JP4870359B2 - Degreasing method of aluminum foil - Google Patents
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- JP4870359B2 JP4870359B2 JP2005001059A JP2005001059A JP4870359B2 JP 4870359 B2 JP4870359 B2 JP 4870359B2 JP 2005001059 A JP2005001059 A JP 2005001059A JP 2005001059 A JP2005001059 A JP 2005001059A JP 4870359 B2 JP4870359 B2 JP 4870359B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
この発明は、アルミニウム硬箔、例えばリチウムイオン二次電池の正極材として用いられるアルミニウム硬箔の脱脂方法に関し、さらにこの方法により脱脂されたアルミニウム硬箔、この硬箔に電極活物質を塗布したアルミニウム硬箔電極材、それを用いたリチウムイオン二次電池に関する。 The present invention relates to a method for degreasing an aluminum hard foil, for example, an aluminum hard foil used as a positive electrode material for a lithium ion secondary battery, and further relates to an aluminum hard foil degreased by this method, and an aluminum obtained by applying an electrode active material to the hard foil. The present invention relates to a hard foil electrode material and a lithium ion secondary battery using the same.
なお、この明細書において、「アルミニウム」の語はアルミニウムおよびその合金を含む意味で用いる。 In this specification, the term “aluminum” is used to include aluminum and its alloys.
上記のようなリチウムイオン二次電池の正極材は、ＬｉＣｏＯ2等の活材物質とカーボン等の導電材とＰＶＤ等の結着材とをペースト状に混練したのち、これを１０〜２０μｍ程度のアルミニウム硬箔の片面または両面に１００〜２００μｍ程度の厚みに塗布し、次いで乾燥、プレス、スリット、裁断の各工程を順次的に実施することにより製作される。ペーストは、例えば図１に示すようにアルミニウム硬箔(1)の圧延方向（長手方向）に沿って間欠的に塗布され、塗工部(2)と未塗工部（符号なし）とが交互に形成される。 The positive electrode material of the lithium ion secondary battery as described above is obtained by kneading an active material such as LiCoO 2 , a conductive material such as carbon, and a binding material such as PVD in a paste form, and then mixing the paste material with about 10 to 20 μm. It is manufactured by applying a thickness of about 100 to 200 μm on one or both sides of a hard aluminum foil, and then sequentially carrying out the steps of drying, pressing, slitting and cutting. For example, as shown in FIG. 1, the paste is intermittently applied along the rolling direction (longitudinal direction) of the hard aluminum foil (1), and the coated part (2) and the uncoated part (not indicated) are alternately arranged. Formed.
このような正極材において、アルミニウム硬箔(1)表面に圧延に用いた潤滑油が残留していると、塗工部(2)の境界部(2a)が両端で湾曲したり（図２）、縁部(2b)が盛り上がる（図３）といった塗工むらが生じ、ひいては電池性能を低下させるという問題が生じる。従って、電極用基材として用いられるアルミニウム硬箔は、表面の残油量の少ないものが要求される。 In such a positive electrode material, if the lubricating oil used for rolling remains on the surface of the hard aluminum foil (1), the boundary part (2a) of the coated part (2) may be curved at both ends (FIG. 2). As a result, coating unevenness occurs such that the edge (2b) rises (FIG. 3), which in turn causes a problem of lowering battery performance. Accordingly, the hard aluminum foil used as the electrode substrate is required to have a small amount of residual oil on the surface.
一般に、アルミニウム箔またはアルミニウム板の脱脂方法に関しては、有機系溶剤、酸、アルカリ等の洗浄液による洗浄が知られている（特許文献１，２、３）。
In general, with respect to a method for degreasing an aluminum foil or an aluminum plate, cleaning with a cleaning liquid such as an organic solvent, an acid, or an alkali is known (
また、アルミニウム箔を焼鈍することによって脱脂する方法も知られている。
しかしながら、洗浄による脱脂は手間がかかり、箔表面に洗浄液が残留するとペーストの塗布性および密着性を低下させるおそれがある。また、焼鈍による脱脂では、硬箔が軟化してリチウムイオン二次電池の正極材として必要な強度を維持することができないという問題点がある。 However, degreasing by washing is time-consuming, and if the cleaning liquid remains on the foil surface, there is a possibility that the applicability and adhesion of the paste may be reduced. In addition, degreasing by annealing has a problem that the hard foil is softened and the strength necessary for the positive electrode material of the lithium ion secondary battery cannot be maintained.
この発明は、このような技術的背景に鑑みてなされたものであって、簡単な工程で実施でき、強度を低下させずに脱脂できるアルミニウム硬箔の脱脂方法の提供を目的とする。 This invention is made in view of such a technical background, Comprising: It aims at provision of the degreasing method of the aluminum hard foil which can be implemented by a simple process and can degrease | degrease without reducing intensity | strength.
前記目的を達成するために、本発明のアルミニウム硬箔の製造方法は、下記（１）〜（３）に記載の構成を有する。
（１） 箔圧延後のアルミニウム箔に、８０〜１６０℃で１時間以上保持する低温熱処理を施すことにより脱脂することを特徴とするアルミニウム硬箔の脱脂方法。
（２） 低温熱処理は、箔をコイルに巻いた状態でバッチ処理する前項（１）に記載のアルミニウム硬箔の脱脂方法。
（３） アルミニウム箔の箔厚が４〜５０μｍである前項（１）または（２）に記載のアルミニウム硬箔の脱脂方法。
In order to achieve the above object, the method for producing an aluminum hard foil of the present invention has a configuration described in the following (1) to (3).
(1) A method for degreasing an aluminum hard foil, characterized in that the aluminum foil after foil rolling is degreased by subjecting the aluminum foil to a low temperature heat treatment at 80 to 160 ° C. for 1 hour or more.
(2) The low temperature heat treatment is a method for degreasing an aluminum hard foil as described in (1) above, wherein batch processing is performed with the foil wound around a coil.
(3) The method for degreasing an aluminum hard foil according to (1) or (2) above, wherein the foil thickness of the aluminum foil is 4 to 50 μm.
本発明のアルミニウム硬箔は、下記（４）〜（６）に記載の構成を有する。
（４） 前項（１）〜（２）のいずれか１項の方法により脱脂されたことを特徴とするアルミニウム硬箔。
（５） 箔表面は、２５℃における表面張力が０．４１Ｎ／ｍのぬれ性試験液によって測定された接触角が４５°未満となされている前項（４）に記載のアルミニウム硬箔。
（６） アルミニウム硬箔は電池電極用基材である前項（４）または（５）に記載のアルミニウム硬箔。
The aluminum hard foil of this invention has the structure as described in following (4)-(6).
(4) An aluminum hard foil that has been degreased by the method according to any one of (1) to (2) above.
(5) The aluminum hard foil according to item (4), wherein the foil surface has a contact angle measured by a wettability test solution having a surface tension at 25 ° C. of 0.41 N / m of less than 45 °.
(6) The aluminum hard foil according to the item (4) or (5), wherein the aluminum hard foil is a battery electrode substrate.
本発明のアルミニウム硬箔電極材は下記（７）（８）に記載の構成を有する。 The aluminum hard foil electrode material of this invention has the structure as described in following (7) (8).
（７） 前項（６）に記載のアルミニウム硬箔を電極用基材とし、この電極用基材上に電極活物質を含む電極材料を塗布してなることを特徴とするアルミニウム硬箔電極材。 (7) An aluminum hard foil electrode material, wherein the hard aluminum foil according to (6) above is used as an electrode base material, and an electrode material containing an electrode active material is applied onto the electrode base material.
（８） 電極活物質を含む電極材料が、リチウムイオン二次電池の正極材料である前項（７）に記載のアルミニウム硬箔電極材。 (8) The aluminum hard foil electrode material according to (7), wherein the electrode material containing an electrode active material is a positive electrode material for a lithium ion secondary battery.
本発明のリチウムイオン二次電池は下記（９）に記載の構成を有する。
（９） 電極用基材または電極材として、前項（６）に記載のアルミニウム硬箔、または前項（７）または（８）に記載のアルミニウム硬箔電極材を用いてなることを特徴とするリチウムイオン二次電池。
The lithium ion secondary battery of this invention has the structure as described in following (9).
(9) Lithium characterized by using the aluminum hard foil described in (6) above or the aluminum hard foil electrode material described in (7) or (8) above as the electrode substrate or electrode material. Ion secondary battery.
（１）の発明にかかるアルミニウム硬箔の脱脂方法によれば、箔圧延によって得た強度を低下させることなく脱脂でき、コーティング材の塗工性および密着性を向上させることができる。また、熱処理のみであるから作業が簡単である。 According to the degreasing method of the aluminum hard foil concerning invention of (1), it can degrease without reducing the intensity | strength obtained by foil rolling, and can improve the applicability | paintability and adhesiveness of a coating material. In addition, the operation is simple because only heat treatment is performed.
（２）の発明によれば、効率良く低温熱処理を行える。 According to the invention of (2), low temperature heat treatment can be performed efficiently.
（３）の発明によれば、リチウムイオン二次電池等の電極用基材に適したアルミニウム硬箔を製造できる。 According to the invention of (3), the aluminum hard foil suitable for electrode base materials, such as a lithium ion secondary battery, can be manufactured.
（４）の発明にかかるアルミニウム硬箔は、箔圧延によって得た強度を維持しつつ箔表面が脱脂され、コーティング材の塗工性および密着性に優れたアルミニウム硬箔である。 The aluminum hard foil according to the invention of (4) is an aluminum hard foil in which the foil surface is degreased while maintaining the strength obtained by foil rolling, and the coating material is excellent in coating property and adhesion.
（５）の発明にかかるアルミニウム硬箔は、特に塗工性および密着性に優れている。 The aluminum hard foil according to the invention of (5) is particularly excellent in coatability and adhesion.
（６）の発明にかかるアルミニウム硬箔は、電極活物質の塗工時に高いロールプレス圧を付与しても伸びにくいため電池電極用基材として好適である。 The aluminum hard foil according to the invention of (6) is suitable as a base material for battery electrodes because it hardly stretches even when a high roll press pressure is applied during application of the electrode active material.
（７）の発明にかかるアルミニウム硬箔電極材は、表面が十分に脱脂されているため、電極活物質を含む電極材料の塗工性および密着性が良好である。 Since the surface of the aluminum hard foil electrode material according to the invention of (7) is sufficiently degreased, the coating property and adhesion of the electrode material containing the electrode active material are good.
（８）の発明にかかるアルミニウム硬箔電極材は、リチウムイオン二次電池用正極材となし得る。 The aluminum hard foil electrode material according to the invention of (8) can be a positive electrode material for a lithium ion secondary battery.
（９）の発明にかかるリチウムイオン二次電池は、電極材において電極用基材への電極材料の塗工性および密着性が達成されるため、高い電池容量が得られるとともに、充放電に対しても高い容量安定性が得られる。 The lithium ion secondary battery according to the invention of (9) achieves high battery capacity as well as charge / discharge because the electrode material can achieve the coating property and adhesion of the electrode material to the electrode substrate. Even high capacity stability can be obtained.
本発明は、箔圧延後のアルミニウム硬箔に低温熱処理を施すことによって箔を軟化させることなく脱脂して箔表面のぬれ性を改善し、電極材料等のコーティング材の塗工性を高め得るものである。また、洗浄液を用いないため、処理が簡単であるとともに、洗浄液の残留によって塗工性やコーティング材の密着性を低下させるおそれもない。 The present invention can improve the wettability of the foil surface by softening the foil by subjecting the aluminum hard foil after foil rolling to low-temperature heat treatment to improve the wettability of the foil surface, and can improve the coatability of coating materials such as electrode materials It is. Further, since no cleaning liquid is used, the process is simple and there is no possibility that the coating property and the adhesion of the coating material are deteriorated due to the remaining cleaning liquid.
低温熱処理は、８０〜１６０℃で１時間以上保持することにより行う。処理温度が８０℃未満では長時間をかけても脱脂効果に乏しく、１６０℃を超えると箔が軟化し、箔圧延によって得た強度が低下するためである。処理時間は１時間未満では脱脂効果に乏しいため、１時間以上とする。本発明は低温熱処理であるから長時間保持しても材料強度が低下するおそれはなく、処理時間の上限に制限はない。ただし、１００時間を超える長時間処理を施しても脱脂効果が飽和してそれ以上の効果が得られない。このため、処理時間は処理効率の点で１００時間以下が好ましい。油分は処理温度が高いほど短時間で脱脂され、また箔の化学組成によって熱影響が異なるため、これらに応じて適宜処理条件を設定すれば良い。例えば、ＪＩＳ Ａ１０００系では８０〜１２０℃で１〜５０時間が好ましく、ＪＩＳ Ａ３０００系では８０〜１３０℃で１〜５０時間が好ましい。 The low temperature heat treatment is performed by holding at 80 to 160 ° C. for 1 hour or longer. If the treatment temperature is less than 80 ° C., the degreasing effect is poor even if it takes a long time, and if it exceeds 160 ° C., the foil softens and the strength obtained by foil rolling decreases. Since the treatment time is less than 1 hour and the degreasing effect is poor, the treatment time is 1 hour or more. Since the present invention is a low-temperature heat treatment, there is no risk that the material strength will decrease even if it is held for a long time, and there is no upper limit on the treatment time. However, even if the treatment is performed for a long time exceeding 100 hours, the degreasing effect is saturated and no further effect can be obtained. For this reason, the processing time is preferably 100 hours or less in terms of processing efficiency. The oil is degreased in a shorter time as the treatment temperature is higher, and the thermal effect differs depending on the chemical composition of the foil. Therefore, the treatment conditions may be set appropriately according to these. For example, in JIS A1000 system, 1 to 50 hours are preferable at 80 to 120 ° C, and in JIS A3000 system, 1 to 50 hours are preferable at 80 to 130 ° C.
本発明における脱脂とは、油分が蒸発して除去されることのみならず、油分が熱処理によって分解または変化して表面張力が低下した状態をも含むものである。従って、脱脂の度合いは、残油量あるいは油分の分解物または変化物の残留量ではなく、コーティング材の塗工性の良否、即ち箔表面のぬれ性によって判断される。前記ぬれ性は、２５℃における表面張力が０．４１Ｎ／ｍのぬれ性試験液によって測定された接触角によって定義される。本発明のアルミニウム硬箔は、箔用途や前記ぬれ性試験液による接触角を限定するものではないが、リチウムイオン二次電池の電極用基材として用いる場合は、コーティング材の塗工性を確保するために前記接触角が４５°未満となされたものを用いることが好ましく、特に４０°以下が好ましい。また、上述したぬれ性試験液として、Ｎ−メチル−２−ピロリドン（N-Methyl-2-pyrrolidone）を例示できる。 The degreasing in the present invention includes not only the fact that the oil is evaporated and removed, but also the state where the oil is decomposed or changed by heat treatment and the surface tension is lowered. Therefore, the degree of degreasing is determined not by the residual oil amount or the residual amount of decomposed or changed oil components but by the quality of the coating material, that is, the wettability of the foil surface. The wettability is defined by the contact angle measured with a wettability test solution having a surface tension at 25 ° C. of 0.41 N / m. The aluminum hard foil of the present invention does not limit the contact angle with the foil application or the wettability test solution, but when used as a base material for an electrode of a lithium ion secondary battery, the coating property of the coating material is ensured. Therefore, it is preferable to use a contact angle of less than 45 °, particularly 40 ° or less. Moreover, N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone) can be illustrated as a wettability test liquid mentioned above.
本発明は、上述した以外のぬれ性試験やそのようなぬれ性試験で規定されたアルミニウム硬箔を排除するものではない。例えば、表面張力の異なる試験液によって測定された接触角が４５°以上である場合や、接触角以外の方法でぬれ性が規定された場合であっても、本発明と同等のぬれ性を有するものは本発明に含まれる。 The present invention does not exclude wettability tests other than those described above and aluminum hard foils defined by such wettability tests. For example, even when the contact angle measured by a test solution having a different surface tension is 45 ° or more, or when the wettability is defined by a method other than the contact angle, the wettability equivalent to the present invention is obtained. Are included in the present invention.
前記低温熱処理は、洗浄液による脱脂のように箔を巻き戻す必要がないため、箔をコイルに巻いた状態でバッチ処理することができ、簡単な装置と処理で脱脂処理を行うことができる。また、同時に多くのアルミニウム硬箔の熱処理を行うことができ、処理効率が良い。ただし、本発明は、箔を巻き戻しながら連続的に低温熱処理することを排除するものではない。 Since the low-temperature heat treatment does not require rewinding the foil as in the case of degreasing with a cleaning liquid, batch processing can be performed with the foil wound around a coil, and degreasing can be performed with a simple apparatus and processing. Moreover, many aluminum hard foil can be heat-processed simultaneously, and processing efficiency is good. However, the present invention does not exclude continuous low temperature heat treatment while rewinding the foil.
アルミニウム硬箔の化学組成は特に限定されることはなく、例えばＪＩＳ Ａ１０８５、Ａ１Ｎ３０等の１０００系合金（純アルミニウム系）、Ａ３００３，Ａ３００４等の３０００系合金（Ａｌ−Ｍｎ系）、Ａ８０７９、Ａ８０２１等の８０００系合金（Ａｌ−Ｆｅ系）等の各種のものを用いれば良い。これらのアルミニウム硬箔は後述のリチウムイオン二次電池の電極用基材として用いられる材料合金である。 The chemical composition of the aluminum hard foil is not particularly limited. For example, 1000 series alloys (pure aluminum series) such as JIS A1085 and A1N30, 3000 series alloys such as A3003 and A3004 (Al-Mn series), A8079, A8021, etc. Various types of alloys such as 8000 series alloys (Al-Fe series) may be used. These aluminum hard foils are material alloys used as an electrode base material for a lithium ion secondary battery described later.
本発明の方法は、対象とする硬箔の厚さを限定するものではないが、厚さが４〜５０μｍの箔への適用を推奨できる。この範囲の厚さの箔はリチウムイオン二次電池の電極材の電極用基材として好適に用いることができ、本発明の適用意義が大きいためである。特に好ましい箔厚は１０〜３０μｍである。 The method of the present invention does not limit the thickness of the target hard foil, but application to a foil having a thickness of 4 to 50 μm can be recommended. This is because a foil having a thickness in this range can be suitably used as an electrode substrate of an electrode material of a lithium ion secondary battery, and the application significance of the present invention is great. A particularly preferred foil thickness is 10 to 30 μm.
上述した低温熱処理に供するアルミニウム箔は、常法に従い熱間圧延、冷間圧延、箔圧延の順次的実施によって製造すれば良い。また、低温熱処理は、アルミニウム箔が箔圧延時の加工硬化によって得た強度を保持している状態で行えば良く、箔圧延直後に連続して行うことも、箔圧延後に時間を隔てて行うこともできる。 The aluminum foil to be subjected to the low-temperature heat treatment described above may be manufactured by sequentially performing hot rolling, cold rolling, and foil rolling according to a conventional method. The low-temperature heat treatment may be performed in a state in which the aluminum foil retains the strength obtained by work hardening at the time of foil rolling, and may be performed continuously immediately after foil rolling or at intervals after foil rolling. You can also.
こうして脱脂したアルミニウム硬箔は、例えばリチウムイオン二次電池等の電極材の正極用基材や負極用基材として用いられる。例えば、電極活物質と導電材と結着材とをペースト状に混練して電極材料とし、この電極材料を前記アルミニウム硬箔の片面または両面に１００〜２００μｍ程度の厚みにコーティングし、次いで乾燥、ロールプレス、溶剤を飛ばすための乾燥、スリット、裁断の各工程を順次的に実施して電極材が作製される。この一連の工程において、基材が軟質箔であるとロールプレス時に箔が伸びて電極活物質が剥離してしまい、電池集電体の役目を果たさない。また、電池容量を上げるためには活物質量を多くする必要があり、ロールプレス圧を上げる必要が生じる。このため、箔は高いロールプレス圧を付与しても伸びにくいことが好ましい。以上の理由により、電池電極用基材には伸びにくい硬箔を用いる必要がある。 The aluminum hard foil thus degreased is used as a positive electrode substrate or a negative electrode substrate of an electrode material such as a lithium ion secondary battery. For example, an electrode active material, a conductive material, and a binder are kneaded into a paste to form an electrode material. This electrode material is coated on one or both sides of the aluminum hard foil to a thickness of about 100 to 200 μm, and then dried. The electrode material is produced by sequentially performing each step of roll press, drying for blowing off the solvent, slitting, and cutting. In this series of steps, if the base material is a soft foil, the foil stretches during roll pressing and the electrode active material is peeled off, and does not serve as a battery current collector. Further, in order to increase the battery capacity, it is necessary to increase the amount of the active material, and it is necessary to increase the roll press pressure. For this reason, it is preferable that the foil is not easily stretched even when a high roll press pressure is applied. For the above reasons, it is necessary to use a hard foil that is difficult to stretch for the battery electrode substrate.
本発明のアルミニウム硬箔は、低温熱処理が施されて塗工性が改善されているから、コーティング工程における塗工むらの発生や活物質の厚みのばらつきを防止できるとともに、高いロールプレス圧を付与しても箔が伸びにくく活物質が剥離しにくい。ひいては電池容量の向上および充放電に対する容量安定性の向上に寄与する。また、洗浄液等の処理液を用いない単なる熱処理であるから、処理液の残留による影響もない。 Since the aluminum hard foil of the present invention has been subjected to low-temperature heat treatment to improve coating properties, it can prevent the occurrence of coating unevenness in the coating process and variation in the thickness of the active material, and provides a high roll press pressure. However, the foil is difficult to stretch and the active material is difficult to peel off. As a result, it contributes to the improvement of the battery capacity and the capacity stability against charge / discharge. In addition, since it is a simple heat treatment that does not use a processing solution such as a cleaning solution, there is no influence of the remaining processing solution.
本発明は、以下の実施例に限定されない。 The present invention is not limited to the following examples.
ＪＩＳ Ａ１０８５およびＡ３００３を用い、定法により鋳塊に熱間圧延、冷間圧延、箔圧延を経て、厚さ１５μｍのアルミニウム硬箔を製作した。箔圧延によって得られたアルミニウム硬箔はＨ１８材に相当するものである。なお、前記冷間圧延および箔圧延においては、圧延油としてケロシン系油で蒸留終点温度が３００℃以下のものを用いた。 Using JIS A1085 and A3003, an aluminum ingot having a thickness of 15 μm was manufactured through hot rolling, cold rolling and foil rolling on the ingot by a conventional method. The aluminum hard foil obtained by foil rolling corresponds to the H18 material. In the cold rolling and foil rolling, a kerosene oil having a distillation end point temperature of 300 ° C. or lower was used as the rolling oil.
これらのアルミニウム箔に対し、表１（Ａ１０８５）および表２（Ａ３００３）に示す温度および時間の熱処理を施した。熱処理は、いずれもコイルの状態でバッチ処理するものとした。 These aluminum foils were heat-treated at the temperatures and times shown in Table 1 (A1085) and Table 2 (A3003). All heat treatments were batch-treated in a coil state.
得られた箔アルミニウム硬箔について、下記のぬれ性試験によって箔表面の脱脂の度合いを評価するとともに、常法により耐力、引張強度、伸びの機械的性質を測定した。これらの結果を表１および表２に併せて示す。 About the obtained foil aluminum hard foil, while evaluating the degree of degreasing of the foil surface by the following wettability test, the mechanical properties of yield strength, tensile strength, and elongation were measured by a conventional method. These results are shown together in Tables 1 and 2.
〔ぬれ性試験〕
試験液：Ｎ−メチル−２−ピロリドン（２５℃における表面張力が０．４１Ｎ／ｍ）０．００５ｃｃを注射器により箔表面に滴下し、液滴の接触角を接触角測定器を用いて測定した。試験液の滴下は、垂直方向に配置した注射器の先端に対して水平に配置した箔を下方から近接させ（箔を下方から上昇させ）、注射器に接触させることなく注射器から排出された試験液の液端が触れたら停止し、約０．５秒後に箔を下降させることにより行う。このように液滴接触後約０．５秒間静止することにより、注射器内部への試験液の残留が防がれ、箔表面に正確な量の液滴を滴下して接触角の測定を正確に行うことができる。
[Wettability test]
Test solution: 0.005 cc of N-methyl-2-pyrrolidone (surface tension at 25 ° C. of 0.41 N / m) was dropped onto the foil surface with a syringe, and the contact angle of the droplet was measured using a contact angle measuring device. . Dropping of the test solution is performed by placing the foil placed horizontally against the tip of the syringe placed in the vertical direction from the lower side (raising the foil from below) and discharging the test solution discharged from the syringe without touching the syringe. Stop by touching the liquid end, and lower the foil after about 0.5 seconds. In this way, by resting for about 0.5 seconds after droplet contact, test liquid remains inside the syringe, and an accurate amount of droplet is dropped on the foil surface to accurately measure the contact angle. It can be carried out.
表１および表２に示すように、所定条件で低温熱処理することによって、熱処理をしない比較例１，１１と比較して、機械的性質を低下させることなく脱脂することができた。一方、８０℃未満または１時間未満の加熱処理では脱脂されなかった。また、１６０℃を超える温度で熱処理した比較例４〜７，１４〜１７では、脱脂されたものの機械的性質が低下した。 As shown in Tables 1 and 2, it was possible to degrease without lowering mechanical properties by performing low temperature heat treatment under a predetermined condition as compared with Comparative Examples 1 and 11 in which heat treatment was not performed. On the other hand, it was not degreased by heat treatment of less than 80 ° C. or less than 1 hour. Moreover, in Comparative Examples 4-7 and 14-17 which heat-processed at the temperature exceeding 160 degreeC, although the degreasing | defatting, the mechanical property fell.
さらに、各アルミニウム硬箔を電極用基材とするリチウムイオン二次電池の正極材（電極材）を製作した。 Furthermore, the positive electrode material (electrode material) of the lithium ion secondary battery which uses each aluminum hard foil as a base material for electrodes was manufactured.
まず、ＬｉＣｏＯ2等の活物質とカーボン等の導電材とＰＶＤ等の結着材とをペースト状に混練して正極材料（電極材料）を作った。そして、この正極材料を上記アルミニウム硬箔の両面に１００μｍの厚みにコーティングした。コーティングは、図１に示すように、箔の圧延方向（長手方向）に沿って塗工部(2)と未塗工部とを交互に形成するものとした。 First, an active material such as LiCoO 2 , a conductive material such as carbon, and a binder such as PVD were kneaded into a paste to produce a positive electrode material (electrode material). And this positive electrode material was coated by the thickness of 100 micrometers on both surfaces of the said aluminum hard foil. As shown in FIG. 1, the coating is such that the coated part (2) and the uncoated part are alternately formed along the rolling direction (longitudinal direction) of the foil.
コーティング後、２００℃×３０分乾燥した。乾燥後、塗工部(2)を観察したところ、各実施例では図２、３に示すような境界部(2a)の湾曲や縁部(2b)の盛り上がりは認められなかった。一方、比較例１〜３および比較例１１〜１３の脱脂が不十分であった箔においては湾曲や盛り上がりが認められた。 After coating, it was dried at 200 ° C. for 30 minutes. After drying, the coated part (2) was observed, and in each example, the bending of the boundary part (2a) and the rising of the edge part (2b) as shown in FIGS. On the other hand, in the foils in which the degreasing of Comparative Examples 1 to 3 and Comparative Examples 11 to 13 was insufficient, bending and swelling were observed.
さらに、実施例１〜２１のアルミニウム硬箔に対し、プレス、スリット、裁断の各工程を実施してリチウムイオン二次電池の正極材を得た。そして、これらの正極材と、リチウム箔の負極と、炭酸プロピレン（ＰＣ）と炭酸ジメチル（ＤＭＣ）を体積比で１：２の割合で混合した非水系電解液にＬｉＰＦ6を１モル／リットルの濃度で溶解したものを電解液として用い、アルミニウムラミネート袋を外装袋とした非水系二次電池（以下、ラミ袋電池と記載）を組み立てた。 Furthermore, each step of pressing, slitting, and cutting was performed on the aluminum hard foils of Examples 1 to 21 to obtain a positive electrode material for a lithium ion secondary battery. Then, LiPF 6 was added at 1 mol / liter to a non-aqueous electrolyte obtained by mixing these positive electrode materials, a lithium foil negative electrode, propylene carbonate (PC) and dimethyl carbonate (DMC) at a volume ratio of 1: 2. A non-aqueous secondary battery (hereinafter referred to as a lami bag battery) having an aluminum laminate bag as an outer bag was assembled using an electrolyte solution dissolved at a concentration.
得られたラミ袋電池に対し、充放電サイクル試験を実施した。試験の条件として、充放電レート１Ｃ（クーロン）、電圧範囲３．１〜４．３Ｖに設定し、３０サイクル充放電を繰り返したところ、容量変化は見られず、良好なサイクル特性が確認された。 A charge / discharge cycle test was performed on the resulting laminated bag battery. As test conditions, a charge / discharge rate of 1 C (coulomb) and a voltage range of 3.1 to 4.3 V were set, and when 30 cycles of charge and discharge were repeated, no change in capacity was observed, and good cycle characteristics were confirmed. .
１…アルミニウム硬箔
２…塗工部
1 ... Aluminum
Claims (3)
The method for degreasing an aluminum hard foil according to claim 1 or 2, wherein the thickness of the aluminum foil is 4 to 50 µm.
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| JP5100441B2 (en) * | 2008-02-26 | 2012-12-19 | 株式会社東芝 | Non-aqueous electrolyte battery |
| JP5498386B2 (en) * | 2008-09-09 | 2014-05-21 | パナソニック株式会社 | Method for producing positive electrode for non-aqueous electrolyte secondary battery and method for producing non-aqueous electrolyte secondary battery |
| JP5495649B2 (en) * | 2009-07-24 | 2014-05-21 | 株式会社Ｕａｃｊ製箔 | Aluminum alloy foil for lithium ion secondary battery and method for producing the same |
| JP5495694B2 (en) * | 2009-09-30 | 2014-05-21 | 株式会社Ｕａｃｊ製箔 | Aluminum alloy foil for lithium ion secondary battery and method for producing the same |
| JP5771436B2 (en) * | 2011-04-25 | 2015-08-26 | 株式会社Uacj | Aluminum foil for current collector |
| JP6051213B2 (en) * | 2011-06-21 | 2016-12-27 | ハイドロ アルミニウム ロールド プロダクツ ゲゼルシャフト ミット ベシュレンクテル ハフツングＨｙｄｒｏ Ａｌｕｍｉｎｉｕｍ Ｒｏｌｌｅｄ Ｐｒｏｄｕｃｔｓ ＧｍｂＨ | Chemically treated aluminum or aluminum alloy current collector foil |
| JP5947593B2 (en) * | 2012-03-30 | 2016-07-06 | 三菱アルミニウム株式会社 | Method for producing aluminum foil for positive electrode current collector of lithium ion secondary battery |
| JP5567719B2 (en) * | 2012-07-26 | 2014-08-06 | 三菱アルミニウム株式会社 | Method for producing aluminum alloy foil for positive electrode current collector of lithium ion secondary battery, aluminum alloy foil for lithium ion secondary battery positive electrode current collector and lithium ion secondary battery |
| JP6003559B2 (en) * | 2012-11-15 | 2016-10-05 | 株式会社豊田自動織機 | Electrode manufacturing method |
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| JP6124076B2 (en) * | 2013-11-21 | 2017-05-10 | 株式会社豊田自動織機 | Method for forming protective layer on aluminum foil, current collector for lithium ion secondary battery, and lithium ion secondary battery |
| JP6120087B2 (en) * | 2013-12-19 | 2017-04-26 | 株式会社豊田自動織機 | Method for forming protective layer on current collector body, current collector for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| JP6338104B2 (en) * | 2014-08-06 | 2018-06-06 | 株式会社豊田自動織機 | Positive electrode for lithium ion secondary battery and method for producing the same, lithium ion secondary battery and method for producing the same |
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| WO2023157981A1 (en) * | 2022-02-21 | 2023-08-24 | パナソニックエナジー株式会社 | Nonaqueous electrolyte secondary battery positive electrode and nonaqueous electrolyte secondary battery |
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