JP2020098721A - Manufacturing method of porous layer, lamination body, separator for nonaqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery - Google Patents
Manufacturing method of porous layer, lamination body, separator for nonaqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery Download PDFInfo
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- JP2020098721A JP2020098721A JP2018236551A JP2018236551A JP2020098721A JP 2020098721 A JP2020098721 A JP 2020098721A JP 2018236551 A JP2018236551 A JP 2018236551A JP 2018236551 A JP2018236551 A JP 2018236551A JP 2020098721 A JP2020098721 A JP 2020098721A
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- coating
- secondary battery
- porous layer
- electrolyte secondary
- aqueous electrolyte
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
Description
本発明は、多孔質層の製造方法、並びに、当該製造方法にて製造される多孔質層を含む、積層体、非水電解液二次電池用セパレータおよび非水電解液二次電池に関する。 The present invention relates to a method for producing a porous layer, and a laminate, a separator for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery including the porous layer produced by the production method.
非水電解液二次電池、特にリチウムイオン二次電池は、エネルギー密度が高いのでパーソナルコンピュータ、携帯電話、携帯情報端末などに用いる電池として広く使用され、また最近では車載用の電池として開発が進められてきている。 Non-aqueous electrolyte secondary batteries, especially lithium-ion secondary batteries, are widely used as batteries for personal computers, mobile phones, personal digital assistants, etc. due to their high energy density, and recently they have been developed as in-vehicle batteries. Has been done.
リチウムイオン二次電池のエネルギー密度あるいは容量の拡大に伴って、より高い安全性を有する機構が求められている。例えば、電極を隔てるセパレータ上に金属酸化物と樹脂バインダーとを含む耐熱性を有する多孔層を塗工した多層多孔フィルム（特許文献１〜４、６）、および、電極上に、金属酸化物と樹脂バインダーとを含む多孔質層を塗工した積層体を含む非水電解液二次電池が提案または実用化されている（特許文献５）。 Along with the expansion of energy density or capacity of lithium-ion secondary batteries, a mechanism having higher safety is required. For example, a multilayer porous film in which a heat-resistant porous layer containing a metal oxide and a resin binder is applied on a separator separating electrodes (Patent Documents 1 to 4 and 6), and a metal oxide on the electrode A non-aqueous electrolyte secondary battery including a laminate coated with a porous layer containing a resin binder has been proposed or put into practical use (Patent Document 5).
さらに近年では、リチウムイオン二次電池のさらなるエネルギー密度拡大あるいは容量拡大を目的として、セパレータおよび電極の集電板などの部材の薄膜化が進んでいる。例えば従来のセパレータは、膜厚が２５μｍであるＣｅｌｇａｒｄ（登録商標）＃２５００に代表されるように、数十μｍ程度の厚みであった。しかし、最近では携帯情報端末など民生用電池用途においては、厚み１０μｍ以下の薄膜セパレータが使用されてきている。これに伴い、電極間に設けられた、セパレータや電極塗工層などの多孔質体の厚み精度に対する要求も高まってきている。 Furthermore, in recent years, for the purpose of further expanding the energy density or capacity of the lithium-ion secondary battery, thinning of members such as a separator and a collector plate of an electrode has been advanced. For example, a conventional separator has a thickness of about several tens of μm as represented by Celgard (registered trademark) #2500 having a film thickness of 25 μm. However, recently, thin film separators having a thickness of 10 μm or less have been used for consumer batteries such as portable information terminals. Along with this, there is an increasing demand for accuracy in the thickness of porous bodies such as separators and electrode coating layers provided between electrodes.
ポリオレフィン多孔質フィルムからなるセパレータとして、製造方法の発達によって膜厚のばらつきの小さい、高い膜厚精度を有するセパレータが製造されている。一方、ポリオレフィン多孔質フィルムを基材として使用し、当該基材上に金属酸化物粒子などを含む多孔質層がコーティングされてなるコーティングタイプのセパレータ、すなわち、積層セパレータにおいては、その膜厚精度が基材であるポリオレフィン多孔質フィルムよりも低下することから、その膜厚精度には改善の余地があった。 As a separator made of a polyolefin porous film, a separator having a small film thickness variation and a high film thickness accuracy has been manufactured due to the development of the manufacturing method. On the other hand, using a polyolefin porous film as a substrate, a coating type separator formed by coating a porous layer containing metal oxide particles and the like on the substrate, that is, in a laminated separator, the film thickness accuracy is Since it is lower than that of the polyolefin porous film as the base material, there is room for improvement in the film thickness accuracy.
従来の技術として、多孔質層を形成する工程において低粘度の塗工液を基材に塗工し、塗工後に塗液がレベリングすることによって平滑な塗工層を形成させる方法が知られている。例えば、特許文献７および８には、前記従来の技術を使用して製造された、耐熱層の膜厚のばらつきが小さい電池用セパレータが開示されている。 As a conventional technique, a method of forming a smooth coating layer by applying a low-viscosity coating liquid to a substrate in the step of forming a porous layer and leveling the coating liquid after coating is known. There is. For example, Patent Documents 7 and 8 disclose battery separators manufactured using the above-described conventional technique, in which the thickness of the heat-resistant layer is small.
しかしながら、前記従来の技術では、塗工時の基材のわずかなシワなどが原因となって、マイクロメートルオーダー以下での膜厚制御は困難であった。例えば、従来の製造方法によって得られるコーティングタイプのセパレータの膜厚精度は、標準分散、つまり膜厚の標準偏差の値が１μｍ以上であり、改善の余地があった。 However, in the above-mentioned conventional technique, it is difficult to control the film thickness on the order of micrometers or less due to slight wrinkles of the base material during coating. For example, the film thickness accuracy of the coating type separator obtained by the conventional manufacturing method has standard dispersion, that is, the standard deviation of the film thickness is 1 μm or more, and there is room for improvement.
すなわち、本発明の目的は、非水電解液二次電池の両極間に、基材上に多孔質層が積層されてなる積層体、すなわち積層セパレータを形成するにあたって、膜厚精度が高い多孔質層を含む積層体を製造する方法を提供することである。 That is, the object of the present invention is to form a laminate having a porous layer laminated on a substrate between both electrodes of a non-aqueous electrolyte secondary battery, that is, a porous separator having a high film thickness accuracy in forming a laminated separator. It is an object of the present invention to provide a method of manufacturing a laminate including layers.
前述の事項を鑑み、鋭意研究を重ねた結果、本発明者らは、多孔質層を形成するために基材上にて塗工液を塗工する工程において、エレクトロレオロジー効果を利用することで、高い厚み精度を持った多孔質層を形成できることを発見した。 In view of the above matters, as a result of intensive studies, the present inventors have utilized the electrorheological effect in the step of applying the coating liquid on the substrate to form the porous layer. , It was discovered that it is possible to form a porous layer with high thickness accuracy.
本発明は、上記発見に基づく発明であり、以下の［１］〜［７］に示す発明を含む。
［１］非導電性の溶媒と、粒子とを含む塗工液を、塗工装置と基材との間を通過させることによって、前記基材の面に塗工する工程と、
前記基材の面に塗工した前記塗工液から、前記非導電性の溶媒を除去する工程と、を含み、
前記塗工液が、前記塗工装置と前記基材との間を通過する時の、前記塗工装置と前記基材との間の電場強度が１．０×１０５Ｖ／ｍ以上である、多孔質層の製造方法。
［２］前記塗工液を前記基材の面に塗工する工程の後から、前記非導電性の溶媒を除去する工程の前にて、
前記塗工液が、レベリングされている、［１］に記載の多孔質層の製造方法。
［３］前記塗工液は、樹脂を含む、［１］または［２］に記載の多孔質層の製造方法。
［４］前記樹脂は、芳香族ポリアミドを含む、［３］に記載の多孔質層の製造方法。
［５］基材と、前記基材の少なくとも１つの面に積層された、粒子を含む多孔質層と、を備える積層体であって、
前記積層体の膜厚の標準偏差が、０．５μｍ以下である、積層体。
［６］前記積層体の膜厚が、１５．０μｍ以下である、請求項５に記載の積層体。
［７］前記多孔質層は、樹脂を含む、［５］または［６］に記載の積層体。
［８］前記樹脂は、芳香族ポリアミドを含む、［７］に記載の積層体。
［９］［５］〜［８］の何れか１つに記載の積層体を含む、非水電解液二次電池用セパレータ。
［１０］［９］に記載の非水電解液二次電池用セパレータを含む、非水電解液二次電池。
The present invention is an invention based on the above discovery and includes the inventions shown in the following [1] to [7].
[1] A step of applying a coating liquid containing a non-conductive solvent and particles to the surface of the base material by passing it between a coating device and the base material,
From the coating liquid applied to the surface of the substrate, a step of removing the non-conductive solvent,
The electric field strength between the coating device and the base material is 1.0×10 5 V/m or more when the coating liquid passes between the coating device and the base material. , A method for producing a porous layer.
[2] After the step of applying the coating liquid on the surface of the base material and before the step of removing the non-conductive solvent,
The method for producing a porous layer according to [1], wherein the coating liquid is leveled.
[3] The method for producing a porous layer according to [1] or [2], wherein the coating liquid contains a resin.
[4] The method for producing a porous layer according to [3], wherein the resin contains an aromatic polyamide.
[5] A laminate comprising a substrate and a porous layer containing particles, which is laminated on at least one surface of the substrate,
A laminate having a standard deviation of the film thickness of the laminate of 0.5 μm or less.
[6] The layered product according to claim 5, wherein the film thickness of the layered product is 15.0 µm or less.
[7] The laminated body according to [5] or [6], wherein the porous layer contains a resin.
[8] The laminate according to [7], wherein the resin contains an aromatic polyamide.
[9] A separator for a non-aqueous electrolyte secondary battery, including the laminate according to any one of [5] to [8].
[10] A non-aqueous electrolyte secondary battery including the separator for non-aqueous electrolyte secondary battery according to [9].
本発明の一実施形態に係る多孔質層の製造方法によれば、膜厚精度に優れる多孔質層を製造できる。 According to the method for producing a porous layer according to one embodiment of the present invention, it is possible to produce a porous layer having excellent film thickness accuracy.
本発明の一実施形態に係る積層体は、当該積層体を非水電解液二次電池用セパレータまたはその部材として含む非水電解液二次電池の電池性能を向上させることができる。 The laminate according to the embodiment of the present invention can improve the battery performance of a non-aqueous electrolyte secondary battery including the laminate as a separator for a non-aqueous electrolyte secondary battery or a member thereof.
本発明の一実施形態に関して以下に説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、特許請求の範囲に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態に関しても本発明の技術的範囲に含まれる。なお、本明細書において特記しない限り、数値範囲を表す「Ａ〜Ｂ」は、「Ａ以上、Ｂ以下」を意味する。 One embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to each configuration described below, various modifications are possible within the scope shown in the claims, and the technical means disclosed in different embodiments are appropriately combined. The obtained embodiments are also included in the technical scope of the present invention. Unless otherwise specified in this specification, “A to B” representing a numerical range means “A or more and B or less”.
［実施形態１：多孔質層の製造方法］
本発明の実施形態１に係る多孔質層の製造方法は、非導電性の溶媒と、粒子とを含む塗工液を、塗工装置と基材との間を通過させることによって、基材の面に塗工する工程と、基材の面に塗工した前記塗工液から、前記非導電性の溶媒を除去する工程と、を含み、前記塗工液が、塗工装置と基材との間を通過する時の、塗工装置と基材との間の電場強度が１．０×１０５Ｖ／ｍ以上である。
[Embodiment 1: Method for producing porous layer]
The method for producing a porous layer according to the first embodiment of the present invention, a coating liquid containing a non-conductive solvent and particles is passed between the coating device and the substrate, A step of coating the surface, and a step of removing the non-conductive solvent from the coating liquid applied to the surface of the substrate, the coating liquid, a coating device and a substrate The electric field strength between the coating device and the base material when passing through the space is 1.0×10 5 V/m or more.
なお、本発明の一実施形態において、非導電性の溶媒は、後述する粒子を分散する分散溶媒であり得、後述する樹脂を溶解する溶媒であり得る。また、本発明の一実施形態において、塗工液は、後述する粒子が分散した分散液であり得、後述する樹脂が溶解した溶液であり得る。よって、本明細書において、前記塗工液は、「分散液」または「溶液」とも呼称され、前記非導電性の溶媒は、「分散溶媒」または「溶媒」とも呼称される。 In addition, in one embodiment of the present invention, the non-conductive solvent may be a dispersion solvent in which particles described below are dispersed, or a solvent in which a resin described below is dissolved. Further, in one embodiment of the present invention, the coating liquid may be a dispersion liquid in which particles described below are dispersed, or a solution in which a resin described below is dissolved. Therefore, in the present specification, the coating liquid is also referred to as “dispersion liquid” or “solution”, and the non-conductive solvent is also referred to as “dispersion solvent” or “solvent”.
＜エレクトロレオロジー効果（ＥＲ効果）＞
ＥＲ効果とは、絶縁性溶媒に粒子を分散させた系である分散液に電場を印加することによって、当該分散液の粘度が増加し、その後、印加した電場を取り去ることによって、元の流動性を回復する効果である。つまり、当該分散液は、電場の印加により粘度が増大し、電場を取り去ることによって粘度が減少する（参考文献１：W.M. Winslow: J. Appl. Phys. 20, 1137 (1949)、参考文献２：表面化学, 22, 2-8(2001)）。
<Electrorheological effect (ER effect)>
The ER effect means that by applying an electric field to a dispersion liquid, which is a system in which particles are dispersed in an insulating solvent, the viscosity of the dispersion liquid is increased, and then the applied electric field is removed so that the original fluidity is improved. Is the effect of recovering. That is, the viscosity of the dispersion liquid increases when an electric field is applied, and the viscosity decreases when the electric field is removed (reference document 1: WM Winslow: J. Appl. Phys. 20, 1137 (1949), reference document 2: Surface Chemistry, 22, 2-8 (2001)).
ＥＲ効果における、前記分散液にせん断を与えた時の降伏応力は、以下の式（１）にて表される。 The yield stress when shearing the dispersion liquid in the ER effect is represented by the following formula (1).
式（１）において、σは、前記分散液にせん断を与えた時の降伏応力を表す。φは、前記分散液中の粒子の体積分率を表す。ε０は、真空の誘電率を表す。εｐは、前記分散液中の溶媒の誘電率を表す。εｃは、前記粒子の誘電率を表す。Ｅは、前記分散液に印加される電場強度を表す。 In Expression (1), σ represents the yield stress when the dispersion liquid is sheared. φ represents the volume fraction of particles in the dispersion. ε 0 represents the dielectric constant of vacuum. ε p represents the dielectric constant of the solvent in the dispersion liquid. ε c represents the dielectric constant of the particles. E represents the electric field strength applied to the dispersion liquid.
ここで、前記降伏応力が大きいことは、ＥＲ効果によって、前記分散液の粘度がより大きく向上することを示す。すなわち、前記分散液に電場を印加する瞬間の当該分散液の粘度は、印加する電場強度の二乗に比例し、溶媒と分散溶媒の誘電率の差が大きいほど高くなることが示唆される。 Here, the large yield stress indicates that the viscosity of the dispersion liquid is further improved by the ER effect. That is, it is suggested that the viscosity of the dispersion liquid at the moment of applying an electric field to the dispersion liquid is proportional to the square of the applied electric field strength, and increases as the difference in dielectric constant between the solvent and the dispersion solvent increases.
よって、本発明の一実施形態に係る多孔質層の製造方法では、後述する塗工液を基材上に塗工する工程において、塗工の瞬間に、塗工装置と基材との間に電場を印加することによって、当該塗工液の粘度を高める。これにより、当該基材のたるみやバタつきなどに起因するわずかなしわなどの影響を少なくすることができる。 Therefore, in the method for producing the porous layer according to the embodiment of the present invention, in the step of applying the coating liquid described below on the base material, at the moment of coating, between the coating device and the base material. By applying an electric field, the viscosity of the coating liquid is increased. As a result, it is possible to reduce the influence of slight wrinkles or the like due to slack or flapping of the base material.
従来の塗工方法においては、基材３のわずかなしわなどの影響によって、塗工装置１と基材３との間の隙間（クリアランス）を一定に保つことができないため、塗工された塗工液２からなる塗工層の膜厚精度が低下し、その結果、当該塗工層から溶媒を除去して得られる多孔質の膜厚精度が低下する。特に基材が薄い場合、基材のたるみやバタつきなどに起因するわずかなしわが発生しやすいため、膜厚精度が低下しやすい。一方、本発明の一実施形態における塗工方法においては、塗工の瞬間にＥＲ効果によって塗工液の粘度が高くなるため、塗工が安定し、前記基材のわずかなしわなどの影響を軽減することができる。その結果、前述の塗工層２の膜厚精度が向上し、製造される多孔質層の膜厚精度を向上させることができる。
In the conventional coating method, the gap between the coating device 1 and the
また、本発明の一実施形態において、前記塗工液を前記基材の面に塗工する工程の後から、前記非導電性の溶媒を除去する工程の前にて、前記塗工液が、レベリングされていることが好ましい。ここで、前記塗工液を前記基材の面に塗工する工程の後に、前記塗工液に印加された電場は解消される。よって、当該塗工液の粘度は、電場を印加する前と同程度まで低下する。その結果、前記塗工液はレベリングされると考えられる。このレベリングによって、塗工された塗工液からなる塗工層の膜厚がより均一となり、得られる多孔質層の膜厚精度をさらに向上させることができる。 Further, in one embodiment of the present invention, after the step of applying the coating solution to the surface of the base material and before the step of removing the non-conductive solvent, the coating solution is It is preferably leveled. Here, the electric field applied to the coating liquid is canceled after the step of coating the surface of the base material with the coating liquid. Therefore, the viscosity of the coating liquid is reduced to the same level as before the application of the electric field. As a result, it is considered that the coating liquid is leveled. By this leveling, the film thickness of the coating layer made of the applied coating liquid becomes more uniform, and the film thickness accuracy of the obtained porous layer can be further improved.
＜塗工工程＞
非導電性の溶媒と、粒子とを含む塗工液を、塗工装置と基材との間を通過させることによって、基材の面に塗工する工程を塗工工程とも称する。前記塗工液を多孔質基材に塗工する方法としては、特に限定されないが、例えば、ナイフ、ブレード、バー、グラビア、ダイ等の公知の塗工方法を用いることができる。電場が均一にかかることから、バー、グラビア、ダイによる塗工が好ましく、その中でも、設備が簡便であることからバーによる塗工が特に好ましい。
<Coating process>
The step of applying a coating liquid containing a non-conductive solvent and particles to the surface of the base material by passing it between the coating device and the base material is also referred to as a coating step. The method of applying the coating liquid onto the porous substrate is not particularly limited, and for example, a known coating method such as knife, blade, bar, gravure, die, etc. can be used. Coating with a bar, gravure, or die is preferable because the electric field is evenly applied, and among these, coating with a bar is particularly preferable because the equipment is simple.
塗工装置は、前記塗工方法において、塗工液を介して基材と接触して、当該基材の面に当該塗工液を塗工する部材である。上記塗工装置は、例えば、ナイフ、ブレード、塗工バー、ダイ、グラビアロールなどの前記塗工方法にて使用する塗工装置を挙げることができる。 In the coating method, the coating device is a member that comes into contact with the base material via the coating liquid to coat the surface of the base material with the coating liquid. Examples of the coating device include a coating device used in the coating method such as a knife, a blade, a coating bar, a die, and a gravure roll.
本明細書において、「塗工液を、塗工装置と基材との間を通過させるとき」とは、前記基材の面に前記塗工液を塗工する工程において、塗工装置と基材との両方が塗工液に接触することによって、塗工液を基材上に実際に塗工する瞬間を意味する。よって、本発明の一実施形態において、塗工する瞬間、図１における塗工液２のうち、塗工装置１と重なっている部分のみに電場が印加される。 In the present specification, “when the coating liquid is passed between the coating device and the base material” means that in the step of applying the coating liquid on the surface of the base material, the coating device and the base material are applied. This means the moment when the coating liquid is actually applied onto the substrate by contacting both the material and the coating liquid. Therefore, in one embodiment of the present invention, the electric field is applied only to the portion of the coating liquid 2 in FIG. 1 overlapping the coating device 1 at the moment of coating.
塗工装置と基材との間の電場強度は、以下の式（２）にて表される。 The electric field strength between the coating device and the base material is represented by the following formula (2).
式（２）中、Ｅ（単位：Ｖ／ｍ）は、本発明の一実施形態における前記塗工液が、塗工装置と基材との間を通過する時の、塗工装置と基材との間の電場強度を表す。Ｅ１（単位：Ｖ）は、塗工装置の電位を表す。Ｅ２（単位：Ｖ）は、基材表面の電位を表す。ｄ（単位：ｍ）は、塗工時における塗工機と基材との距離を表す。この距離をクリアランスとも称する。 In the formula (2), E (unit: V/m) is a coating device and a base material when the coating liquid in one embodiment of the present invention passes between the coating device and the base material. Represents the electric field strength between and. E 1 (unit: V) represents the potential of the coating device. E 2 (unit: V) represents the electric potential on the surface of the base material. d (unit: m) represents the distance between the coating machine and the substrate during coating. This distance is also called clearance.
塗工装置と基材との間の電場強度は、塗工液の粘度が、ＥＲ効果により好適に向上するとの観点から、１．０×１０５Ｖ／ｍ以上、すなわち０．１ＭＶ／ｍ以上であり、０．３ＭＶ／ｍ以上であることが好ましく、０．５ＭＶ／ｍ以上であることがより好ましい。また、塗工装置と基材との間の電場強度が過剰に高くなることに起因して、絶縁破壊が発生し、基材の内部がトリーイングによって破壊されることを防止する観点から、本発明の一実施形態における、塗工装置と基材との間の電場強度は、１００ＭＶ／ｍ以下であることが好ましく、１０ＭＶ／ｍ以下であることがより好ましい。 The electric field strength between the coating device and the base material is 1.0×10 5 V/m or more, that is, 0.1 MV/m or more, from the viewpoint that the viscosity of the coating liquid is suitably improved by the ER effect. And is preferably 0.3 MV/m or more, more preferably 0.5 MV/m or more. Further, from the viewpoint of preventing dielectric breakdown from occurring due to excessively high electric field strength between the coating apparatus and the base material and the interior of the base material from being destroyed by treeing, In one embodiment of the invention, the electric field strength between the coating device and the base material is preferably 100 MV/m or less, and more preferably 10 MV/m or less.
塗工装置と基材との間の電場強度を制御する方法は、特に限定されないが、例えば、前記基材および前記塗工装置の一方または双方を帯電させる方法を採用することができる。前記基材を帯電させる方法としては、例えば、塗工前に帯電ガンによって電位を変える方法、および塗工直前に基材と搬送ローラ等とを接触させ、次いで剥離することによって当該基材を剥離帯電させる方法などが挙げられる。また、塗工装置を帯電させる方法として、例えば、塗工装置に帯電ガンを当てる方法などが挙げられる。塗工装置は一般的に金属製であってアースを取っていることが多く、帯電させることが困難であることから、基材を帯電させる方法が簡便であり、より好ましい。 The method for controlling the electric field strength between the coating apparatus and the base material is not particularly limited, but for example, a method of charging one or both of the base material and the coating apparatus can be adopted. As a method of charging the base material, for example, a method of changing the electric potential with a charging gun before coating, or a method of contacting the base material with a transport roller immediately before coating and then peeling the base material is peeled. Examples thereof include a method of charging. Further, as a method of charging the coating device, for example, a method of applying a charging gun to the coating device can be mentioned. Since the coating device is generally made of metal and often grounded and difficult to be charged, the method of charging the base material is simple and more preferable.
＜塗工液＞
本発明の一実施形態における塗工液は、非導電性の溶媒と後述の本発明の一実施形態に係る多孔質層を構成する粒子とを含み、当該粒子が、非導電性の溶媒中に分散した溶液である。
<Coating liquid>
The coating liquid in one embodiment of the present invention contains a non-conductive solvent and particles constituting a porous layer according to one embodiment of the present invention described below, and the particles are in a non-conductive solvent. It is a dispersed solution.
本発明の一実施形態における粒子は、後述の非導電性の溶媒中に分散する粒子であれば、特に限定されない。前記粒子としては、例えば、アルミナ、ベーマイト、シリカ、チタニア、ジルコニア、マグネシア、水酸化アルミニウム、チタン酸バリウム、炭酸カルシウムなどの無機酸化物からなるフィラー、マイカ、ゼオライト、カオリン、タルクなどの鉱物からなるフィラー、架橋ポリスチレン、フェノール系樹脂、メラミン系樹脂、レゾルシン‐ホルマリン樹脂（ＲＦ樹脂）、架橋ポリメチルメタクリレート、アクリルコアシェル、ポリオレフィンビーズなどの樹脂からなるフィラーが挙げられる。前記粒子は、単独で用いてもよいし、２種類以上を組み合わせて使用することもできる。また、前記粒子は、電気化学的に安定で電気絶縁性を有していることが好ましい。さらに、前記粒子は、溶媒および電解液に対して溶出しないことが好ましい。 The particles in one embodiment of the present invention are not particularly limited as long as they are particles dispersed in a non-conductive solvent described below. As the particles, for example, alumina, boehmite, silica, titania, zirconia, magnesia, aluminum hydroxide, barium titanate, filler made of inorganic oxides such as calcium carbonate, mica, zeolite, kaolin, consisting of minerals such as talc. Examples of fillers include fillers, crosslinked polystyrene, phenolic resins, melamine resins, resorcin-formalin resins (RF resins), crosslinked polymethylmethacrylate, acrylic core shells, and polyolefin beads. The particles may be used alone or in combination of two or more. Further, it is preferable that the particles are electrochemically stable and have electric insulation. Furthermore, it is preferable that the particles do not elute with respect to the solvent and the electrolytic solution.
比誘電率が大きい粒子を含む塗工液は、電場を印加した際にＥＲ効果によってその粘度がより大きく向上する。このことから、前記粒子は、比較的誘電率の高い無機酸化物である、アルミナ、チタン酸バリウムなどが好ましく、その中でも材料価格の観点から、アルミナが最も好ましい。 The viscosity of the coating liquid containing particles having a large relative dielectric constant is greatly improved by the ER effect when an electric field is applied. From this, the particles are preferably inorganic oxides having a relatively high dielectric constant, such as alumina and barium titanate. Among them, alumina is most preferable from the viewpoint of material cost.
前記粒子の体積平均粒子径は、良好な接着性と滑り性の確保、および積層体の成形性の観点から、０．０１μｍ〜１１μｍの範囲であることが好ましい。その下限値としては０．０５μｍ以上がより好ましく、０．１μｍ以上がさらに好ましい。その上限値としては１０μｍ以下がより好ましく、５μｍ以下がさらに好ましく、１μｍ以下が特に好ましい。 The volume average particle diameter of the particles is preferably in the range of 0.01 μm to 11 μm from the viewpoint of ensuring good adhesiveness and slipperiness, and moldability of the laminate. The lower limit value is more preferably 0.05 μm or more, further preferably 0.1 μm or more. The upper limit thereof is more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 1 μm or less.
前記粒子の形状は、任意であり、特に限定されない。前記粒子の形状は、例えば、球形状；楕円形状；板状；棒状；鱗片状；不定形状；繊維状；ピーナッツ状および／またはテトラポット状のように単一粒子が熱融着した形状の何れでもよい。電池の短絡防止の観点から、前記粒子は、板状の粒子、および／または、凝集していない一次粒子であることが好ましい。イオン透過の観点からは、前記粒子は、多孔質中の粒子が最密充填され難い、不定形状；繊維状；ピーナッツ状および／またはテトラポット状のように単一粒子が熱融着した形状であることが好ましい。特に、前記粒子は、ピーナッツ状および／またはテトラポット状のように単一粒子が熱融着した形状であることが、さらに好ましい。 The shape of the particles is arbitrary and is not particularly limited. The shape of the particles is, for example, a spherical shape; an elliptical shape; a plate shape; a rod shape; a scale shape; an indefinite shape; a fibrous shape; a peanut shape and/or a tetrapot shape; But it's okay. From the viewpoint of preventing a short circuit in the battery, the particles are preferably plate-like particles and/or primary particles that are not aggregated. From the viewpoint of ion permeation, the particles have a shape in which single particles are heat-sealed such as an indeterminate shape; a fibrous shape; a peanut shape and/or a tetrapot shape, in which it is difficult for the particles in the porous body to be densely packed. It is preferable to have. In particular, it is more preferable that the particles have a shape in which single particles are heat-sealed, such as a peanut shape and/or a tetrapot shape.
前記粒子の濃度は、前記塗工液全体の体積に対して、５０体積％以下が好ましく、３０体積％以下がより好ましい。また、１体積％以上が好ましく、３体積％以上がより好ましい。粒子濃度が５０体積％以下であると、塗工液の送液性などの生産上の観点から好ましい側面がある。また、粒子濃度が１体積％以上であると経済性の観点から好ましい側面がある。 The concentration of the particles is preferably 50% by volume or less, more preferably 30% by volume or less, based on the volume of the entire coating liquid. Moreover, 1 volume% or more is preferable and 3 volume% or more is more preferable. When the particle concentration is 50% by volume or less, there is a preferable aspect from the viewpoint of production such as liquid feeding property of the coating liquid. Further, when the particle concentration is 1% by volume or more, there is a preferable aspect from the viewpoint of economy.
本発明の一実施形態における非導電性の溶媒は、ＥＲ効果を発現するために、絶縁性であれば特に限定されない。前記非導電性の溶媒の導電率は、通常、１μＳ／ｃｍ以下である。前記非導電性の溶媒は、例えば、メタノール、エタノール、プロパノール、イソプロピルアルコールなどのアルコール類、アセトン、メチルエチルケトン、ジエチルケトンなどのケトン類、エーテル類、Ｎ−メチルピロリドンなどのアミン類、ヘキサン、オクタン、ベンゼンなどの炭化水素類、シリコーンオイルなどが挙げられる。前記非導電性の溶媒は、１種類の溶媒であってもよく、２種類以上の溶媒の混合溶媒であってもよい。 The non-conductive solvent in one embodiment of the present invention is not particularly limited as long as it is insulative in order to exhibit the ER effect. The conductivity of the non-conductive solvent is usually 1 μS/cm or less. The non-conductive solvent, for example, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, ethers, amines such as N-methylpyrrolidone, hexane, octane, Hydrocarbons such as benzene, silicone oil and the like can be mentioned. The non-conductive solvent may be one kind of solvent or a mixed solvent of two or more kinds of solvents.
前記非導電性の溶媒は、塗工後の工程において、当該非導電性の溶媒を蒸発または洗浄によって除去し易いとの観点から、アルコール類、ケトン類、アミン類が好ましい。その中でも価格の観点から、エタノール、イソプロピルアルコール、アセトン、メチルエチルケトン、Ｎ-メチルピロリドンなどがより好ましい。 The non-conductive solvent is preferably alcohols, ketones, and amines from the viewpoint that the non-conductive solvent can be easily removed by evaporation or washing in the step after coating. Among them, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, N-methylpyrrolidone and the like are more preferable from the viewpoint of price.
前記塗工液は、樹脂を含み得る。前記樹脂は、前記粒子同士および前記多孔質層と前記基材とを良好に結着することができ、さらに電気化学的に安定であり、かつ、電解液に対して溶出しないものであれば、特に限定されない。前記樹脂の具体例としては、例えば、ポリオレフィン；（メタ）アクリレート系樹脂；含フッ素樹脂；ポリアミド系樹脂；ポリイミド系樹脂；ポリエステル系樹脂；ゴム類；融点またはガラス転移温度が１８０℃以上の樹脂；水溶性ポリマー；ポリカーボネート、ポリアセタール、ポリエーテルエーテルケトン等が挙げられる。 The coating liquid may include a resin. The resin is capable of satisfactorily binding the particles to each other and the porous layer and the base material, and is electrochemically stable, and as long as it does not elute into the electrolytic solution, It is not particularly limited. Specific examples of the resin include polyolefin; (meth)acrylate resin; fluorine-containing resin; polyamide resin; polyimide resin; polyester resin; rubbers; resins having a melting point or glass transition temperature of 180° C. or higher; Water-soluble polymer; examples thereof include polycarbonate, polyacetal, and polyether ether ketone.
前述の樹脂のうち、ポリオレフィン、ポリエステル系樹脂、（メタ）アクリレート系樹脂、含フッ素樹脂、ポリアミド系樹脂および水溶性ポリマーが好ましい。 Of the above-mentioned resins, polyolefins, polyester resins, (meth)acrylate resins, fluorine-containing resins, polyamide resins and water-soluble polymers are preferable.
ポリオレフィンとしては、ポリエチレン、ポリプロピレン、ポリブテン、およびエチレン−プロピレン共重合体等が好ましい。 As the polyolefin, polyethylene, polypropylene, polybutene, ethylene-propylene copolymer and the like are preferable.
ポリアミド系樹脂としては、芳香族ポリアミドおよび全芳香族ポリアミドなどのアラミド樹脂が好ましい。 As the polyamide resin, aramid resins such as aromatic polyamide and wholly aromatic polyamide are preferable.
また、前記アラミド樹脂としては、具体的には、例えば、ポリ（パラフェニレンテレフタルアミド）、ポリ（メタフェニレンイソフタルアミド）、ポリ（パラベンズアミド）、ポリ（メタベンズアミド）、ポリ（４，４’−ベンズアニリドテレフタルアミド）、ポリ（パラフェニレン−４，４’−ビフェニレンジカルボン酸アミド）、ポリ（メタフェニレン−４，４’−ビフェニレンジカルボン酸アミド）、ポリ（パラフェニレン−２，６−ナフタレンジカルボン酸アミド）、ポリ（メタフェニレン−２，６−ナフタレンジカルボン酸アミド）、ポリ（２−クロロパラフェニレンテレフタルアミド）、パラフェニレンテレフタルアミド／２，６−ジクロロパラフェニレンテレフタルアミド共重合体、メタフェニレンテレフタルアミド／２，６−ジクロロパラフェニレンテレフタルアミド共重合体等が挙げられる。このうち、ポリ（パラフェニレンテレフタルアミド）がより好ましい。 Specific examples of the aramid resin include poly(paraphenylene terephthalamide), poly(metaphenylene isophthalamide), poly(parabenzamide), poly(metabenzamide), poly(4,4′-). Benzanilide terephthalamide), poly(paraphenylene-4,4'-biphenylene dicarboxylic acid amide), poly(metaphenylene-4,4'-biphenylene dicarboxylic acid amide), poly(paraphenylene-2,6-naphthalene dicarboxylic acid) Amide), poly(metaphenylene-2,6-naphthalenedicarboxylic acid amide), poly(2-chloroparaphenylene terephthalamide), paraphenylene terephthalamide/2,6-dichloroparaphenylene terephthalamide copolymer, metaphenylene terephthalate Examples thereof include amide/2,6-dichloroparaphenylene terephthalamide copolymer. Of these, poly(paraphenylene terephthalamide) is more preferable.
ポリエステル系樹脂としては、ポリアリレートなどの芳香族ポリエステルおよび液晶ポリエステルが好ましい。 As the polyester resin, aromatic polyesters such as polyarylate and liquid crystal polyesters are preferable.
ゴム類としては、スチレン−ブタジエン共重合体およびその水素化物、メタクリル酸エステル共重合体、アクリロニトリル−アクリル酸エステル共重合体、スチレン−アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリ酢酸ビニル等を挙げることができる。 As the rubber, styrene-butadiene copolymer and its hydride, methacrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl acetate, etc. Can be mentioned.
融点又はガラス転移温度が１８０℃以上の樹脂としては、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリアミドイミド、ポリエーテルアミド等を挙げることができる。 Examples of the resin having a melting point or glass transition temperature of 180° C. or higher include polyphenylene ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyamideimide, and polyetheramide.
水溶性ポリマーとしては、ポリビニルアルコール、ポリエチレングリコール、セルロースエーテル、アルギン酸ナトリウム、ポリアクリル酸、ポリアクリルアミド、ポリメタクリル酸等を挙げることができる。 Examples of the water-soluble polymer include polyvinyl alcohol, polyethylene glycol, cellulose ether, sodium alginate, polyacrylic acid, polyacrylamide and polymethacrylic acid.
含フッ素樹脂としては、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−トリフルオロエチレン共重合体、フッ化ビニリデン−トリクロロエチレン共重合体、フッ化ビニリデン−フッ化ビニル共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体、およびエチレン−テトラフルオロエチレン共重合体等、並びに、前記含フッ素樹脂の中でもガラス転移温度が２３℃以下である含フッ素ゴムを挙げることができる。 Examples of the fluorine-containing resin include polyvinylidene fluoride (PVDF), polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. Coal, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-trichloroethylene copolymer, vinylidene fluoride-vinyl fluoride copolymer, vinylidene fluoride-hexafluoro Examples thereof include a propylene-tetrafluoroethylene copolymer, an ethylene-tetrafluoroethylene copolymer and the like, and a fluorine-containing rubber having a glass transition temperature of 23° C. or lower among the fluorine-containing resins.
前記樹脂は、１種類の樹脂でもよく、２種類以上の樹脂を併用してもよい。 The resin may be one type of resin or two or more types of resin in combination.
前記樹脂は、ポリアミド、ポリエステル、アクリル、ポリフッ化ビニリデン（ＰＶＤＦ）、エチレンアクリレート共重合体、スチレンブタジエンゴム（ＳＢ）およびポリビニルアルコール（ＰＶＡ）からなる一群から少なくとも１種選択される樹脂が好ましく、芳香族ポリアミドを含む樹脂であることがより好ましく、芳香族ポリアミドを主成分として含む樹脂であることがさらに好ましい。ここで、「芳香族ポリアミドを主成分として含む」とは、前記樹脂全体における芳香族ポリアミドの含有量が、５０体積％以上、好ましくは９０体積％以上、より好ましくは９５体積％以上であることを意味する。 The resin is preferably a resin selected from at least one selected from the group consisting of polyamide, polyester, acrylic, polyvinylidene fluoride (PVDF), ethylene acrylate copolymer, styrene butadiene rubber (SB) and polyvinyl alcohol (PVA). A resin containing a group polyamide is more preferable, and a resin containing an aromatic polyamide as a main component is more preferable. Here, "containing aromatic polyamide as a main component" means that the content of the aromatic polyamide in the whole resin is 50% by volume or more, preferably 90% by volume or more, more preferably 95% by volume or more. Means
塗工液の調製方法は、得られる多孔質層の膜厚を制御可能な程度に前記粒子を前記非導電性の溶媒中に均一に分散させることができれば、特に限定されない。塗工液の調製方法として一般に、前記非導電性の溶媒中に、前記粒子を分散させ、任意で前記樹脂を溶解させる方法を挙げることができる。前記粒子を前記非導電性の溶媒中に分散させる方法としては、例えば、高圧分散、対向衝突型分散、ボールミル、ビーズミル、ペイントシェイカー、高速インペラ分散、超音波分散、ホモジナイザー、および撹拌羽による機械撹拌法などが挙げられる。 The method for preparing the coating solution is not particularly limited as long as the particles can be uniformly dispersed in the non-conductive solvent to the extent that the thickness of the resulting porous layer can be controlled. As a method for preparing the coating liquid, generally, a method of dispersing the particles in the non-conductive solvent and optionally dissolving the resin can be mentioned. As a method of dispersing the particles in the non-conductive solvent, for example, high pressure dispersion, opposed collision type dispersion, ball mill, bead mill, paint shaker, high speed impeller dispersion, ultrasonic dispersion, homogenizer, and mechanical stirring by stirring blades. Law, etc.
前記塗工液の塗工前の粘度は、前記レベリングを好適に発生させるとの観点から、１００Ｐａ・Ｓｅｃ以下であることが好ましく、１０Ｐａ・Ｓｅｃ以下であることがより好ましい。また、前記ＥＲ効果によって、塗工時の粘度を好適な範囲に向上させるとの観点から、０．００１Ｐａ・Ｓｅｃ以上であることが好ましく、０．０１Ｐａ・Ｓｅｃ以上であることがより好ましい。 The viscosity of the coating liquid before coating is preferably 100 Pa·Sec or less, and more preferably 10 Pa·Sec or less, from the viewpoint of suitably generating the leveling. Further, from the viewpoint of improving the viscosity during coating to a suitable range by the ER effect, it is preferably 0.001 Pa·Sec or more, and more preferably 0.01 Pa·Sec or more.
＜基材＞
本発明の一実施形態における基材は、例えば、後述する多孔質基材および電極板を挙げることができ、多孔質基材であることが好ましい。前記多孔質基材としては、樹脂製の多孔質膜、不織布、織物、紙様シートなどが挙げられる。また、前記電極板としては、正極、または負極を挙げることができる。
<Substrate>
Examples of the base material in the embodiment of the present invention include a porous base material and an electrode plate described later, and the porous base material is preferable. Examples of the porous substrate include a resin-made porous film, a non-woven fabric, a woven fabric, and a paper-like sheet. The electrode plate may be a positive electrode or a negative electrode.
前記基材の膜厚は、１２μｍ以下であることが好ましく、１１μｍ以下であることがより好ましく、１０μｍ以下であることがさらに好ましい。また、前記基材の膜厚は、４μｍ以上であることが好ましく、５μｍ以上であることがより好ましい。 The film thickness of the base material is preferably 12 μm or less, more preferably 11 μm or less, and further preferably 10 μm or less. Further, the film thickness of the base material is preferably 4 μm or more, and more preferably 5 μm or more.
＜多孔質基材＞
多孔質基材は、主成分として、ポリオレフィン、ポリアミド、ポリエステル、ポリフェニレンスルフィド、またはポリスルフォンなどの樹脂成分を含むことが好ましい。ここで、「主成分として含む」とは、前記多孔質基材全体に対する含有量が５０体積％以上、好ましくは９０体積％以上、より好ましくは９５体積％以上であることを表す。
<Porous substrate>
The porous substrate preferably contains a resin component such as polyolefin, polyamide, polyester, polyphenylene sulfide, or polysulfone as a main component. Here, “containing as a main component” means that the content with respect to the entire porous substrate is 50% by volume or more, preferably 90% by volume or more, and more preferably 95% by volume or more.
前記多孔質基材は、その内部に連結した細孔を多数有しており、一方の面から他方の面に気体および液体を通過させることが可能となっている。前記多孔質基材は、単独で非水電解液二次電池用セパレータとなり得る。また、後述の本発明の一実施形態に係る積層体の基材となり得る。 The porous substrate has a large number of pores connected to the inside thereof, and is capable of passing gas and liquid from one surface to the other surface. The porous substrate can be used alone as a separator for a non-aqueous electrolyte secondary battery. Further, it can be a base material for a laminate according to one embodiment of the present invention described later.
前記多孔質基材は、ポリオレフィンを主成分とする樹脂製の多孔質膜であり得る。以下、当該多孔質膜を「ポリオレフィン多孔質フィルム」と称する。 The porous substrate may be a resin-made porous film containing polyolefin as a main component. Hereinafter, the porous membrane is referred to as "polyolefin porous film".
前記ポリオレフィンには、重量平均分子量が５×１０５〜１５×１０６の高分子量成分が含まれていることがより好ましい。特に、ポリオレフィンに重量平均分子量が１００万以上の高分子量成分が含まれていると、非水電解液二次電池用セパレータの強度が向上するのでより好ましい。 More preferably, the polyolefin contains a high molecular weight component having a weight average molecular weight of 5×10 5 to 15×10 6 . In particular, it is more preferable that the polyolefin contains a high molecular weight component having a weight average molecular weight of 1,000,000 or more because the strength of the separator for a non-aqueous electrolyte secondary battery is improved.
熱可塑性樹脂である前記ポリオレフィンとしては、具体的には、例えば、エチレン、プロピレン、１−ブテン、４−メチル−１−ペンテンおよび１−ヘキセン等の単量体を重合してなる、単独重合体または共重合体が挙げられる。前記単独重合体としては、例えばポリエチレン、ポリプロピレン、ポリブテンを挙げることができる。また、前記共重合体としては、例えばエチレン−プロピレン共重合体を挙げることができる。 Specific examples of the polyolefin that is a thermoplastic resin include homopolymers obtained by polymerizing monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. Alternatively, a copolymer may be used. Examples of the homopolymer include polyethylene, polypropylene and polybutene. Moreover, as said copolymer, an ethylene-propylene copolymer can be mentioned, for example.
このうち、過大電流が流れることをより低温で阻止することができるため、ポリエチレンがより好ましい。なお、この過大電流が流れることを阻止することをシャットダウンともいう。前記ポリエチレンとしては、低密度ポリエチレン、高密度ポリエチレン、線状ポリエチレン（エチレン−α−オレフィン共重合体）、重量平均分子量が１００万以上の超高分子量ポリエチレン等が挙げられる。このうち、重量平均分子量が１００万以上の超高分子量ポリエチレンがさらに好ましい。 Of these, polyethylene is more preferable because it can prevent an excessive current from flowing at a lower temperature. Note that blocking the flow of this excessive current is also referred to as shutdown. Examples of the polyethylene include low density polyethylene, high density polyethylene, linear polyethylene (ethylene-α-olefin copolymer), and ultrahigh molecular weight polyethylene having a weight average molecular weight of 1,000,000 or more. Among these, ultrahigh molecular weight polyethylene having a weight average molecular weight of 1,000,000 or more is more preferable.
前記多孔質基材の単位面積当たりの目付は、強度、膜厚、重量およびハンドリング性を考慮して適宜決定することができる。ただし、非水電解液二次電池の重量エネルギー密度および体積エネルギー密度を高くすることができるように、前記目付は、４〜２０ｇ／ｍ２であることが好ましく、４〜１２ｇ／ｍ２であることがより好ましく、５〜１０ｇ／ｍ２であることがさらに好ましい。 The basis weight per unit area of the porous substrate can be appropriately determined in consideration of strength, film thickness, weight and handleability. However, to be able to increase the weight energy density and volume energy density of the nonaqueous electrolyte secondary battery, wherein the basis weight is preferably 4~20g / m 2, is 4~12g / m 2 More preferably, it is more preferably 5 to 10 g/m 2 .
前記多孔質基材の透気度は、ガーレ値で３０〜５００ｓｅｃ／１００ｍＬであることが好ましく、５０〜３００ｓｅｃ／１００ｍＬであることがより好ましい。前記多孔質基材が前記透気度を有することにより、充分なイオン透過性を得ることができる。 The air permeability of the porous substrate is preferably a Gurley value of 30 to 500 sec/100 mL, more preferably 50 to 300 sec/100 mL. When the porous substrate has the air permeability, sufficient ion permeability can be obtained.
前記多孔質基材の空隙率は、電解液の保持量を高めると共に、過大電流が流れることをより低温で確実に阻止する機能を得ることができるように、２０〜８０体積％であることが好ましく、３０〜７５体積％であることがより好ましい。また、多孔質基材が有する細孔の孔径は、充分なイオン透過性を得ることができ、かつ、正極および負極への粒子の入り込みを防止することができるように、０．３μｍ以下であることが好ましく、０．１４μｍ以下であることがより好ましい。 The porosity of the porous substrate is 20 to 80% by volume so as to increase the holding amount of the electrolytic solution and to surely prevent an excessive current from flowing at a lower temperature. It is more preferably 30 to 75% by volume. The pore size of the pores of the porous substrate is 0.3 μm or less so that sufficient ion permeability can be obtained and particles can be prevented from entering the positive electrode and the negative electrode. The thickness is preferably 0.14 μm or less, more preferably 0.14 μm or less.
＜ポリオレフィン多孔質フィルムの製造方法＞
前記ポリオレフィン多孔質フィルムの製造方法は特に限定されるものではない。例えば、ポリオレフィン系樹脂と、無機充填剤および可塑剤等の孔形成剤と、任意で酸化防止剤等を混練した後に押し出すことで、シート状のポリオレフィン樹脂組成物を作製する。適当な溶媒にて当該孔形成剤を当該シート状のポリオレフィン樹脂組成物から除去した後、当該孔形成剤が除去されたポリオレフィン樹脂組成物を延伸することで、ポリオレフィン多孔質フィルムを製造することができる。
<Method for producing polyolefin porous film>
The method for producing the polyolefin porous film is not particularly limited. For example, a sheet-shaped polyolefin resin composition is produced by kneading a polyolefin resin, a pore-forming agent such as an inorganic filler and a plasticizer, and optionally an antioxidant and the like and then extruding the kneaded product. After removing the pore-forming agent from the sheet-shaped polyolefin resin composition with a suitable solvent, the polyolefin resin composition from which the pore-forming agent has been removed may be stretched to produce a polyolefin porous film. it can.
上記無機充填剤としては、特に限定されるものではなく、無機フィラー、具体的には炭酸カルシウム等が挙げられる。上記可塑剤としては、特に限定されるものではなく、流動パラフィン等の低分子量の炭化水素が挙げられる。 The inorganic filler is not particularly limited, and examples thereof include inorganic fillers, specifically calcium carbonate. The plasticizer is not particularly limited, and examples thereof include low molecular weight hydrocarbons such as liquid paraffin.
具体的には、以下に示すような工程を含む方法を挙げることができる。
（Ａ）超高分子量ポリエチレンと、重量平均分子量１万以下の低分子量ポリエチレンと炭酸カルシウムまたは可塑剤等の孔形成剤と、酸化防止剤とを混練してポリオレフィン樹脂組成物を得る工程、
（Ｂ）得られたポリオレフィン樹脂組成物を一対の圧延ローラで圧延し、速度比を変えた巻き取りローラで引っ張りながら段階的に冷却し、シートを成形する工程、
（Ｃ）得られたシートの中から適当な溶媒にて孔形成剤を除去する工程、
（Ｄ）孔形成剤が除去されたシートを適当な延伸倍率にて延伸する工程。
Specifically, a method including the steps shown below can be mentioned.
(A) a step of kneading an ultrahigh molecular weight polyethylene, a low molecular weight polyethylene having a weight average molecular weight of 10,000 or less, a pore forming agent such as calcium carbonate or a plasticizer, and an antioxidant to obtain a polyolefin resin composition,
(B) a step of rolling the obtained polyolefin resin composition with a pair of rolling rollers and gradually cooling it while pulling it with a winding roller having a different speed ratio to form a sheet,
(C) a step of removing the pore forming agent from the obtained sheet with a suitable solvent,
(D) A step of stretching the sheet from which the pore-forming agent has been removed at an appropriate stretching ratio.
ここで、前記（Ｃ）と（Ｄ）とは順が逆でもよい。つまり、（Ｂ）工程で得られたシートを適当な延伸倍率にて延伸した後に、延伸されたシートの中から適当な溶媒にて孔形成剤を除去してもよい。 Here, the order of (C) and (D) may be reversed. That is, after the sheet obtained in the step (B) is stretched at an appropriate stretching ratio, the pore-forming agent may be removed from the stretched sheet with an appropriate solvent.
＜正極＞
正極としては、一般に非水電解液二次電池の正極として使用されるものであれば、特に限定されない。例えば、正極として、正極活物質および結着剤を含む活物質層が正極集電体上に成形された構造を備える正極シートを使用することができる。なお、前記活物質層は、更に導電剤を含んでもよい。
<Positive electrode>
The positive electrode is not particularly limited as long as it is generally used as the positive electrode of a non-aqueous electrolyte secondary battery. For example, a positive electrode sheet having a structure in which an active material layer containing a positive electrode active material and a binder is molded on a positive electrode current collector can be used as the positive electrode. The active material layer may further contain a conductive agent.
前記正極活物質としては、例えば、リチウムイオンまたはナトリウムイオン等の金属イオンをドープ・脱ドープ可能な材料が挙げられる。当該材料としては、具体的には、例えば、Ｖ、Ｍｎ、Ｆｅ、ＣｏおよびＮｉ等の遷移金属を少なくとも１種類含んでいるリチウム複合酸化物が挙げられる。 Examples of the positive electrode active material include materials that can be doped or dedoped with metal ions such as lithium ions or sodium ions. Specific examples of the material include a lithium composite oxide containing at least one transition metal such as V, Mn, Fe, Co, and Ni.
前記導電剤としては、例えば、天然黒鉛、人造黒鉛、コークス類、カーボンブラック、熱分解炭素類、炭素繊維および有機高分子化合物焼成体等の炭素質材料等が挙げられる。前記導電剤は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of the conductive agent include natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and carbonaceous materials such as fired organic polymer compounds. The conductive agent may be used alone or in combination of two or more.
前記結着剤としては、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）等のフッ素系樹脂、アクリル樹脂、スチレンブタジエンゴムが挙げられる。なお、結着剤は、増粘剤としての機能も有している。 Examples of the binder include fluororesin such as polyvinylidene fluoride (PVDF), acrylic resin, and styrene-butadiene rubber. The binder also has a function as a thickener.
前記正極集電体としては、例えば、Ａｌ、Ｎｉおよびステンレス等の導電体が挙げられる。中でも、薄膜に加工し易く、安価であることから、Ａｌがより好ましい。 Examples of the positive electrode current collector include conductors such as Al, Ni and stainless steel. Of these, Al is more preferable because it is easily processed into a thin film and is inexpensive.
正極シートの製造方法としては、例えば、正極活物質、導電剤および結着剤を正極集電体上で加圧成型する方法；適当な有機溶剤を用いて正極活物質、導電剤および結着剤をペースト状にした後、当該ペーストを正極集電体に塗工し、乾燥した後に加圧して正極集電体に固着する方法；等が挙げられる。 Examples of the method for producing the positive electrode sheet include a method in which a positive electrode active material, a conductive agent and a binder are pressure-molded on a positive electrode current collector; a positive electrode active material, a conductive agent and a binder using an appropriate organic solvent. Is applied to a positive electrode current collector, dried, and then pressed to fix it to the positive electrode current collector; and the like.
＜負極＞
負極としては、一般に非水電解液二次電池の負極として使用されるものであれば、特に限定されない。例えば、負極として、負極活物質および結着剤を含む活物質層が負極集電体上に成形された構造を備える負極シートを使用することができる。なお、前記活物質層は、更に導電剤を含んでもよい。
<Negative electrode>
The negative electrode is not particularly limited as long as it is generally used as a negative electrode of a non-aqueous electrolyte secondary battery. For example, a negative electrode sheet having a structure in which an active material layer containing a negative electrode active material and a binder is formed on a negative electrode current collector can be used as the negative electrode. The active material layer may further contain a conductive agent.
上記負極活物質としては、例えば、リチウムイオンをドープ・脱ドープ可能な材料、リチウム金属またはリチウム合金等が挙げられる。当該材料としては、具体的には、例えば、天然黒鉛、人造黒鉛、コークス類、カーボンブラック、熱分解炭素類、炭素繊維、有機高分子化合物焼成体等の炭素質材料；正極よりも低い電位でリチウムイオンのドープ・脱ドープを行う酸化物、硫化物等のカルコゲン化合物；アルカリ金属と合金化するアルミニウム（Ａｌ）、鉛（Ｐｂ）、錫（Ｓｎ）、ビスマス（Ｂｉ）、シリコン（Ｓｉ）などの金属、アルカリ金属を格子間に挿入可能な立方晶系の金属間化合物（ＡｌＳｂ、Ｍｇ２Ｓｉ、ＮｉＳｉ２）、リチウム窒素化合物（Ｌｉ３-ｘＭｘＮ（Ｍ：遷移金属））等を用いることができる。 Examples of the negative electrode active material include materials that can be doped/dedoped with lithium ions, lithium metal, lithium alloys, and the like. Specific examples of the material include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and organic polymer compound fired bodies; at a potential lower than that of the positive electrode. Chalcogen compounds such as oxides and sulfides for doping/dedoping with lithium ions; aluminum (Al), lead (Pb), tin (Sn), bismuth (Bi), silicon (Si), etc. that alloy with alkali metals Metals, cubic intermetallic compounds (AlSb, Mg 2 Si, NiSi 2 ) capable of intercalating an alkali metal, lithium nitrogen compounds (Li 3 -x M x N (M: transition metal)), etc. Can be used.
前記負極集電体としては、例えば、Ｃｕ、Ｎｉおよびステンレス等が挙げられる。リチウムと合金を作り難く、かつ薄膜に加工し易いことから、Ｃｕがより好ましい。 Examples of the negative electrode current collector include Cu, Ni, and stainless steel. Cu is more preferable because it is difficult to form an alloy with lithium and is easily processed into a thin film.
負極シートの製造方法としては、例えば、負極活物質を負極集電体上で加圧成型する方法；適当な有機溶剤を用いて負極活物質をペースト状にした後、当該ペーストを負極集電体に塗工し、乾燥した後に加圧して負極集電体に固着する方法；等が挙げられる。前記ペーストには、好ましくは前記導電剤および前記結着剤が含まれる。 Examples of the method for producing the negative electrode sheet include a method in which the negative electrode active material is pressure-molded on the negative electrode current collector; the negative electrode active material is made into a paste using an appropriate organic solvent, and then the paste is used as the negative electrode current collector. A method in which the negative electrode current collector is adhered to the negative electrode current collector by applying it to the negative electrode current collector after drying. The paste preferably contains the conductive agent and the binder.
＜多孔質層＞
前記塗工液を前記基材上に塗工した後、当該塗工液から非導電性の溶媒を除去することによって多孔質層を得ることができる。本発明の一実施形態に係る多孔質層の製造方法にて製造された多孔質層は、前述のＥＲ効果および任意のレベリングの効果によって、膜厚精度に優れる。
<Porous layer>
The porous layer can be obtained by applying the coating liquid on the base material and then removing the non-conductive solvent from the coating liquid. The porous layer manufactured by the method for manufacturing a porous layer according to the embodiment of the present invention has excellent film thickness accuracy due to the above-mentioned ER effect and the effect of arbitrary leveling.
前記多孔質層の膜厚は、電池特性の低下を防ぐとの観点から、一層当たり、５μｍ以下であることが好ましく、一層当たり、４μｍ以下であることがより好ましい。また、前記多孔質層の膜厚は、電池の破損等による内部短絡を十分に防止することができ、かつ、電解液の保持量の低下を防ぐとの観点から、一層当たり、０．５μｍ以上であることが好ましく、一層当たり、１μｍ以上であることがより好ましい。 The thickness of the porous layer is preferably 5 μm or less per layer, and more preferably 4 μm or less per layer from the viewpoint of preventing deterioration of battery characteristics. In addition, the thickness of the porous layer is 0.5 μm or more per layer from the viewpoint of being able to sufficiently prevent an internal short circuit due to breakage of a battery and preventing a decrease in the amount of electrolyte retained. Is preferable, and more preferably 1 μm or more per layer.
前記多孔質層は、接着性多孔質層または耐熱多孔質層であることが好ましく、耐熱多孔質層であることがより好ましい。 The porous layer is preferably an adhesive porous layer or a heat resistant porous layer, more preferably a heat resistant porous layer.
多孔質層の単位面積当たりの目付は、多孔質層の強度、膜厚、重量およびハンドリング性を考慮して適宜決定することができる。多孔質層の単位面積当たりの目付は、多孔質層一層当たり、０．５〜１０ｇ／ｍ２であることが好ましく、０．５〜５ｇ／ｍ２であることがより好ましい。 The basis weight per unit area of the porous layer can be appropriately determined in consideration of the strength, film thickness, weight and handleability of the porous layer. The basis weight per unit area of the porous layer is preferably 0.5 to 10 g/m 2 and more preferably 0.5 to 5 g/m 2 per porous layer.
多孔質層の単位面積当たりの目付をこれらの数値範囲とすることにより、非水電解液二次電池の重量エネルギー密度および体積エネルギー密度を高くすることができる。多孔質層の目付が前記範囲を超える場合には、非水電解液二次電池が重くなる傾向がある。 By setting the basis weight per unit area of the porous layer within these numerical ranges, the weight energy density and volume energy density of the non-aqueous electrolyte secondary battery can be increased. When the basis weight of the porous layer exceeds the above range, the non-aqueous electrolyte secondary battery tends to be heavy.
前記多孔質層は、イオン透過性の観点から十分に多孔化された構造であることが好ましい。具体的には、前記多孔質層は、空孔率が３０％〜６０％の範囲であることが好ましい。また、前記多孔質層は、平均孔径が２０ｎｍ〜１００ｎｍの範囲であることが好ましい。 The porous layer preferably has a sufficiently porous structure from the viewpoint of ion permeability. Specifically, the porosity of the porous layer is preferably in the range of 30% to 60%. Further, the porous layer preferably has an average pore size in the range of 20 nm to 100 nm.
［実施形態２：積層体、実施形態３：非水電解液二次電池用セパレータ］
本発明の実施形態２に係る積層体は、基材と、前記基材の少なくとも１つの面に積層された、粒子を含む多孔質層と、を備える積層体であって、前記積層体の膜厚の標準偏差が、０．５μｍ以下である。
[Embodiment 2: laminated body, Embodiment 3: separator for non-aqueous electrolyte secondary battery]
A laminated body according to Embodiment 2 of the present invention is a laminated body including a substrate and a porous layer containing particles, which is laminated on at least one surface of the substrate, and is a film of the laminated body. The standard deviation of the thickness is 0.5 μm or less.
本発明の実施形態３に係る非水電解液二次電池用セパレータは、本発明の実施形態２に係る積層体を含み、前記基材が、多孔質基材である。すなわち、本発明の一実施形態に係る非水電解液二次電池用セパレータに含まれる積層体は、電極板を含まない。
The separator for a non-aqueous electrolyte secondary battery according to
本発明の実施形態２に係る積層体および本発明の実施形態３に係る非水電解液二次電池用セパレータは、本発明の実施形態１に係る多孔質層の製造方法にて、基材上に多孔質層を形成することによって製造され得る。
The laminate according to Embodiment 2 of the present invention and the separator for a non-aqueous electrolyte secondary battery according to
本発明の一実施形態に係る積層体および非水電解液二次電池用セパレータを構成する各部材は、本発明の実施形態１における各部材を適用することができる。 The respective members in Embodiment 1 of the present invention can be applied to the respective members constituting the laminate and the non-aqueous electrolyte secondary battery separator according to the embodiment of the present invention.
本発明の一実施形態に係る積層体の膜厚の標準偏差は、０．５μｍ以下であり、０．４５μｍ以下であることが好ましく、０．４３μｍ以下であることがより好ましい。また、本発明の一実施形態に係る積層体の膜厚の標準偏差は、０．１μｍ以上であり得る。 The standard deviation of the film thickness of the laminate according to one embodiment of the present invention is 0.5 μm or less, preferably 0.45 μm or less, and more preferably 0.43 μm or less. Further, the standard deviation of the film thickness of the laminate according to the embodiment of the present invention may be 0.1 μm or more.
本発明の一実施形態に係る積層体は、膜厚の標準偏差が前述の範囲であることによって、当該積層体を非水電解液二次電池用セパレータまたはその部材として非水電解液二次電池に組み込んだ場合に、当該非水電解液二次電池の電極間の距離の均一性を向上させ、イオンの流れが電極間距離の狭い局所に集中することを防ぐことによって、当該非水電解液二次電池の電池性能を向上させることができる。同様に、本発明の一実施形態に係る非水電解液二次電池用セパレータは、非水電解液二次電池に組み込んだ場合に、当該非水電解液二次電池の電池性能を向上させることができる。 The laminate according to one embodiment of the present invention has a standard deviation of the film thickness within the above range, and thus the laminate is used as a separator for a non-aqueous electrolyte secondary battery or a non-aqueous electrolyte secondary battery as a member thereof. When incorporated into the non-aqueous electrolyte solution, the non-aqueous electrolyte solution improves the uniformity of the distance between the electrodes and prevents the flow of ions from concentrating locally in the narrow inter-electrode distance. The battery performance of the secondary battery can be improved. Similarly, the non-aqueous electrolyte secondary battery separator according to an embodiment of the present invention, when incorporated in a non-aqueous electrolyte secondary battery, to improve the battery performance of the non-aqueous electrolyte secondary battery. You can
本発明の一実施形態に係る積層体の膜厚は、当該積層体を非水電解液二次電池用セパレータまたはその部材として非水電解液二次電池に組み込んだ場合に、電池特性の低下を防ぐとの観点から、１５．０μｍ以下であることが好ましく、１０．０μｍ以下であることがより好ましい。また、非水電解液二次電池の膜厚は、当該非水電解液二次電池の破損等による内部短絡を十分に防止するとの観点から、５．５μｍ以上であることが好ましく、６．０μｍ以上であることがより好ましい。 The film thickness of the laminate according to one embodiment of the present invention, when the laminate is incorporated into a non-aqueous electrolyte secondary battery as a separator for a non-aqueous electrolyte secondary battery or a member thereof, a decrease in battery characteristics. From the viewpoint of prevention, it is preferably 15.0 μm or less, more preferably 10.0 μm or less. In addition, the film thickness of the non-aqueous electrolyte secondary battery is preferably 5.5 μm or more, and 6.0 μm, from the viewpoint of sufficiently preventing an internal short circuit due to damage of the non-aqueous electrolyte secondary battery. The above is more preferable.
本発明の一実施形態に係る積層体の透気度は、ガーレ値で３０〜１０００ｓｅｃ／１００ｍＬであることが好ましく、５０〜８００ｓｅｃ／１００ｍＬであることがより好ましい。本発明の一実施形態に係る積層体は、前記透気度を有することにより、非水電解液二次電池において、充分なイオン透過性を得ることができる。 The air permeability of the laminate according to the embodiment of the present invention is preferably 30 to 1000 sec/100 mL as a Gurley value, and more preferably 50 to 800 sec/100 mL. Since the laminate according to the embodiment of the present invention has the above air permeability, it is possible to obtain sufficient ion permeability in the non-aqueous electrolyte secondary battery.
本発明の一実施形態に係る積層体は、前記基材および前記多孔質層以外の部材として、接着層、耐熱層、保護層等のその他の層をさらに備えていてもよい。 The laminated body according to one embodiment of the present invention may further include other layers such as an adhesive layer, a heat resistant layer, and a protective layer as members other than the base material and the porous layer.
本発明の一実施形態に係る非水電解液二次電池用セパレータは、前記多孔質基材の面上に前記多孔質層が積層されてなる積層体を含む、いわゆる、「非水電解液二次電池用積層セパレータ」または「積層セパレータ」とも称される非水電解液二次電池用セパレータである。 A separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention includes a laminate in which the porous layer is laminated on the surface of the porous substrate, so-called "non-aqueous electrolyte secondary. It is also a separator for non-aqueous electrolyte secondary batteries, which is also referred to as a “secondary battery laminated separator” or a “laminated separator”.
［実施形態４：非水電解液二次電池］
本発明の実施形態４に係る非水電解液二次電池は、本発明の実施形態３に係る非水電解液二次電池用セパレータを含む。
[Embodiment 4: Non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery according to Embodiment 4 of the present invention includes the separator for non-aqueous electrolyte secondary battery according to
本発明の一実施形態に係る非水電解液二次電池を構成する各部材は、本発明の実施形態１〜３における各部材を適用することができる。 Each member in Embodiments 1 to 3 of the present invention can be applied to each member constituting the non-aqueous electrolyte secondary battery according to one embodiment of the present invention.
＜非水電解液＞
本発明の一実施形態に係る非水電解液二次電池における非水電解液は、一般に非水電解液二次電池に使用される非水電解液であり、特に限定されないが、例えば、リチウム塩を有機溶媒に溶解してなる非水電解液を用いることができる。リチウム塩としては、例えば、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、Ｌｉ２Ｂ１０Ｃｌ１０、低級脂肪族カルボン酸リチウム塩、ＬｉＡｌＣｌ４等が挙げられる。前記リチウム塩は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。前記リチウム塩のうち、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２、およびＬｉＣ（ＣＦ３ＳＯ２）３からなる群から選択される少なくとも１種のフッ素含有リチウム塩がより好ましい。
<Non-aqueous electrolyte>
The non-aqueous electrolytic solution in the non-aqueous electrolytic solution secondary battery according to an embodiment of the present invention is a non-aqueous electrolytic solution generally used in non-aqueous electrolytic solution secondary batteries, but is not particularly limited, for example, lithium salt It is possible to use a non-aqueous electrolytic solution prepared by dissolving Examples of the lithium salt include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , Li 2 B 10 Cl. 10 , lower aliphatic carboxylic acid lithium salt, LiAlCl 4 and the like. The lithium salt may be used alone or in combination of two or more kinds. At least 1 selected from the group consisting of LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , and LiC(CF 3 SO 2 ) 3 among the lithium salts. More preferred are fluorine-containing lithium salts.
本発明における非水電解液を構成する有機溶媒としては、具体的には、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、４−トリフルオロメチル−１，３−ジオキソラン−２−オン、１，２−ジ（メトキシカルボニルオキシ）エタン等のカーボネート類；１，２−ジメトキシエタン、１，３−ジメトキシプロパン、ペンタフルオロプロピルメチルエーテル、２，２，３，３−テトラフルオロプロピルジフルオロメチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフラン等のエーテル類；ギ酸メチル、酢酸メチル、γ−ブチロラクトン等のエステル類；アセトニトリル、ブチロニトリル等のニトリル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類；３−メチル−２−オキサゾリドン等のカーバメート類；スルホラン、ジメチルスルホキシド、１，３−プロパンサルトン等の含硫黄化合物；並びに、前記有機溶媒にフッ素基が導入されてなる含フッ素有機溶媒；等が挙げられる。前記有機溶媒は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。前記有機溶媒のうち、カーボネート類がより好ましく、環状カーボネートと非環状カーボネートとの混合溶媒、または、環状カーボネートとエーテル類との混合溶媒がさらに好ましい。環状カーボネートと非環状カーボネートとの混合溶媒としては、作動温度範囲が広く、かつ、負極活物質として天然黒鉛や人造黒鉛等の黒鉛材料を用いた場合においても難分解性を示すことから、エチレンカーボネート、ジメチルカーボネートおよびエチルメチルカーボネートを含む混合溶媒がさらに好ましい。 Specific examples of the organic solvent that constitutes the non-aqueous electrolyte in the present invention include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolane-. Carbonates such as 2-one and 1,2-di(methoxycarbonyloxy)ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoro Ethers such as propyldifluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; Esters such as methyl formate, methyl acetate, γ-butyrolactone; Nitriles such as acetonitrile, butyronitrile; N,N-dimethylformamide, N,N-dimethyl Amides such as acetamide; carbamates such as 3-methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 1,3-propanesultone; and fluorine-containing groups introduced into the organic solvent. Fluorine organic solvent; and the like. The organic solvent may be used alone or in combination of two or more. Among the organic solvents, carbonates are more preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or a mixed solvent of cyclic carbonate and ethers is further preferable. As a mixed solvent of a cyclic carbonate and a non-cyclic carbonate, a wide operating temperature range, and since it exhibits a persistent property even when using a graphite material such as natural graphite or artificial graphite as the negative electrode active material, ethylene carbonate A mixed solvent containing dimethyl carbonate and ethyl methyl carbonate is more preferable.
＜非水電解液二次電池の製造方法＞
本発明の一実施形態に係る非水電解液二次電池用の製造方法としては、従来公知の方法を適用できる。例えば、前記正極、本発明の一実施形態に係る非水電解液二次電池用セパレータ、および負極をこの順で配置して非水電解液二次電池用部材を形成した後、非水電解液二次電池の筐体となる容器に当該非水電解液二次電池用部材を入れ、次いで、当該容器内を非水電解液で満たした後、減圧しつつ密閉することにより、本発明の一実施形態に係る非水電解液二次電池を製造することができる。
<Method of manufacturing non-aqueous electrolyte secondary battery>
A conventionally known method can be applied as a manufacturing method for the non-aqueous electrolyte secondary battery according to the embodiment of the present invention. For example, the positive electrode, a separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention, and a negative electrode are arranged in this order to form a member for a non-aqueous electrolyte secondary battery, and then a non-aqueous electrolyte solution is formed. The non-aqueous electrolyte secondary battery member is placed in a container that serves as a casing of the secondary battery, and then the container is filled with the non-aqueous electrolyte, and then sealed while depressurizing. The non-aqueous electrolyte secondary battery according to the embodiment can be manufactured.
非水電解液二次電池の形状は、特に限定されるものではなく、薄板（ペーパー）型、円盤型、円筒型、直方体等の角柱型等のどのような形状であってもよい。尚、非水電解液二次電池用部材および非水電解液二次電池の製造方法は、特に限定されるものではなく、従来公知の製造方法を採用することができる。 The shape of the non-aqueous electrolyte secondary battery is not particularly limited, and may be any shape such as a thin plate (paper) type, a disc type, a cylindrical type, and a prismatic type such as a rectangular parallelepiped. The manufacturing method of the non-aqueous electrolyte secondary battery member and the non-aqueous electrolyte secondary battery is not particularly limited, and a conventionally known manufacturing method can be adopted.
本発明は前述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。さらに、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。 The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments Is also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each of the embodiments.
以下、実施例および比較例により、本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
［測定］
＜平均膜厚および標準偏差（単位：μｍ）＞
膜厚は、ミツトヨ製膜厚計ＶＬ−５０Ａを用いて測定した。実施例１〜４、比較例１〜２にて製造されたそれぞれの積層体の任意の１５点において、膜厚を測定し、その平均値を算出し、平均膜厚とした。さらに、前記の１５点における膜厚の測定値に基づき、膜厚の標準偏差を算出した。続いて、「膜厚の標準偏差／平均膜厚」の値の算出を行った。
[Measurement]
<Average film thickness and standard deviation (unit: μm)>
The film thickness was measured using a thickness meter VL-50A manufactured by Mitutoyo. The film thickness was measured at an arbitrary 15 points of each of the laminates produced in Examples 1 to 4 and Comparative Examples 1 and 2, and the average value thereof was calculated to be the average film thickness. Furthermore, the standard deviation of the film thickness was calculated based on the measured values of the film thickness at the above 15 points. Then, the value of "standard deviation of film thickness/average film thickness" was calculated.
＜電場強度（単位：ＭＶ／ｍ）＞
白光製の非接触式電位計ハッコーＦＧ−４５０を用いて、実施例１〜４、比較例１〜２における、塗工装置である塗工バーと基材の電位（単位：Ｖ）を測定した。得られた測定値から、塗工装置と基材との電位差を算出した。続けて、算出された電位差をクリアランスの値（単位：μｍ）で割ることによって、電場強度を算出した。
<Electric field strength (unit: MV/m)>
Using a non-contact type electrometer Hakko FG-450 manufactured by Hakuko, the potentials (unit: V) of the coating bar and the substrate in Examples 1 to 4 and Comparative Examples 1 and 2 were measured. .. The potential difference between the coating device and the substrate was calculated from the obtained measured values. Subsequently, the electric field strength was calculated by dividing the calculated potential difference by the clearance value (unit: μm).
［化合物の略称］
実施例および比較例にて使用した化合物の略称を以下に示す。
[Compound Abbreviation]
The abbreviations of the compounds used in Examples and Comparative Examples are shown below.
ＮＭＰ：Ｎ−メチルピロリドン
ＰＰＤ：パラフェニレンジアミン
ＴＰＣ：テレフタル酸ジクロライド
ＰＥ：ポリエチレン
［実施例１］
＜塗工液の調製＞
撹拌翼、温度計、窒素流入管及び粉体添加口を有する５Ｌのセパラブルフラスコを使用してパラアラミドの合成を行った。具体的には、前記セパラブルフラスコを充分乾燥した後、ＮＭＰ４２００ｇを仕込み、２００℃にて２時間乾燥させた塩化カルシウム２７２．６５ｇを添加して１００℃に昇温した。塩化カルシウムが完全に溶解した後、当該フラスコ内の温度を室温に戻して、次いで、ＰＰＤ１３２．９１ｇを添加した。当該ＰＰＤを完全に溶解させ、第１溶液を得た。得られた第１溶液の温度を２０±２℃に保ったまま、当該第１溶液に対して、ＴＰＣ２４３．３２ｇを１０分割して約５分間おきに添加し、第２溶液を得た。その後、得られた第２溶液の温度を２０±２℃に保ったまま、当該第２溶液を１時間熟成させ、次いで気泡を抜くため減圧下にて３０分間撹拌し、パラアラミド／ＮＭＰ溶液を得た。得られたパラアラミド／ＮＭＰ溶液中のパラアラミド１００重量部に対し、平均粒径０．０２μｍのアルミナ粉末（ＥＶＯＮＩＫ製：Ａｌｕｍｉｎａ Ｃ）と、平均粒径０．３μｍのアルミナ粉末（住友化学（株）製：高純度アルミナＡＡ−０３）とをそれぞれ１００重量部ずつ添加した。続いて前記溶液を、固形分濃度が６％となるようにＮＭＰを用いて希釈した。その後、ホモジナイザーを用いて撹拌し、さらに圧力式分散機にて５０ＭＰａ×２回処理することにより、塗工液１を得た。
NMP: N-methylpyrrolidone PPD: Paraphenylenediamine TPC: Terephthalic acid dichloride PE: Polyethylene [Example 1]
<Preparation of coating liquid>
Para-aramid was synthesized using a 5 L separable flask having a stirring blade, a thermometer, a nitrogen inflow tube, and a powder addition port. Specifically, after the separable flask was sufficiently dried, 4200 g of NMP was charged, 272.65 g of calcium chloride dried at 200° C. for 2 hours was added, and the temperature was raised to 100° C. After the calcium chloride was completely dissolved, the temperature in the flask was returned to room temperature, and then 132.91 g of PPD was added. The PPD was completely dissolved to obtain a first solution. While maintaining the temperature of the obtained first solution at 20±2° C., 243.32 g of TPC was divided into 10 parts and added to the first solution at intervals of about 5 minutes to obtain a second solution. Then, while maintaining the temperature of the obtained second solution at 20±2° C., the second solution was aged for 1 hour, and then stirred under reduced pressure for 30 minutes to remove air bubbles to obtain a para-aramid/NMP solution. It was With respect to 100 parts by weight of para-aramid in the obtained para-aramid/NMP solution, an alumina powder having an average particle size of 0.02 μm (manufactured by EVONIK: Alumina C) and an alumina powder having an average particle size of 0.3 μm (manufactured by Sumitomo Chemical Co., Ltd.) : High-purity alumina AA-03) and 100 parts by weight each were added. Subsequently, the solution was diluted with NMP so that the solid content concentration was 6%. Then, the mixture was stirred using a homogenizer, and further treated with a pressure type disperser at 50 MPa×2 times to obtain a coating liquid 1.
＜多孔質層の形成＞
塗工にはＴＥＣＨＮＯ ＳＵＰＰＬＹ製バーコータを用い、塗工バーにはベーカー式アプリケーターを使用した。塗工バーのクリアランスは７５μｍに設定した。市販のポリエチレン基材（膜厚１０．８μｍ）をガラス製の板に貼り付け、除電装置イオナイザーを用いて電位を０Ｖに調整した。その後、帯電ガンを用いてポリエチレン基材を帯電させることにより、バーとの間に電場を発生させた。この時、バーと基材との電位差は１６０Ｖであり、電場強度は２．１３ＭＶ／ｍであった。
<Formation of porous layer>
A TECHNO SUPPLY bar coater was used for coating, and a baker type applicator was used for the coating bar. The clearance of the coating bar was set to 75 μm. A commercially available polyethylene base material (film thickness 10.8 μm) was attached to a glass plate, and the potential was adjusted to 0 V using a static eliminator ionizer. Then, an electric field was generated between the polyethylene base material and the bar by charging the polyethylene base material with a charging gun. At this time, the potential difference between the bar and the substrate was 160 V, and the electric field strength was 2.13 MV/m.
塗工液１を前記バーコータに供給して、７０ｃｍ／ｍｉｎの速度で、塗工液１を前記ポリエチレン基材上に塗工した。その後、直ちに蒸留水で洗浄することで多孔質層を析出させるとともに、溶媒の除去を行った。次いで８０℃のオーブン内にて、多孔質層が積層されたポリエチレン基材を乾燥させることにより、塗工フィルムを得た。得られた塗工フィルムを積層体１とした。 The coating liquid 1 was supplied to the bar coater, and the coating liquid 1 was coated on the polyethylene base material at a speed of 70 cm/min. Then, the porous layer was precipitated by immediately washing with distilled water, and the solvent was removed. Then, the coated polyethylene film was dried in an oven at 80° C. to obtain a coated film. The obtained coated film was used as a laminate 1.
［実施例２］
塗工バーと基材の電位差を４２０Ｖ、塗工バーのクリアランスを５１μｍに設定することにより、電場強度を８．２７ＭＶ／ｍに制御したこと以外は、実施例１と同様の方法にて塗工フィルムを得た。得られた塗工フィルムを積層体２とした。
[Example 2]
Coating was performed in the same manner as in Example 1 except that the electric field strength was controlled to 8.27 MV/m by setting the potential difference between the coating bar and the base material to 420 V and the clearance between the coating bar to 51 μm. I got a film. The obtained coated film was used as a laminate 2.
［実施例３］
ポリエチレン基材を帯電させ、塗工バーと基材の電位差を２０Ｖ、塗工バーのクリアランスを６５μｍに設定することにより、電場強度を０．３１ＭＶ／ｍに制御したこと以外は、実施例１と同様の方法にて塗工フィルムを得た。得られた塗工フィルムを積層体３とした。
[Example 3]
Example 1 was repeated except that the electric field strength was controlled to 0.31 MV/m by charging the polyethylene base material, setting the potential difference between the coating bar and the base material to 20 V, and setting the clearance between the coating bar to 65 μm. A coated film was obtained by the same method. The obtained coated film was used as a
［実施例４］
アルミナＡＡ０３の代わりに、ベーマイト（Ｅｓｔｏｎｅ社製 ＢＧ‐６０１）を用いたこと以外は、実施例２と同様の方法にて塗工フィルムを得た。得られた塗工フィルムを積層体４とした。
[Example 4]
A coated film was obtained in the same manner as in Example 2 except that boehmite (BG-601 manufactured by Estone) was used instead of alumina AA03. The obtained coated film was used as a laminate 4.
［比較例１］
帯電ガンを用いて電場を発生させなかったこと以外は、実施例２と同様の方法にて塗工フィルムを得た。得られた塗工フィルムを積層体５とした。
[Comparative Example 1]
A coated film was obtained in the same manner as in Example 2 except that an electric field was not generated using a charging gun. The obtained coated film was used as a laminate 5.
［比較例２］
帯電ガンを用いて電場を発生させなかったこと以外は、実施例４と同様の方法にて塗工フィルムを得た。得られた塗工フィルムを積層体６とした。
[Comparative example 2]
A coated film was obtained in the same manner as in Example 4 except that an electric field was not generated using a charging gun. The obtained coated film was used as a laminate 6.
［結果］
実施例１〜４、比較例１〜２における、塗工液中の「粒子」、「樹脂」および「分散溶媒」、並びに、「基材の構成物質」を以下の表１に示す。また、実施例１〜４、比較例１〜２における、「電位差」、「クリアランス」および「電場強度」、並びに、得られた積層体の「平均膜厚」、「膜厚の標準偏差」および「膜厚の標準偏差／平均膜厚」の値を表２に示す。
[result]
Table 1 below shows "particles", "resin" and "dispersion solvent" in the coating liquid and "constituent substances of the base material" in Examples 1 to 4 and Comparative Examples 1 and 2. In addition, in Examples 1 to 4 and Comparative Examples 1 and 2, “potential difference”, “clearance” and “electric field strength”, and “average film thickness”, “standard deviation of film thickness” of the obtained laminated body and The value of “standard deviation of film thickness/average film thickness” is shown in Table 2.
表１に記載の通り、実施例１〜４にて得られる積層体１〜４は、比較例１、２にて得られる積層体５、６と比較して、平均膜厚が同程度である一方、膜厚の標準偏差が小さい。 As shown in Table 1, the laminates 1 to 4 obtained in Examples 1 to 4 have the same average film thickness as the laminates 5 and 6 obtained in Comparative Examples 1 and 2. On the other hand, the standard deviation of the film thickness is small.
よって、塗工液を基材上に塗工する瞬間に、当該塗工液に対して０．１ＭＶ／ｍ以上の電場を印加することによって、得られる積層体の膜厚精度が向上することが分かった。 Therefore, by applying an electric field of 0.1 MV/m or more to the coating liquid at the moment of applying the coating liquid on the substrate, the film thickness accuracy of the obtained laminate can be improved. Do you get it.
本発明の一実施形態に係る多孔質層の製造方法によって製造される多孔質層および当該多孔質層を含む積層体、並びに、本発明の一実施形態に係る積層体は、膜厚精度に優れる。よって、前記積層体は、電池性能に優れる非水電解液二次電池の部材として好適に使用できる。 A porous layer produced by a method for producing a porous layer according to an embodiment of the present invention, a laminate including the porous layer, and a laminate according to an embodiment of the present invention have excellent film thickness accuracy. .. Therefore, the laminate can be suitably used as a member of a non-aqueous electrolyte secondary battery having excellent battery performance.
従って、本発明は、非水電解液二次電池を取り扱う各種産業において、好適に利用され得る。 Therefore, the present invention can be preferably used in various industries handling non-aqueous electrolyte secondary batteries.
１ 塗工装置
２ 塗工液
３ 基材
1 coating device 2
Claims (10)
前記基材の面に塗工した前記塗工液から、前記非導電性の溶媒を除去する工程と、を含み、
前記塗工液が、前記塗工装置と前記基材との間を通過する時の、前記塗工装置と前記基材との間の電場強度が１．０×１０５Ｖ／ｍ以上である、多孔質層の製造方法。 Non-conductive solvent, and a coating liquid containing particles, by passing between the coating device and the substrate, the step of coating on the surface of the substrate,
From the coating liquid applied to the surface of the substrate, a step of removing the non-conductive solvent,
The electric field strength between the coating device and the base material is 1.0×10 5 V/m or more when the coating liquid passes between the coating device and the base material. , A method for producing a porous layer.
前記積層体の膜厚の標準偏差が、０．５μｍ以下である、積層体。 A laminate comprising a substrate and a porous layer containing particles, which is laminated on at least one surface of the substrate,
A laminate having a standard deviation of the film thickness of the laminate of 0.5 μm or less.
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| KR1020217018501A KR20210104054A (en) | 2018-12-18 | 2019-12-03 | Manufacturing method of porous layer, laminate, separator for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN201980083409.5A CN113195113A (en) | 2018-12-18 | 2019-12-03 | Method for producing porous layer, laminate, separator for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| PCT/JP2019/047109 WO2020129598A1 (en) | 2018-12-18 | 2019-12-03 | Method for producing porous layer, stack, separator for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
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| JP7289194B2 (en) | 2023-06-09 |
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