieve both internal resistance and self-discharge at the best level, it is necessary that the coating amount distribution in the surface is uniform. However, in the separator formed by forming a layer containing heat-resistant particles on the nonwoven fabric base material, the in-plane uniformity of the coating amount has not reached a sufficient level, and the internal resistance There was also a limit to the degree of compatibility between self-discharge and self-discharge.
この問題を避けるため、不織布基材の両面から塗工液を付与する製造方法（例えば、特許文献１および２参照）が提案されている。しかし、このような製造方法を用いた場合、不織布基材の走行速度が速くなると、不織布基材内部のポアに存在する空気が十分に除去（塗工液により置換）されず、残存した気泡に起因するボイドが発生し、耐熱性粒子の存在しない微小空間が形成されやすい。このようなボイドが形成された場合、自己放電が抑制された良好なセパレータを得ることができない。そのため、不織布基材の両面から塗工液を付与する製造方法を用いる場合には、ボイドの形成を避けるために、不織布基材の走行速度を相当に低くせざるを得ず、高い生産性は得られない。具体例として、特許文献１の実施例における走行速度は１．９ｍ／ｍｉｎであり、特許文献２の実施例における走行速度は２ｍ／ｍｉｎであり、どちらもかなりの低速で塗工している。 In order to avoid this problem, a manufacturing method (see, for example, Patent Documents 1 and 2) in which a coating liquid is applied from both surfaces of a nonwoven fabric substrate has been proposed. However, when such a manufacturing method is used, if the running speed of the nonwoven fabric substrate increases, the air present in the pores inside the nonwoven fabric substrate is not sufficiently removed (replaced by the coating liquid), and remains in the remaining bubbles. The resulting voids are generated, and a minute space without heat-resistant particles is easily formed. When such voids are formed, a good separator with suppressed self-discharge cannot be obtained. Therefore, when using a manufacturing method for applying a coating liquid from both sides of the nonwoven fabric substrate, the traveling speed of the nonwoven fabric substrate has to be considerably reduced in order to avoid formation of voids, and high productivity is I can't get it. As a specific example, the traveling speed in the embodiment of Patent Document 1 is 1.9 m / min, and the traveling speed in the embodiment of Patent Document 2 is 2 m / min, both of which are applied at a considerably low speed.
本発明の課題は、不織布基材に塗工層を形成してなるリチウムイオン二次電池用セパレータの製造方法および製造装置において、内部抵抗および自己放電性を良好な水準で両立できるリチウムイオン二次電池用セパレータを高い生産性で製造することができる製造方法および製造装置を提供することにある。 An object of the present invention is to provide a lithium ion secondary battery capable of achieving both internal resistance and self-discharge properties at a good level in a method and apparatus for producing a separator for a lithium ion secondary battery in which a coating layer is formed on a nonwoven fabric substrate. It is providing the manufacturing method and manufacturing apparatus which can manufacture the separator for batteries with high productivity.
本発明者らは、上記課題を解決するために鋭意研究し、
（１）不織布基材に塗工層を形成してなるリチウムイオン二次電池用セパレータの製造方法において、不織布基材に塗工液を付与後、乾燥させるまでの間の搬送ロールが、直径２５ｍｍ以下のロールであり、塗工液が付与された面とは反対側の面を該搬送ロールで支持することを特徴とするリチウムイオン二次電池用セパレータの製造方法、
（２）該搬送ロールの素材が、炭素繊維強化プラスチックである（１）記載のリチウムイオン二次電池用セパレータの製造方法、
（３）不織布基材に塗工層を形成してなるリチウムイオン二次電池用セパレータの製造装置において、不織布基材に塗工液を付与後、乾燥させるまでの間の搬送ロールが、直径２５ｍｍ以下のロールであり、塗工液が付与された面とは反対側の面を該搬送ロールで支持することを特徴とするリチウムイオン二次電池用セパレータの製造装置、
（４）該搬送ロールの素材が、炭素繊維強化プラスチックである（３）記載のリチウムイオン二次電池用セパレータの製造装置、
を見出した。
The present inventors have intensively studied to solve the above problems,
(1) In the manufacturing method of the separator for lithium ion secondary batteries which forms a coating layer in a nonwoven fabric base material, a conveyance roll until it dries after applying a coating liquid to a nonwoven fabric base material is 25 mm in diameter A method for producing a separator for a lithium ion secondary battery, characterized in that the following roll is used, and the surface opposite to the surface to which the coating liquid is applied is supported by the transport roll,
(2) The manufacturing method of the separator for lithium ion secondary batteries as described in (1) whose raw material of this conveyance roll is a carbon fiber reinforced plastic,
(3) In an apparatus for manufacturing a separator for a lithium ion secondary battery in which a coating layer is formed on a nonwoven fabric base material, a transport roll until the coating roll is dried after the coating liquid is applied to the nonwoven fabric base material has a diameter of 25 mm. An apparatus for manufacturing a separator for a lithium ion secondary battery, characterized in that the roll is the following roll, and the surface opposite to the surface to which the coating liquid is applied is supported by the transport roll,
(4) The separator manufacturing apparatus for a lithium ion secondary battery according to (3), wherein the material of the transport roll is a carbon fiber reinforced plastic,
I found.
本発明によれば、内部抵抗および自己放電性を良好な水準で両立できるリチウムイオン二次電池用セパレータを高い生産性で製造することができる製造方法および製造装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method and manufacturing apparatus which can manufacture the separator for lithium ion secondary batteries which can make internal resistance and self-discharge property compatible in a favorable level with high productivity can be provided.
本発明は、不織布基材に塗工層を形成してなるリチウムイオン二次電池用セパレータの製造方法および製造装置であり、耐熱性粒子を含む塗工液を不織布基材に付与してセパレータを製造するのに用いる製造装置および製造方法である。本発明では、不織布基材の片面に塗工液を付与する工程（塗工工程）後、塗工液を付与したのとは反対面を搬送ロールで適宜支持しながら、不織布基材を乾燥する工程（乾燥工程）にまで搬送する。この搬送ロールが、直径２５ｍｍ以下の小径ロールであり、塗工液が付与された面とは反対側の面を該搬送ロールで支持することを特徴とする。「搬送ロール」とは、不織布基材のバタツキや自重による垂れ下がりを防ぎ、走行を安定させるために不織布基材を支持するための円筒状の回転機構である。以下、「搬送ロール」と記した場合は、塗工工程から乾燥工程までの間の搬送ロールを示す。 The present invention relates to a method and an apparatus for manufacturing a separator for a lithium ion secondary battery in which a coating layer is formed on a nonwoven fabric substrate, and the separator is formed by applying a coating liquid containing heat-resistant particles to the nonwoven fabric substrate. A manufacturing apparatus and a manufacturing method used for manufacturing. In the present invention, after the step of applying the coating liquid to one side of the nonwoven fabric substrate (coating step), the nonwoven fabric substrate is dried while appropriately supporting the opposite surface of the nonwoven fabric substrate with the transport roll. It conveys to a process (drying process). The transport roll is a small-diameter roll having a diameter of 25 mm or less, and the transport roll supports the surface opposite to the surface to which the coating liquid is applied. The “conveying roll” is a cylindrical rotating mechanism for supporting the nonwoven fabric base material in order to prevent the nonwoven fabric base material from fluttering or drooping due to its own weight and to stabilize traveling. Hereinafter, when described as “transport roll”, it indicates a transport roll from the coating process to the drying process.
搬送ロールとして、大径ロールを用いた場合、不織布基材表面の塗工液が搬送ロールにランダムに転写され、さらに、搬送ロールに転写された塗工液やその乾固物が不織布基材に再転写することが繰り返されることによって、不織布基材の面内において塗工量のムラが生じやすい。このような問題を避けるために、塗工工程を経た不織布基材を、ロールに接触させること無く乾燥工程に搬送することも考えられるが、乾燥用空気の風圧等によって不織布基材がばたつき、塗工工程に振動が伝播することから、面内の塗工量分布が均一にならないという問題が発生する。 When a large-diameter roll is used as the transport roll, the coating liquid on the surface of the nonwoven fabric substrate is randomly transferred to the transport roll, and the coating liquid transferred to the transport roll and the dried product thereof are transferred to the nonwoven fabric base material. By repeating the retransfer, unevenness in the coating amount tends to occur within the surface of the nonwoven fabric substrate. In order to avoid such problems, it is conceivable that the nonwoven fabric substrate that has undergone the coating process is transported to the drying process without being brought into contact with the roll, but the nonwoven fabric substrate flutters due to the wind pressure of the drying air, etc. Since vibration propagates to the construction process, there arises a problem that the in-plane coating amount distribution is not uniform.
本発明では、搬送ロールが直径２５ｍｍ以下であることで、不織布基材表面から搬送ロールへの塗工液の転写、搬送ロールから不織布基材表面への塗工液の再転写が均一になり、不織布基材面内の塗工量分布が均一なセパレータを製造することができる。すなわち、内部抵抗および自己放電性を良好な水準で両立するセパレータを製造することができる。 In the present invention, since the transport roll has a diameter of 25 mm or less, the transfer of the coating liquid from the nonwoven fabric substrate surface to the transport roll, the retransfer of the coating liquid from the transport roll to the nonwoven fabric substrate surface becomes uniform, A separator having a uniform coating amount distribution in the surface of the nonwoven fabric substrate can be produced. That is, it is possible to manufacture a separator that achieves both internal resistance and self-discharge properties at good levels.
本発明では塗工液が付与された面とは反対側の面を搬送ロールで支持することで、不織布基材表面から搬送ロールへの塗工液の転写、搬送ロールから不織布基材表面への塗工液の再転写が生じにくく、不織布基材面内の塗工量分布が均一なセパレータを製造することができる。すなわち、内部抵抗および自己放電性を良好な水準で両立するセパレータを製造することができる。 In the present invention, the surface opposite to the surface to which the coating liquid is applied is supported by the transport roll, so that the coating liquid is transferred from the nonwoven fabric substrate surface to the transport roll, and from the transport roll to the nonwoven fabric substrate surface. It is difficult to re-transfer the coating liquid, and it is possible to produce a separator having a uniform coating amount distribution within the nonwoven fabric substrate surface. That is, it is possible to manufacture a separator that achieves both internal resistance and self-discharge properties at good levels.
直径２５ｍｍ以下の搬送ロールは、任意の素材から製作することができる。しかし、不織布基材の幅が広い場合や、搬送ロールの直径が特に細い場合には、搬送ロールが撓んで不織布基材との接触圧が幅方向で均一にならない場合があり、幅方向に均一なセパレータが得られない場合がある。このような事象を避けるためには、軽量で高剛性の素材であることが好ましい。具体的には炭素繊維強化プラスチックや、その表面にクロムめっきなどの金属めっきを施したものが、好ましく用いられる。なお、搬送ロールの撓みを防ぐ見地から、その直径は１０ｍｍ以上であることが好ましい。より好ましい搬送ロールの直径は、１０〜１５ｍｍである。 A conveyance roll having a diameter of 25 mm or less can be manufactured from any material. However, when the width of the nonwoven fabric substrate is wide or the diameter of the transport roll is particularly thin, the transport roll may bend and the contact pressure with the nonwoven fabric substrate may not be uniform in the width direction. May not be obtained. In order to avoid such an event, it is preferable that the material is light and highly rigid. Specifically, carbon fiber reinforced plastics or those whose surfaces are plated with a metal such as chromium plating are preferably used. From the viewpoint of preventing the conveyance roll from being bent, the diameter is preferably 10 mm or more. The diameter of a more preferable conveyance roll is 10-15 mm.
搬送ロールは、不織布基材と連れ回転（連れ回り、不織布基材と搬送ロールとの間の摩擦により、その周速が不織布基材の走行速度と一致して回転すること）するように用いても、本発明の効果を得ることができる。しかし、この場合、長時間連続でセパレータを製造し続けると、搬送ロールに塗工液の凝集物等が堆積し、セパレータに欠陥が生じる原因となる場合がある。これを防ぐためには、搬送ロールを、非等速回転させることが好ましい。すなわち、搬送ロールの周速と不織布基材の走行速度とが異なる速度になるように、外部動力により搬送ロールを駆動することが好ましい。なお、搬送ロールの周速が、不織布基材の走行速度よりも、遅くなってもよいし、速くなってもよい。 The transport roll is used so as to rotate with the nonwoven fabric base material (with rotation, the peripheral speed of the nonwoven fabric base material and the transport roll rotates in accordance with the traveling speed of the nonwoven fabric base material). Also, the effects of the present invention can be obtained. However, in this case, if the separator is continuously manufactured for a long time, agglomerates and the like of the coating liquid may accumulate on the transport roll, which may cause defects in the separator. In order to prevent this, it is preferable to rotate the transport roll at a non-constant speed. That is, it is preferable to drive the transport roll with external power so that the peripheral speed of the transport roll and the running speed of the nonwoven fabric substrate are different. In addition, the circumferential speed of a conveyance roll may become slower than the running speed of a nonwoven fabric base material, and may become faster.
図１は、本発明の製造装置の一例を示す概略図である。不織布基材はアンワインダーによって、不織布基材ロールＭより引き出される。次に、塗工装置Ｈで、不織布基材の片面に塗工液が付与される。塗工液が付与された不織布基材は、塗工液を付与されたのと反対面を１本または複数本の搬送ロールＴに支持されながら走行し、乾燥装置Ｄによって乾燥される。乾燥は、塗工液の付着量が少ない点および迅速に乾燥することができる点から、塗工液を付与したのとは反対の面を先に乾燥させることが好ましい。少なくとも溶媒の一部が蒸発し、付与された塗工液が流動性を失った後の不織布基材を支持するために用いる搬送ロールには、直径２５ｍｍ以下のロールを用いる必要は無く、直径２５ｍｍを超えるロールも用いることができる。 FIG. 1 is a schematic view showing an example of the production apparatus of the present invention. The nonwoven fabric substrate is pulled out from the nonwoven fabric substrate roll M by an unwinder. Next, a coating liquid is applied to one side of the nonwoven fabric substrate by the coating apparatus H. The nonwoven fabric substrate to which the coating liquid has been applied travels while being supported by one or a plurality of transport rolls T on the opposite side to which the coating liquid has been applied, and is dried by the drying device D. In terms of drying, it is preferable to dry the surface opposite to that applied with the coating liquid first from the viewpoint that the amount of the coating liquid adhered is small and that the coating liquid can be quickly dried. It is not necessary to use a roll having a diameter of 25 mm or less as a transport roll used to support the nonwoven fabric substrate after at least a part of the solvent evaporates and the applied coating liquid loses fluidity. More rolls can be used.
本発明において、塗工装置に特に制限は無い。不織布基材に過剰量の塗工液を付与した後、ドクター装置により過剰分の塗工液の除去および塗工面の平滑化を行う後計量方式の装置、基材に所定量の塗工液を付与しつつ、同時に塗工面の平滑化を行う前計量方式の装置等を用いることができる。後計量方式の装置としては、例えば、エアドクターコーター、ブレードコーター、ロッドコーター、スクイズコーター、含浸（ディップ）コーター等が代表的である。前計量方式の装置としては、例えばグラビアコーター、キスロールコーター、ダイコーター、リバースロールコーター、トランスファーロールコーター、スプレーコーター、ローターダンプニング等が代表的である。 In the present invention, the coating apparatus is not particularly limited. After applying an excessive amount of coating solution to the nonwoven fabric substrate, remove the excess coating solution with a doctor device and smooth the coated surface. It is possible to use a pre-weighing type apparatus or the like that simultaneously smoothes the coated surface while applying. Typical examples of the post-measuring device include an air doctor coater, a blade coater, a rod coater, a squeeze coater, and an impregnation (dip) coater. Typical examples of the pre-measuring device include a gravure coater, a kiss roll coater, a die coater, a reverse roll coater, a transfer roll coater, a spray coater, and a rotor dampening.
本発明において、乾燥装置にも特に制限は無く、不織布基材の表面に熱風や乾燥空気を吹きつけて乾燥するエアドライヤー、加熱した金属製円筒の表面に不織布基材を接触させることで加熱乾燥するシリンダードライヤー、赤外線により不織布基材を加熱する赤外線ドライヤー等の乾燥装置を用いることができる。 In the present invention, the drying apparatus is not particularly limited, and is an air dryer that blows hot air or dry air on the surface of the nonwoven fabric substrate to dry, and heat drying by bringing the nonwoven fabric substrate into contact with the surface of a heated metal cylinder. A drying device such as a cylinder dryer or an infrared dryer that heats the nonwoven fabric substrate with infrared rays can be used.
本発明において、不織布基材は、直径が３．５μｍ以下の繊維を５０質量％以上含むことが好ましい。これによって、面内の塗工量分布が不均一になることをより確実に防止することができる。また、不織布基材の厚みは、好ましくは１０μｍ以上であり、より好ましくは１５μｍ以上である。これによって、面内の塗工量分布が不均一になることをより確実に防止することができる。一方、不織布基材の厚みが厚すぎる場合は、セパレータの厚みが厚くなりすぎることから、不織布基材の厚みは好ましくは３０μｍ以下であり、より好ましくは２５μｍ以下である。 In this invention, it is preferable that a nonwoven fabric base material contains 50 mass% or more of fibers with a diameter of 3.5 micrometers or less. This can more reliably prevent the in-plane coating amount distribution from becoming uneven. The thickness of the nonwoven fabric substrate is preferably 10 μm or more, more preferably 15 μm or more. This can more reliably prevent the in-plane coating amount distribution from becoming uneven. On the other hand, when the thickness of the nonwoven fabric substrate is too thick, the thickness of the nonwoven fabric substrate is preferably 30 μm or less, more preferably 25 μm or less, because the thickness of the separator becomes too thick.
本発明において、塗工液としては、耐熱性粒子として、不定形シリカ等の珪素酸化物、αアルミナ、γアルミナ、ベーマイト等のアルミナ水和物、ダイアスポア、ギプサイト等のアルミニウム酸化物およびその水和物、アルミナ−シリカ複合酸化物、チタン酸バリウム等の耐熱性無機粒子；架橋ポリスチレン、架橋メタクリル酸メチル等の耐熱性有機粒子を用いることができる。スチレンブタジエンゴム（ＳＢＲ）、アクリル系ポリマー等のバインダー、各種の界面活性剤、カルボキシメチルセルロース、ポリエチレンオキサイド等の液性調整剤等の各種添加剤を加えたものを用いることができる、溶媒としては、水を用いても良いし、有機溶媒を用いても良い。 In the present invention, the coating liquid includes heat-resistant particles such as silicon oxide such as amorphous silica, alumina hydrate such as α alumina, γ alumina and boehmite, aluminum oxide such as diaspore and gypsite, and hydration thereof. , Heat-resistant inorganic particles such as alumina-silica composite oxide and barium titanate; heat-resistant organic particles such as crosslinked polystyrene and crosslinked methyl methacrylate can be used. What added various additives, such as binders, such as styrene butadiene rubber (SBR) and an acrylic polymer, various surfactants, liquid modifiers, such as carboxymethylcellulose and polyethylene oxide, As a solvent, Water or an organic solvent may be used.
以下、本発明を実施例によりさらに詳細に説明するが、本発明は本実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a present Example.
実施例１
［不織布基材］
繊度０．１ｄｔｅｘ、カット長３ｍｍの延伸結晶化ポリエチレンテレフタレートステープル７０質量部および繊度０．２ｄｔｅｘ、カット長３ｍｍの非延伸ポリエチレンテレフタレートステープル３０質量部からなり、表面温度２００℃の熱カレンダーにより繊維間を融着させつつ、厚み調整を行った、坪量１０ｇ／ｍ２、厚み１８μｍの湿式抄造不織布を不織布基材として用いた。
Example 1
[Nonwoven fabric substrate]
It consists of 70 parts by mass of stretched crystallized polyethylene terephthalate staples with a fineness of 0.1 dtex and a cut length of 3 mm, and 30 parts by mass of non-stretched polyethylene terephthalate staples with a fineness of 0.2 dtex and a cut length of 3 mm. A wet papermaking nonwoven fabric having a basis weight of 10 g / m 2 and a thickness of 18 μm, which was adjusted in thickness while being fused, was used as a nonwoven fabric substrate.
［塗工液］
固形分の質量構成比が、アルミナ水和物（ベーマイト）：アクリル系ポリマーのラテックス：マレイン酸−アクリル酸共重合体のナトリウム塩：１質量％水溶液の粘度が７０００ｍＰａ・ｓｅｃであるカルボキシメチルセルロース＝４０．０：２．０：０．４：０．２である、固形分濃度４０質量％の塗工液を調製した。
[Coating fluid]
Carboxymethylcellulose having a mass composition ratio of solid content of alumina hydrate (boehmite): latex of acrylic polymer: sodium salt of maleic acid-acrylic acid copolymer: viscosity of 1% by mass aqueous solution is 7000 mPa · sec = 40 A coating solution having a solid content concentration of 40% by mass and 0.0: 2.0: 0.4: 0.2 was prepared.
［セパレータの製造］
搬送ロールＴとして、有効幅４００ｍｍ、直径２５ｍｍのアルミニウム製中空ロールを用い、塗工装置Ｈとしてリバースダイレクトグラビアコーターを備えた、概要を図１に示した製造装置を用いて、幅３００ｍｍの前記不織布基材に、前記塗工液を、乾燥後の塗工量が１０．０ｇ／ｍ２になるように塗工し、セパレータを得た。不織布基材の走行速度は１５ｍ／ｍｉｎであった。
[Manufacture of separators]
The non-woven fabric having a width of 300 mm using the manufacturing apparatus shown in FIG. 1 as an outline, using an aluminum hollow roll having an effective width of 400 mm and a diameter of 25 mm as the transport roll T and a reverse direct gravure coater as the coating apparatus H. The separator was obtained by coating the substrate with the coating solution so that the coating amount after drying was 10.0 g / m 2 . The running speed of the nonwoven fabric substrate was 15 m / min.
実施例２
搬送ロールの直径を２０ｍｍとした以外は、実施例１と同様にして、セパレータを作製した。
Example 2
A separator was produced in the same manner as in Example 1 except that the diameter of the transport roll was 20 mm.
実施例３
搬送ロールの直径を１５ｍｍとした以外は、実施例１と同様にして、セパレータを作製した。
Example 3
A separator was produced in the same manner as in Example 1 except that the diameter of the transport roll was 15 mm.
実施例４
搬送ロールの直径を１０ｍｍとした以外は、実施例１と同様にして、セパレータを作製した。
Example 4
A separator was produced in the same manner as in Example 1 except that the diameter of the transport roll was 10 mm.
比較例１
搬送ロールの直径を３０ｍｍとした以外は、実施例１と同様にして、セパレータを作製した。
Comparative Example 1
A separator was produced in the same manner as in Example 1 except that the diameter of the transport roll was 30 mm.
比較例２
塗工装置Ｈとして、リバースダイレクトグラビアコーターの代わりに、過剰の塗工液を付与した後、ロッドを用いて過剰の塗工液を除去しながら塗工面を平滑化するロッドコーターを用い、かつ塗工液の付与面を反対面にした以外は、実施例３と同様にして、セパレータを作製した。
Comparative Example 2
Instead of the reverse direct gravure coater, as the coating apparatus H, a rod coater that smoothes the coating surface while applying an excess coating solution and removing the excess coating solution using a rod is used. A separator was produced in the same manner as in Example 3 except that the surface to which the working liquid was applied was changed to the opposite surface.
比較例３
塗工装置Ｈとして、不織布基材の両面に塗工液を付与しながらロール間を通過させて塗工量を調整するスクイズコーターを用いた以外は、実施例３と同様にして、セパレータを作製した。
Comparative Example 3
A separator is produced in the same manner as in Example 3 except that a squeeze coater that adjusts the coating amount by passing between rolls while applying the coating liquid to both surfaces of the nonwoven fabric substrate is used as the coating apparatus H. did.
＜評価＞
各実施例および各比較例で作製したリチウムイオン二次電池用セパレータについて、下記の評価を行い、結果を表１に示した。
<Evaluation>
The separators for lithium ion secondary batteries produced in each example and each comparative example were evaluated as follows, and the results are shown in Table 1.
［評価用電池の作製］
正極活物質がマンガン酸リチウム、負極活物質がメソフェーズカーボンマイクロビーズ、電解液がＬｉＰＦ６の１Ｍ ＥＣ：ＤＥＣ（３０：７０ ｖｏｌ％）溶液であり、セパレータが各実施例および比較例のセパレータである、設計容量３０ｍＡｈのパウチ型リチウムイオン二次電池を作製した。各評価用電池につき、下記［評価用電池の充電］による充電→３０ｍＡの定電流放電（端子間電圧２．８Ｖで放電終了）を３回繰り返し、以降の試験に用いた。
[Production of evaluation battery]
The positive electrode active material is lithium manganate, the negative electrode active material is mesophase carbon microbeads, the electrolyte is a 1M EC: DEC (30:70 vol%) solution of LiPF 6 , and the separator is the separator of each example and comparative example. A pouch-type lithium ion secondary battery with a design capacity of 30 mAh was produced. For each evaluation battery, charging by the following [charging of evaluation battery] → constant current discharge of 30 mA (discharging was completed at a terminal voltage of 2.8 V) was repeated three times and used for the subsequent tests.
［評価用電池の充電］
評価用電池に対して、３０ｍＡで定電流充電を行った。正負極間の電圧が４．２Ｖに達した後は、この電圧で定電圧充電を行った。充電電流が３ｍＡに低下した時点で充電終了とした。
[Charging the evaluation battery]
The battery for evaluation was charged with a constant current at 30 mA. After the voltage between the positive and negative electrodes reached 4.2 V, constant voltage charging was performed at this voltage. The charging was terminated when the charging current decreased to 3 mA.
［内部抵抗の測定］
充電済みの各評価用電池について、３０ｍＡの定電流放電を行い、放電開始６分後の電圧Ｅ３０（Ｖ）を記録した。次いで各評価用電池を再度充電した後、６０ｍＡで定電流放電を行い、放電開始３分後の電圧Ｅ６０（Ｖ）を記録した。内部抵抗Ｒ（Ω）＝（Ｅ３０−Ｅ６０）／０．０３（Ａ）を算出した。
[Measurement of internal resistance]
Each test battery in a charged, a constant current discharge of 30 mA, was recorded discharge starting 6 minutes after the voltage E 30 (V). Subsequently, after charging each evaluation battery again, constant current discharge was performed at 60 mA, and voltage E 60 (V) 3 minutes after the start of discharge was recorded. Internal resistance R (Ω) = (E 30 −E 60 ) /0.03 (A) was calculated.
［自己放電性］
各評価用電池について、上記の条件で再度充電を行い、４５℃で１４日間保存後端子間電圧（Ｖ）を測定した。保存後の端子間電圧が高い程、自己放電が少なく良好な電池である。
[Self-discharge]
About each battery for evaluation, it charged again on said conditions, and after storing for 14 days at 45 degreeC, the voltage (V) between terminals was measured. The higher the voltage between terminals after storage, the better the battery with less self-discharge.
表１に示されるように、不織布基材に塗工液を付与し、直径２５ｍｍ以下の搬送ロールを用い、塗工液が付与された面とは反対側の面を搬送ロールで支持しながら乾燥工程に搬送する本発明により、１５ｍ／ｍｉｎという高速で、内部抵抗が低く、自己放電も少ないリチウムイオン二次電池を製造することが可能になった。これに対し、直径２５ｍｍを超える搬送ロールを用いた比較例１では、内部抵抗・自己放電共に大きい。塗工液を付与した面を搬送ロールで支持した比較例２や、基材の両面から塗工液を付与した比較例３では、自己放電が著しく大きい。 As shown in Table 1, the coating liquid is applied to the nonwoven fabric substrate, and a transport roll having a diameter of 25 mm or less is used, and the surface opposite to the surface to which the coating liquid is applied is dried while being supported by the transport roll. The present invention conveyed to the process makes it possible to produce a lithium ion secondary battery at a high speed of 15 m / min, low internal resistance, and low self-discharge. On the other hand, in the comparative example 1 using the conveyance roll exceeding 25 mm in diameter, both internal resistance and self-discharge are large. In Comparative Example 2 in which the surface to which the coating liquid is applied is supported by a transport roll and in Comparative Example 3 in which the coating liquid is applied from both surfaces of the substrate, self-discharge is remarkably large.
本発明の好適な実施態様である、搬送ロールの直径を１０〜１５ｍｍとした実施例３および４と比較すると、搬送ロールの直径が１５ｍｍを超える実施例１および２では、内部抵抗がやや上昇しており、自己放電もやや大きい。 Compared with Examples 3 and 4 in which the diameter of the transport roll is 10 to 15 mm, which is a preferred embodiment of the present invention, in Examples 1 and 2 in which the diameter of the transport roll exceeds 15 mm, the internal resistance slightly increases. The self-discharge is slightly large.
実施例５
搬送ロールＴの有効幅が１２００ｍｍ、不織布基材の幅が１０００ｍｍである以外は、実施例３と同様にして、セパレータを作製した。
Example 5
A separator was produced in the same manner as in Example 3 except that the effective width of the transport roll T was 1200 mm and the width of the nonwoven fabric substrate was 1000 mm.
実施例６
搬送ロールの材質を、無電解ニッケルメッキの下地メッキおよび硬質クロムメッキの表面メッキを表面に施した炭素繊維強化プラスチック（ＣＦＲＰ）とした以外は、実施例５と同様にして、セパレータを作製した。
Example 6
A separator was produced in the same manner as in Example 5 except that the material of the transport roll was carbon fiber reinforced plastic (CFRP) having a surface plated with electroless nickel plating and hard chrome plating.
＜評価＞
［幅方向の均一性］
実施例５および６で作製したセパレータに関しては、幅方向の中央部および端部より切り出したシートを用いて評価用電池を作製し、前記同様の評価を行った。
<Evaluation>
[Uniformity in the width direction]
Regarding the separators produced in Examples 5 and 6, evaluation batteries were produced using sheets cut out from the center and end portions in the width direction, and the same evaluation as described above was performed.
実施例５と実施例６を比較すると、搬送ロールの素材に金属を用いた実施例５よりも、搬送ロールの素材に炭素繊維強化プラスチックを用いた実施例６の方が、不織布基材の全幅にわたって、内部抵抗と自己放電の両立度合いが良好なセパレータを得ることができる。 Comparing Example 5 and Example 6, the full width of the nonwoven fabric substrate in Example 6 using carbon fiber reinforced plastic as the material for the transport roll is greater than Example 5 using metal as the material for the transport roll. In addition, it is possible to obtain a separator having a good compatibility between internal resistance and self-discharge.
本発明のリチウムイオン二次電池用セパレータの製造方法はリチウムイオン二次電池用セパレータの製造方法として好適に使用できる。 The manufacturing method of the separator for lithium ion secondary batteries of this invention can be used conveniently as a manufacturing method of the separator for lithium ion secondary batteries.
Ｄ 乾燥装置
Ｔ 搬送ロール
Ｈ 塗工装置
Ｍ 不織布基材ロール
D Drying device T Transport roll H Coating device M Non-woven fabric base roll
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