JP2015032554A - Method for producing negative electrode for lithium ion secondary battery - Google Patents
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Abstract
【課題】本発明は、負極活物質の割れや欠けを抑制して、リチウムイオン二次電池の電池特性を向上できる、リチウムイオン二次電池用負極の製造方法を提供する。
【解決手段】負極活物質と、増粘剤と、溶媒とを混合して造粒体を得る湿潤工程と、前記造粒体を混練機に投入して固練りする固練り工程と、前記固練り工程にて固練りした混練物に溶媒を添加して希釈する希釈工程とを有する、リチウムイオン二次電池用負極の製造方法であって、前記負極活物質の亜麻仁油吸油量が、３５ｍｌ／１００ｇ以上である。
【選択図】図１The present invention provides a method for producing a negative electrode for a lithium ion secondary battery, which can improve the battery characteristics of the lithium ion secondary battery by suppressing cracking and chipping of the negative electrode active material.
A wet process for obtaining a granulated body by mixing a negative electrode active material, a thickener, and a solvent, a kneading process for putting the granulated body into a kneader and kneading, and the solid process A method for producing a negative electrode for a lithium ion secondary battery, wherein the negative electrode active material has a linseed oil absorption of 35 ml / 100 g or more.
[Selection] Figure 1
Description
本発明は、負極活物質の割れを抑制することができるリチウムイオン二次電池用負極の製造方法に関する。 The present invention relates to a method for producing a negative electrode for a lithium ion secondary battery that can suppress cracking of a negative electrode active material.
従来、リチウムイオン二次電池においては、例えば負極は、負極活物質、増粘剤および結着剤を含むペースト状の負極合材を負極用の集電体に塗布して乾燥させることにより作製されており、前記ペースト状の負極合材は、図２に示すように、負極活物質、増粘剤および溶媒の混合物を混練する固練り工程、ならびに前記固練り工程にて得られた混練物に結着剤および溶媒を加えて前記混練物を希釈するとともに、前記混練物中に前記負極活物質を分散させる希釈・分散工程とを経て構成されている。 Conventionally, in a lithium ion secondary battery, for example, a negative electrode is produced by applying a paste-like negative electrode mixture containing a negative electrode active material, a thickener, and a binder to a negative electrode current collector and drying it. As shown in FIG. 2, the paste-like negative electrode mixture is mixed into a kneading step for kneading a mixture of a negative electrode active material, a thickener and a solvent, and a kneaded product obtained in the kneading step. The kneaded product is diluted by adding a binder and a solvent, and is subjected to a dilution / dispersing step in which the negative electrode active material is dispersed in the kneaded product.
また、電極を高密度化してリチウムイオン二次電池の高容量化を図るため、および電極合材ペーストの生産能力を向上するために、高せん断力にて電極合材材料の混練を行って電極合材ペーストを作製することが行われている。
高せん断力にて混練を行って電極合材ペーストを作製する方法としては、例えば活物質、導電助材、結着剤、および溶媒といった電極合材材料を連続式二軸混練機に投入し、前記連続式二軸混練機の混練部にてこれらの各材料を混練することが、特許文献１に開示されている。
In addition, in order to increase the density of the electrode to increase the capacity of the lithium ion secondary battery and to improve the production capacity of the electrode mixture paste, the electrode mixture material is kneaded with a high shear force and the electrode is mixed. Preparation of a composite paste is performed.
As a method of preparing an electrode mixture paste by kneading with high shear force, for example, an electrode mixture material such as an active material, a conductive additive, a binder, and a solvent is put into a continuous biaxial kneader, Patent Document 1 discloses that these materials are kneaded in a kneading section of the continuous biaxial kneader.
しかし、前述のように電極合材材料の混練を、連続式二軸混練機を用いて高せん断力にて行う場合、例えば負極合材ペーストを作製する際には、電極合材材料として用いられる活物質や増粘剤は粉体の状態で連続式二軸混練機に投入されており、活物質が溶媒に十分湿潤されていない状態で混練部に導入されることとなる。
そして、活物質が溶媒に十分湿潤されていない状態で前記混練部での混練が開始されると、混練初期において湿潤が不十分な活物質に大きなせん断力がかかり、活物質に割れや欠けが生じ易くなる。活物質に割れや欠けが生じると、活物質の活性が高くなり、リチウムイオン二次電池のサイクル特性（充放電サイクル後の容量維持率）等の電池特性が悪化するといった問題が発生する。
However, as described above, when the electrode mixture material is kneaded with a high shear force using a continuous biaxial kneader, for example, when preparing a negative electrode mixture paste, it is used as an electrode mixture material. The active material and the thickener are put into a continuous biaxial kneader in the form of powder, and the active material is introduced into the kneading part in a state where the active material is not sufficiently wetted with the solvent.
Then, when kneading in the kneading part is started in a state where the active material is not sufficiently wetted with the solvent, a large shearing force is applied to the active material that is insufficiently wet in the initial stage of kneading, and the active material is not cracked or chipped. It tends to occur. When the active material is cracked or chipped, the activity of the active material is increased, resulting in a problem that battery characteristics such as cycle characteristics (capacity maintenance ratio after charge / discharge cycle) of the lithium ion secondary battery are deteriorated.
そこで、本発明においては、負極活物質の割れや欠けを抑制して、リチウムイオン二次電池の電池特性を向上することができる、リチウムイオン二次電池用負極の製造方法を提供するものである。 Therefore, the present invention provides a method for producing a negative electrode for a lithium ion secondary battery, which can improve the battery characteristics of the lithium ion secondary battery by suppressing cracking and chipping of the negative electrode active material. .
上記課題を解決するリチウムイオン二次電池用負極の製造方法は、以下の特徴を有する。
即ち、請求項１記載の如く、負極活物質と、増粘剤と、溶媒とを混合して造粒体を得る湿潤工程と、前記造粒体を混練機に投入して固練りする固練り工程と、前記固練り工程にて固練りした混練物に溶媒を添加して希釈する希釈工程とを有する、リチウムイオン二次電池用負極の製造方法であって、前記負極活物質の亜麻仁油吸油量が、３５ｍｌ／１００ｇ以上である。
The manufacturing method of the negative electrode for lithium ion secondary batteries which solves the said subject has the following characteristics.
That is, as described in claim 1, a wetting step of mixing a negative electrode active material, a thickener, and a solvent to obtain a granulated body, and a kneading process in which the granulated body is put into a kneader and kneaded. And a method for producing a negative electrode for a lithium ion secondary battery, the method comprising: a dilution step of adding a solvent to the kneaded material kneaded in the kneading step and diluting, wherein linseed oil absorption of the negative electrode active material The amount is 35 ml / 100 g or more.
また、請求項２記載の如く、前記負極活物質の亜麻仁油吸油量が、６５ｍｌ／１００ｇ以下である。 According to a second aspect of the present invention, the linseed oil absorption of the negative electrode active material is 65 ml / 100 g or less.
本発明によれば、負極活物質の割れや欠けを抑制して、リチウムイオン二次電池の電池特性を向上することができる。 According to the present invention, it is possible to improve the battery characteristics of the lithium ion secondary battery by suppressing cracking and chipping of the negative electrode active material.
次に、本発明を実施するための形態を、添付の図面を用いて説明する。 Next, modes for carrying out the present invention will be described with reference to the accompanying drawings.
図１には、本発明に係るリチウムイオン二次電池用負極の製造方法を用いた、リチウムイオン二次電池の負極合材ペーストの製造工程を示している。
図１に示す負極合材ペーストの製造工程においては、まず負極活物質と増粘剤と溶媒とを混合して造粒体を生成する。
負極活物質としては、例えば黒鉛を用いることができ、増粘剤としては、例えばＣＭＣ（カルボキシメチルセルロース）を用いることができ、溶媒としては、例えば水を用いることができる。
In FIG. 1, the manufacturing process of the negative mix paste of a lithium ion secondary battery using the manufacturing method of the negative electrode for lithium ion secondary batteries which concerns on this invention is shown.
In the manufacturing process of the negative electrode mixture paste shown in FIG. 1, first, a negative electrode active material, a thickener, and a solvent are mixed to produce a granulated body.
For example, graphite can be used as the negative electrode active material, CMC (carboxymethyl cellulose) can be used as the thickener, and water can be used as the solvent, for example.
前記造粒体の生成は、攪拌機の容器内に負極活物質、増粘剤、および溶媒を投入して攪拌することにより行われる。前記攪拌機としては、例えば、攪拌容器内に回転駆動可能な攪拌羽を備えたハイスピードミキサを用いることができる。
負極活物質、増粘剤、および溶媒の混合物を攪拌して造粒することにより、負極活物質は溶媒である水により十分に湿潤した状態となる。
また、生成された造粒体は、ペンデュラー状態となっている。ここで、「ペンデュラー状態」とは、「粉体（負極活物質および増粘剤）同士が接触し、かつ空気が連続相で液体が不連続相にある状態」をいう。
The granulated body is produced by introducing a negative electrode active material, a thickener and a solvent into a container of a stirrer and stirring. As the stirrer, for example, a high-speed mixer provided with a stirring blade that can be rotationally driven in a stirring vessel can be used.
By stirring and granulating the mixture of the negative electrode active material, the thickener, and the solvent, the negative electrode active material is sufficiently wetted with water as a solvent.
Moreover, the produced | generated granulated body is a pendulum state. Here, the “pendular state” refers to “a state in which powders (negative electrode active material and thickener) are in contact with each other, air is in a continuous phase, and liquid is in a discontinuous phase”.
このように、負極合材ペーストの製造工程では、まず負極合材材料である負極活物質と、増粘剤と、溶媒とを混合して造粒体を得て、前記造粒体における負極活物質を湿潤状態とする湿潤工程（Ｓ１）が実施される。 Thus, in the process for producing the negative electrode mixture paste, first, a negative electrode active material that is a negative electrode mixture material, a thickener, and a solvent are mixed to obtain a granulated body, and the negative electrode active material in the granulated body is obtained. A wetting step (S1) for bringing the substance into a wet state is performed.
次に、負極合材ペーストの製造工程では、得られた造粒体を混練する混練工程（Ｓ２）が実施される。混練工程は混練機を用いて行われ、前記混練機としては、例えば連続式二軸混練機を用いることができる。
連続式二軸混練機は、外装をなす中空のバレルと、当該バレルの内部に互いに平行に設けられた二つの回転軸と、当該回転軸に設けられ、前記バレルの内部に投入された材料を混練するための複数のパドルとを具備する混練機である。
Next, in the production process of the negative electrode mixture paste, a kneading step (S2) for kneading the obtained granulated body is performed. The kneading step is performed using a kneader, and as the kneader, for example, a continuous biaxial kneader can be used.
The continuous twin-screw kneader is a hollow barrel that forms an exterior, two rotary shafts provided in parallel to each other inside the barrel, and a material that is provided in the rotary shaft and is charged into the barrel. A kneading machine including a plurality of paddles for kneading.
前記混練工程は、前記造粒体を固練りする固練り工程（Ｓ２１）と、固練りされた混練物を希釈する希釈工程（Ｓ２２）とを有する。
前記固練り工程では、前記造粒体と溶媒である水とを混練機に投入して混練することにより、固練りが行われる。固練りが行われた混練物は、ファニキュラー状態となっている。ここで、「ファニキュラー状態」とは、「液体が連続相であるが空気が存在して粉末同士も接触している状態」をいう。
The kneading step includes a kneading step (S21) for kneading the granulated body and a dilution step (S22) for diluting the kneaded kneaded product.
In the kneading step, the kneading is performed by putting the granulated body and water as a solvent into a kneader and kneading. The kneaded product that has been kneaded is in a funicular state. Here, the “funicular state” means “a state in which the liquid is a continuous phase but air is present and the powders are in contact with each other”.
希釈工程では、前記固練り工程にて固練りされた混練物が投入されている混練機に、負極合材材料である結着剤と、溶媒である水とをさらに投入して混練することにより、前記混練物の希釈、および負極活物質の分散が行われる。前記混練物が希釈工程を経ることにより、スラリー状の負極合材である負極合材ペーストが生成される。
希釈工程を経て生成された負極合材ペーストにおいては、負極活物質が均一に分散している。また、希釈工程を経て得られた負極合材ペーストは、スラリー状態となっている。ここで、「スラリー状態」とは、「液体中に粉末が懸濁した状態で流動性を示す状態をいう。
これらの湿潤工程、固練り工程、および希釈工程を経て生成された負極合材ペーストを負極集電体に塗着して乾燥することで、リチウムイオン電池用負極板が製造される。
In the diluting step, the binder, which is the negative electrode mixture material, and the water, which is the solvent, are further added to the kneader in which the kneaded material kneaded in the kneading step is added, and kneaded. The kneaded product is diluted and the negative electrode active material is dispersed. When the kneaded material undergoes a dilution step, a negative electrode mixture paste that is a slurry-like negative electrode mixture is generated.
In the negative electrode mixture paste produced through the dilution step, the negative electrode active material is uniformly dispersed. Moreover, the negative electrode mixture paste obtained through the dilution step is in a slurry state. Here, “slurry state” means “a state in which fluidity is exhibited in a state where powder is suspended in a liquid.
A negative electrode plate for a lithium ion battery is manufactured by applying the negative electrode mixture paste produced through these wetting step, kneading step, and dilution step to a negative electrode current collector and drying it.
なお、希釈工程にて混練機に投入される結着剤としては、例えばスチレン−ブタジエンゴム（ＳＢＲ）を用いることができる。
また、前記希釈工程は、固練り工程での混練物が投入されている混練機を用いて、固練り工程に連続して実施することが可能である。
In addition, as a binder thrown into a kneading machine at a dilution process, a styrene-butadiene rubber (SBR) can be used, for example.
Moreover, the said dilution process can be implemented continuously to a kneading process using the kneader in which the kneaded material in the kneading process is thrown.
このように、本実施形態におけるリチウムイオン二次電池用負極の製造方法を用いた負極合材ペーストの製造工程では、負極活物質を溶媒に湿潤させて造粒体を生成する湿潤工程、前記造粒体に溶媒を加えて固練りする固練り工程、および固練りした混練物に溶媒を加えて希釈する希釈工程の３つの工程を経て負極合材ペーストを製造している。つまり、負極活物質を前記湿潤工程にて湿潤状態としたうえで混練機に投入して固練り工程を開始している、即ち負極活物質等の電極合材材料を混練機にて混練する前に負極活物質の溶媒による湿潤を行っているため、負極活物質の割れや欠けを抑制して、リチウムイオン二次電池のサイクル特性等の電池特性の悪化を防止することが可能となっている。
この場合、混練機により負極活物質に付与されるせん断力を低減する等の処置を講じることなく、負極活物質の割れや欠けを抑制することができるので、負極合材ペーストの生産性が低下することもない。
Thus, in the manufacturing process of the negative electrode mixture paste using the negative electrode manufacturing method for a lithium ion secondary battery in the present embodiment, a wetting process in which the negative electrode active material is wetted with a solvent to generate a granulated body, The negative electrode mixture paste is manufactured through three steps: a kneading step in which a solvent is added to the granules and kneaded, and a dilution step in which the solvent is added to the kneaded kneaded product to dilute. That is, after the negative electrode active material is wetted in the wet step, the solid kneading step is started by adding it to the kneader, that is, before the electrode mixture material such as the negative electrode active material is kneaded in the kneader. In addition, since the negative electrode active material is wetted with the solvent, it is possible to prevent cracking and chipping of the negative electrode active material and prevent deterioration of battery characteristics such as cycle characteristics of the lithium ion secondary battery. .
In this case, since the cracking and chipping of the negative electrode active material can be suppressed without taking measures such as reducing the shearing force applied to the negative electrode active material by the kneader, the productivity of the negative electrode mixture paste is reduced. I don't have to.
また、混練機での混練の前に負極活物質を溶媒に湿潤させることにより、負極活物質の割れや欠けを抑制する効果は、せん断力が大きな連続式二軸混練機にて混練を行う場合に顕著であるが、プラネタリーミキサーにて混練を行う場合にも、負極活物質の割れや欠けの抑制効果を奏することが可能である。 Moreover, the effect of suppressing cracking and chipping of the negative electrode active material by wetting the negative electrode active material in a solvent before kneading in the kneader is effective when the kneading is performed in a continuous biaxial kneader having a large shear force Although it is remarkable, even when kneading with a planetary mixer, the effect of suppressing cracking and chipping of the negative electrode active material can be exhibited.
また、負極合材ペーストの負極活物質として用いる黒鉛は、亜麻仁油の吸油量が３５ｍｌ／１００ｇ以上であるものを用いるようにしている。
これは、黒鉛の亜麻仁油の吸油量が３５ｍｌ／１００ｇよりも少ないと、黒鉛におけるＣＭＣの吸着サイトが少なくなり、混練機による混練時に黒鉛に割れや欠けが発生し易くなるためである。
亜麻仁油の吸油量が３５ｍｌ／１００ｇ以上である黒鉛を負極活物質として用いることで、前記負極合材ペーストの製造工程における混練機による混練時に、黒鉛に割れや欠けが発生することを効果的に抑制することができる。
Moreover, the graphite used as the negative electrode active material of the negative electrode mixture paste is such that the amount of linseed oil absorbed is 35 ml / 100 g or more.
This is because if the amount of graphite linseed oil absorbed is less than 35 ml / 100 g, the number of CMC adsorption sites in the graphite decreases, and cracking and chipping tend to occur in the graphite during kneading with a kneader.
By using graphite having an oil absorption of linseed oil of 35 ml / 100 g or more as a negative electrode active material, it is possible to effectively cause cracks and chips in the graphite during kneading by a kneader in the production process of the negative electrode mixture paste. Can be suppressed.
但し、黒鉛の亜麻仁油の吸油量が６５ｍｌ／１００ｇを越えると、黒鉛におけるＣＭＣの吸着サイトが多くなり過ぎるため、当該負極合材ペーストを用いたリチウムイオン二次電池の反応抵抗が高くなって、放電特性等の電池特性が悪化するおそれがある。
従って、負極活物質として用いる黒鉛の亜麻仁油の吸油量は、６５ｍｌ／１００ｇ以下とすることが好ましい。
However, if the amount of graphite linseed oil absorbed exceeds 65 ml / 100 g, the number of CMC adsorption sites in the graphite becomes excessive, so the reaction resistance of the lithium ion secondary battery using the negative electrode mixture paste increases, Battery characteristics such as discharge characteristics may be deteriorated.
Therefore, the oil absorption amount of the linseed oil of graphite used as the negative electrode active material is preferably 65 ml / 100 g or less.
また、負極活物質として用いる黒鉛の亜麻仁油の吸油量は、リチウムイオン二次電池の電池特性を考慮すると、４５ｍｌ／１００ｇ以上、かつ５５ｍｌ／１００ｇ以下とすることが、さらに好ましい。
さらに、このような負極活物質を用いて生成される負極合材ペーストは、固形分率を５４％〜６２％の範囲内に設定することが好ましい。
In addition, the oil absorption of graphite linseed oil used as the negative electrode active material is more preferably 45 ml / 100 g or more and 55 ml / 100 g or less in consideration of the battery characteristics of the lithium ion secondary battery.
Furthermore, it is preferable that the negative electrode mixture paste produced using such a negative electrode active material has a solid content within a range of 54% to 62%.
なお、黒鉛の亜麻仁油の吸油量の測定は、次のようにして行う。
つまり、所定量の負極活物質に亜麻仁油を一定速度で滴下して吸油させながら混練する。すると、油の滴下量の増加に応じて混練時のトルクが上昇していくが、やがて油の滴下量が増加してもトルクが上昇せずに一定となる。このトルクが上昇しなくなって一定となったときのトルク値を最大トルクとし、負極活物質への油の滴下を開始してからトルクが最大トルクとなるまでの間で、最大トルクの７０％のトルクを生じた時点での負極活物質への油の滴下量を、吸油量として測定する。
In addition, the measurement of the oil absorption amount of graphite linseed oil is performed as follows.
In other words, linseed oil is dropped into a predetermined amount of the negative electrode active material at a constant speed and kneaded while absorbing the oil. Then, the torque at the time of kneading increases as the amount of oil dripping increases, but even if the amount of oil dripping eventually increases, the torque does not increase and becomes constant. The torque value when the torque stops increasing and becomes constant is set as the maximum torque, and 70% of the maximum torque from when the oil starts dropping to the negative electrode active material until the torque reaches the maximum torque. The amount of oil dripped onto the negative electrode active material at the time when torque is generated is measured as the amount of oil absorption.
また、本実施形態における負極合材ペーストの製造工程にて負極合材ペーストを製造した場合、黒色度が１〜５の負極合材ペーストを得ることができる。
負極合材ペーストの黒色度とは、当該負極合材ペーストが含有する負極活物質の割れや欠けの度合いの指標となるものであり、値が小さいほど負極活物質の割れや欠けが少ないことを意味する。そして、黒色度が１〜５の負極合材ペーストを用いて負極を構成することで、良好な電池特性のリチウムイオン二次電池を得ることが可能となる。
Moreover, when the negative electrode mixture paste is manufactured in the manufacturing process of the negative electrode mixture paste in the present embodiment, a negative electrode mixture paste having a blackness of 1 to 5 can be obtained.
The blackness of the negative electrode mixture paste is an index of the degree of cracking or chipping of the negative electrode active material contained in the negative electrode mixture paste, and the smaller the value, the fewer the cracking or chipping of the negative electrode active material. means. And it becomes possible to obtain the lithium ion secondary battery of a favorable battery characteristic by comprising a negative electrode using the negative mix paste of 1-5 blackness.
なお、負極合材ペーストの黒色度は、以下のようにして測定する。
例えば、ペースト状の負極合材を重量で１０倍に希釈したものを、１５０００ｒｐｍで３０分間遠心分離し、当該負極合材ペーストから遊離する負極活物質および増粘剤を含む上澄み液を回収し、回収した上澄み液をさらに溶媒で体積で５倍に希釈し、希釈した前記上澄み液の４００ｎｍ〜７００ｎｍの波長領域における吸光スペクトルを測定し、当該波長領域の吸光度（０〜１）の値の平均値を５倍したものを、黒色度として測定する。
The blackness of the negative electrode mixture paste is measured as follows.
For example, a paste-like negative electrode mixture diluted 10 times by weight is centrifuged at 15000 rpm for 30 minutes, and the supernatant liquid containing the negative electrode active material and the thickener released from the negative electrode mixture paste is recovered. The recovered supernatant is further diluted 5 times by volume with a solvent, the absorption spectrum in the 400 nm to 700 nm wavelength region of the diluted supernatant is measured, and the average value of the absorbance (0 to 1) in the wavelength region is measured. Is measured as blackness.
次に、本願発明に係る実施例について説明する。
本実施例においては、表１に示すような実施例１〜６に係る負極合材ペーストおよび負極板を作製し、負極活物質の割れ状態、および電池特性の評価を行った。また、比較例１〜５に係る負極合材ペーストおよび負極板を作製し、同様の評価を行った。
Next, examples according to the present invention will be described.
In this example, negative electrode mixture pastes and negative electrode plates according to Examples 1 to 6 as shown in Table 1 were prepared, and the cracked state of the negative electrode active material and battery characteristics were evaluated. Moreover, the negative mix paste and negative electrode plate which concern on Comparative Examples 1-5 were produced, and the same evaluation was performed.
[実施例１]
実施例１に係る負極合材ペーストは、負極活物質として亜麻仁油の吸油量が４５ｍｌ／１００ｇの黒鉛を用い、増粘剤としてＣＭＣを用い、溶媒として水を用いて作成した。
負極合材ペーストの作成においては、まず９８重量部の黒鉛、１重量部のＣＭＣ、および３７重量部の水からなる混合物を、ハイスピードミキサを用いて攪拌することにより造粒する、湿潤工程を実施して造粒体を得た。この造粒体はペンデュラー状態となっている。
次に、１３６重量部の前記造粒体と１８重量部の水とを連続式二軸混練機の上流部に投入して混練することで固練りを行う、固練り工程を実施した。固練り工程が実施された混練物は、ファニキュラー状態となっている。
次に、連続式二軸混練機の下流部にて、前記混練物に３０重量部の水を加えて希釈し、さらに、１重量部（固形分で）のＳＢＲを加えて混練することにより希釈工程を実施し、負極合材ペーストを得た。得られた負極合材ペーストの固形分は５４％であった。
さらに、得られた負極合材ペーストを集電体となる銅箔に塗布し乾燥することで、負極板を作製した。
[Example 1]
The negative electrode mixture paste according to Example 1 was prepared using graphite having a linseed oil absorption of 45 ml / 100 g as a negative electrode active material, CMC as a thickener, and water as a solvent.
In preparation of the negative electrode mixture paste, first, a wet process is performed in which a mixture of 98 parts by weight of graphite, 1 part by weight of CMC, and 37 parts by weight of water is granulated by stirring using a high speed mixer. It was carried out to obtain a granulated body. This granulated body is in a pendulum state.
Next, a kneading step was performed in which 136 parts by weight of the granulated body and 18 parts by weight of water were put into the upstream part of the continuous biaxial kneader and kneaded to perform kneading. The kneaded product subjected to the solidifying step is in a funicular state.
Next, in the downstream part of the continuous twin-screw kneader, 30 parts by weight of water is added to the kneaded product to dilute, and further, 1 part by weight (in solid content) of SBR is added to dilute. The process was implemented and the negative electrode compound paste was obtained. The obtained negative electrode mixture paste had a solid content of 54%.
Furthermore, the obtained negative electrode mixture paste was applied to a copper foil serving as a current collector and dried to prepare a negative electrode plate.
[実施例２]
負極活物質として亜麻仁油の吸油量が３５ｍｌ／１００ｇの黒鉛を用い、固練り工程において連続式二軸混練機に投入する水を９重量部とし、希釈工程において加える水を３９重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は５４％であった。
[Example 2]
In addition to graphite with linseed oil absorption of 35 ml / 100 g as the negative electrode active material, 9 parts by weight of water to be added to the continuous biaxial kneader in the kneading process and 39 parts by weight of water added in the dilution process Produced a negative electrode mixture paste and a negative electrode plate in the same manner as in Example 1. The obtained negative electrode mixture paste had a solid content of 54%.
[実施例３]
負極活物質として亜麻仁油の吸油量が５５ｍｌ／１００ｇの黒鉛を用い、固練り工程において連続式二軸混練機に投入する水を２８重量部とし、希釈工程において加える水を２１重量部とし、希釈工程において加えるＳＢＲを２重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は５４％であった。
[Example 3]
Using graphite with linseed oil absorption of 55 ml / 100 g as the negative electrode active material, 28 parts by weight of water added to the continuous twin-screw kneader in the kneading step and 21 parts by weight of water added in the dilution step are diluted. A negative electrode mixture paste and a negative electrode plate were produced in the same manner as in Example 1 except that 2 parts by weight of SBR added in the process was changed. The obtained negative electrode mixture paste had a solid content of 54%.
[実施例４]
負極活物質として亜麻仁油の吸油量が６５ｍｌ／１００ｇの黒鉛を用い、固練り工程において連続式二軸混練機に投入する水を３９重量部とし、希釈工程において加える水を９重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は５４％であった。
[Example 4]
Graphite with a linseed oil absorption of 65 ml / 100 g was used as the negative electrode active material. The amount of water added to the continuous twin-screw kneader in the solidification process was 39 parts by weight, and the amount of water added in the dilution process was 9 parts by weight. Produced a negative electrode mixture paste and a negative electrode plate in the same manner as in Example 1. The obtained negative electrode mixture paste had a solid content of 54%.
[実施例５]
固練り工程において連続式二軸混練機に投入する水を１３重量部とし、希釈工程において加える水を２２重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は５８％であった。
実施例５における負極合材ペーストの固形分は５８％と実施例１の負極合材ペーストに比べて固形分割合が高かったため、負極板作成時に要した負極合材ペーストの乾燥時間が実施例１の場合よりも短かった。
[Example 5]
A negative electrode mixture paste and a negative electrode plate were prepared in the same manner as in Example 1 except that 13 parts by weight of water was added to the continuous twin-screw kneader in the solidifying process and 22 parts by weight of water was added in the dilution process. did. The obtained negative electrode composite paste had a solid content of 58%.
Since the solid content of the negative electrode mixture paste in Example 5 was 58%, which was higher than that of the negative electrode mixture paste of Example 1, the drying time of the negative electrode mixture paste required for preparing the negative electrode plate was Example 1. It was shorter than the case.
[実施例６]
固練り工程において連続式二軸混練機に投入する水を９重量部とし、希釈工程において加える水を１５重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は６２％であった。
実施例６における負極合材ペーストの固形分は６２％と実施例１の負極合材ペーストに比べて固形分割合が高かったため、負極板作成時に要した負極合材ペーストの乾燥時間が実施例１の場合よりも短かった。
[Example 6]
A negative electrode mixture paste and a negative electrode plate were produced in the same manner as in Example 1 except that the amount of water added to the continuous twin-screw kneader in the solidifying step was 9 parts by weight and the amount of water added in the dilution step was 15 parts by weight. did. The obtained negative electrode mixture paste had a solid content of 62%.
Since the solid content of the negative electrode mixture paste in Example 6 was 62%, which was higher than that of the negative electrode mixture paste of Example 1, the drying time of the negative electrode mixture paste required at the time of preparing the negative electrode plate was Example 1. It was shorter than the case.
[比較例１]
比較例１に係る負極合材ペーストは、負極活物質として亜麻仁油の吸油量が４５ｍｌ／１００ｇの黒鉛を用い、増粘剤としてＣＭＣを用い、溶媒として水を用いて作成した。
負極合材ペーストの作成においては、まず９８重量部の黒鉛、１重量部のＣＭＣ、および５５重量部の水を連続式二軸混練機の上流部に投入して混練することにより、固練り工程を実施した。つまり、黒鉛、ＣＭＣ、および水を、造粒することなく連続式二軸混練機にて固練りした。固練り工程が実施された混練物は、ファニキュラー状態となっている。
次に、連続式二軸混練機の下流部にて、前記混練物に３０重量部の水を加えて希釈し、さらに、１重量部（固形分で）のＳＢＲを加えて混練することにより希釈工程を実施し、負極合材ペーストを得た。得られた負極合材ペーストの固形分は５４％であった。
さらに、得られた負極合材ペーストを集電体となる銅箔に塗布し乾燥することで、負極板を作製した。
[Comparative Example 1]
The negative electrode mixture paste according to Comparative Example 1 was prepared using graphite having a linseed oil absorption of 45 ml / 100 g as a negative electrode active material, CMC as a thickener, and water as a solvent.
In the preparation of the negative electrode mixture paste, first, 98 parts by weight of graphite, 1 part by weight of CMC, and 55 parts by weight of water are introduced into the upstream part of the continuous twin-screw kneader and kneaded to form a kneading step. Carried out. That is, graphite, CMC, and water were kneaded with a continuous biaxial kneader without granulation. The kneaded product subjected to the solidifying step is in a funicular state.
Next, in the downstream part of the continuous twin-screw kneader, 30 parts by weight of water is added to the kneaded product to dilute, and further, 1 part by weight (in solid content) of SBR is added to dilute. The process was implemented and the negative electrode compound paste was obtained. The obtained negative electrode mixture paste had a solid content of 54%.
Furthermore, the obtained negative electrode mixture paste was applied to a copper foil serving as a current collector and dried to prepare a negative electrode plate.
[比較例２]
比較例２に係る負極合材ペーストは、負極活物質として亜麻仁油の吸油量が４５ｍｌ／１００ｇの黒鉛を用い、増粘剤としてＣＭＣを用い、溶媒として水を用いて作成した。
負極合材ペーストの作成においては、９８重量部の黒鉛、１重量部のＣＭＣ、および８５重量部の水を振り混ぜて分散し、分散後に１重量部（固形分で）のＳＢＲを加えることにより、負極合材ペーストを得た。得られた負極合材ペーストの固形分は５４％であった。
さらに、得られた負極合材ペーストを集電体となる銅箔に塗布し乾燥することで、負極板を作製した。
[Comparative Example 2]
The negative electrode mixture paste according to Comparative Example 2 was prepared using graphite having a linseed oil absorption of 45 ml / 100 g as a negative electrode active material, CMC as a thickener, and water as a solvent.
In preparation of the negative electrode mixture paste, 98 parts by weight of graphite, 1 part by weight of CMC, and 85 parts by weight of water are shaken and dispersed, and after dispersion, 1 part by weight (in solid content) of SBR is added. A negative electrode mixture paste was obtained. The obtained negative electrode mixture paste had a solid content of 54%.
Furthermore, the obtained negative electrode mixture paste was applied to a copper foil serving as a current collector and dried to prepare a negative electrode plate.
[比較例３]
比較例３に係る負極合材ペーストは、負極活物質として亜麻仁油の吸油量が３０ｍｌ／１００ｇの黒鉛を用い、固練り工程において連続式二軸混練機に投入する水を５重量部とし、希釈工程において加える水を４３重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は５４％であった。
[Comparative Example 3]
The negative electrode mixture paste according to Comparative Example 3 uses graphite having a linseed oil absorption amount of 30 ml / 100 g as a negative electrode active material, and 5 parts by weight of water charged into a continuous biaxial kneader in a kneading process. A negative electrode mixture paste and a negative electrode plate were produced in the same manner as in Example 1 except that the amount of water added in the step was 43 parts by weight. The obtained negative electrode mixture paste had a solid content of 54%.
[比較例４]
比較例４に係る負極合材ペーストは、負極活物質として亜麻仁油の吸油量が７０ｍｌ／１００ｇの黒鉛を用い、固練り工程において連続式二軸混練機に投入する水を４６重量部とし、希釈工程において加える水を３重量部としたほかは、実施例１と同様にして負極合材ペーストおよび負極板を作製した。得られた負極合材ペーストの固形分は５４％であった。
[Comparative Example 4]
The negative electrode mixture paste according to Comparative Example 4 uses graphite having a linseed oil absorption of 70 ml / 100 g as a negative electrode active material, and 46 parts by weight of water charged into a continuous biaxial kneader in a kneading process. A negative electrode mixture paste and a negative electrode plate were produced in the same manner as in Example 1 except that the amount of water added in the step was 3 parts by weight. The obtained negative electrode mixture paste had a solid content of 54%.
[比較例５]
比較例５に係る負極合材ペーストは、負極活物質として亜麻仁油の吸油量が４５ｍｌ／１００ｇの黒鉛を用い、増粘剤としてＣＭＣを用い、溶媒として水を用いて作成した。
負極合材ペーストの作成においては、まず９８重量部の黒鉛、１重量部のＣＭＣ、および８８重量部の水を連続式二軸混練機の上流部に投入して混練することにより、固練り工程を実施した。つまり、黒鉛、ＣＭＣ、および水を、造粒することなく連続式二軸混練機にて固練りした。固練り工程が実施された混練物は、ファニキュラー状態となっている。
次に、連続式二軸混練機の下流部にて、前記混練物に５重量部の水を加えて希釈し、さらに、１重量部（固形分で）のＳＢＲを加えて混練することにより希釈工程を実施し、負極合材ペーストを得た。得られた負極合材ペーストの固形分は５２％であった。
さらに、得られた負極合材ペーストを集電体となる銅箔に塗布し乾燥することで、負極板を作製した。
比較例５における負極合材ペーストの固形分は５２％と比較例１の負極合材ペーストに比べて固形分割合が低かったため、負極板作成時の負極合材ペーストの乾燥に比較例１の場合よりも長時間を要した。
[Comparative Example 5]
The negative electrode mixture paste according to Comparative Example 5 was prepared using graphite having a linseed oil absorption of 45 ml / 100 g as a negative electrode active material, CMC as a thickener, and water as a solvent.
In the preparation of the negative electrode mixture paste, first, 98 parts by weight of graphite, 1 part by weight of CMC, and 88 parts by weight of water are introduced into the upstream part of the continuous biaxial kneader and kneaded, whereby a kneading step. Carried out. That is, graphite, CMC, and water were kneaded with a continuous biaxial kneader without granulation. The kneaded product subjected to the solidifying step is in a funicular state.
Next, in the downstream part of the continuous twin-screw kneader, 5 parts by weight of water is added to the kneaded material to dilute, and further, 1 part by weight (in solid content) of SBR is added to dilute. The process was implemented and the negative electrode compound paste was obtained. The obtained negative electrode mixture paste had a solid content of 52%.
Furthermore, the obtained negative electrode mixture paste was applied to a copper foil serving as a current collector and dried to prepare a negative electrode plate.
In the case of Comparative Example 1, the solid content of the negative electrode mixture paste in Comparative Example 5 was 52%, which was lower than the negative electrode mixture paste of Comparative Example 1, so that the negative electrode mixture paste was dried when the negative electrode plate was prepared. Took longer than.
［負極活物質の割れ状態の評価方法］
上述のように作成した実施例１〜６および比較例１〜５について黒色度を測定し、負極活物質の割れ状態を評価した。
[Method for evaluating cracking state of negative electrode active material]
The blackness was measured for Examples 1 to 6 and Comparative Examples 1 to 5 prepared as described above, and the cracked state of the negative electrode active material was evaluated.
黒色度の測定は以下のようにして行った。
まず、実施例１〜６および比較例１〜５における各負極板から負極合材を剥離し、剥離した負極合材１重量部に対して１９重量部の水を加えて分散することにより負極合材をペースト状にする。
次に、ペースト状の負極合材を１５０００ｒｐｍで３０分間遠心分離し、当該負極合材ペーストから遊離する負極活物質および増粘剤を含む上澄み液を回収する。回収した上澄み液に水を加えて体積で５倍に希釈し、希釈した前記上澄み液の４００ｎｍ〜７００ｎｍの波長領域における吸光スペクトルを測定し、当該波長領域の吸光度（０〜１）の値の平均値を５倍したものを、黒色度として測定した。
このように測定した黒色度に基づいて実施例１〜６および比較例１〜５における負極活物質の割れ状態の評価を行った。
The blackness was measured as follows.
First, the negative electrode mixture was peeled from each of the negative electrode plates in Examples 1 to 6 and Comparative Examples 1 to 5, and 19 parts by weight of water was added to 1 part by weight of the peeled negative electrode mixture to be dispersed. Paste the material.
Next, the paste-like negative electrode mixture is centrifuged at 15000 rpm for 30 minutes, and the supernatant liquid containing the negative electrode active material and the thickener released from the negative electrode mixture paste is collected. Water was added to the collected supernatant to dilute it 5 times by volume, the absorption spectrum in the wavelength region of 400 nm to 700 nm of the diluted supernatant was measured, and the average of the absorbance (0 to 1) values in the wavelength region The value multiplied by 5 was measured as the blackness.
Based on the blackness measured in this manner, the cracked state of the negative electrode active materials in Examples 1 to 6 and Comparative Examples 1 to 5 was evaluated.
［リチウムイオン二次電池の電池特性の評価方法］
上述のように作成した実施例１〜６および比較例１〜５の負極板を用いてリチウムイオン二次電池のサンプルを作製し、作製したリチウムイオン二次電池のサンプルに対して初期充放電を行った後、初期反応抵抗の測定を行った。その後、リチウムイオン二次電池のサンプルに対して充放電サイクルを実施し、充放電サイクル後の容量維持率を算出した。
このように測定・算出したリチウムイオン二次電池の初期反応抵抗および容量維持率を、リチウムイオン二次電池の電池特性として評価した。
[Method for evaluating battery characteristics of lithium ion secondary battery]
Samples of lithium ion secondary batteries were prepared using the negative electrode plates of Examples 1 to 6 and Comparative Examples 1 to 5 prepared as described above, and initial charge / discharge was performed on the prepared samples of lithium ion secondary batteries. After the initial reaction resistance was measured. Then, the charge / discharge cycle was implemented with respect to the sample of the lithium ion secondary battery, and the capacity | capacitance maintenance factor after a charge / discharge cycle was computed.
The initial reaction resistance and capacity retention rate of the lithium ion secondary battery thus measured and calculated were evaluated as battery characteristics of the lithium ion secondary battery.
［負極活物質の割れ状態および電池特性の評価結果］
実施例１〜６については、負極活物質の割れや欠けの状態を示す指標となる黒色度が、１〜５の範囲内に収まっており、負極活物質の割れや欠けの発生が少なく良好であることがわかる。
また、実施例１〜６の負極合材ペーストにおいては、リチウムイオン二次電池の初期反応抵抗が２８００ｍΩ程度以下の値となっているとともに、充放電サイクル後の容量維持率も９０％以上の値を示しており、リチウムイオン二次電池の電池特性が良好であることがわかる。
About Examples 1-6, the blackness used as the parameter | index which shows the state of the crack of a negative electrode active material, and a chip | tip is settled in the range of 1-5, there are few generation | occurrence | production of the crack and chip | tip of a negative electrode active material, and it is favorable. I know that there is.
In the negative electrode mixture pastes of Examples 1 to 6, the initial reaction resistance of the lithium ion secondary battery is a value of about 2800 mΩ or less, and the capacity retention rate after the charge / discharge cycle is also a value of 90% or more. This shows that the battery characteristics of the lithium ion secondary battery are good.
実施例５、６については、実施例１よりも黒色度が高くなっているが、これは固練り固形分率を実施例１よりも高くしたためである。固練り固形分率を高くすることにより、負極合材ペーストのペースト固形分率を高くしても、塗工可能なペースト粘度を維持することが可能となっている。また、ペースト固形分率が高いため、負極板作製時の負極合材ペーストの乾燥時間を短くすることができ、生産性の高い負極板を構成することが可能となる。 In Examples 5 and 6, the blackness is higher than in Example 1, but this is because the solid content ratio of kneading was higher than in Example 1. By increasing the solid content ratio of the kneaded paste, it is possible to maintain a paste viscosity that can be applied even if the paste solid ratio of the negative electrode mixture paste is increased. Moreover, since the paste solid content rate is high, the drying time of the negative electrode mixture paste at the time of producing the negative electrode plate can be shortened, and a negative electrode plate with high productivity can be configured.
一方、比較例１については、黒色度が５．６といった５を超す大きな値となっており、負極合材材料の造粒を行う湿潤工程が実施されずに負極活物質の湿潤が不十分となったため、負極活物質に割れが発生したことがわかる。また、負極活物質に割れが生じていることから、負極活物質の活性面が多くなっており、充放電サイクル後の容量維持率も８０％以下の低い値となっている。 On the other hand, for Comparative Example 1, the blackness is a large value exceeding 5 such as 5.6, and the wet process of granulating the negative electrode composite material is not performed, and the negative electrode active material is insufficiently wet. Therefore, it can be seen that the negative electrode active material was cracked. Moreover, since the negative electrode active material is cracked, the active surface of the negative electrode active material is increased, and the capacity retention rate after the charge / discharge cycle is a low value of 80% or less.
比較例２については、負極合材ペーストの作製時に黒鉛とＣＭＣと水とを振り混ぜることよって分散しており、負極活物質の攪拌が非常に小さな負荷で行われているため黒色度の値は小さくなっているが、負極活物質の分散性が悪く、充放電サイクル後の容量維持率も８１％と低い値となっている。また、比較例２の負極合材ペーストは量産性がない。 For Comparative Example 2, the negative electrode mixture paste is dispersed by shaking and mixing graphite, CMC, and water, and the negative electrode active material is stirred with a very small load. Although it is small, the dispersibility of the negative electrode active material is poor, and the capacity retention rate after the charge / discharge cycle is as low as 81%. Moreover, the negative electrode mixture paste of Comparative Example 2 has no mass productivity.
比較例３については、黒色度が５．２といった５を超す大きな値となっており、負極活物質の吸油量が小さくＣＭＣの吸着サイトが少ないため、負極活物質の湿潤が不十分となり割れやすくなっていることがわかる。また、負極活物質に割れが多く生じているため、充放電サイクル後の容量維持率も８３％と低い値となっている。 In Comparative Example 3, the blackness is a large value exceeding 5 such as 5.2, and the amount of oil absorption of the negative electrode active material is small and the number of CMC adsorption sites is small. You can see that In addition, since many cracks are generated in the negative electrode active material, the capacity retention rate after the charge / discharge cycle is a low value of 83%.
比較例４については、負極活物質の吸油量が大きくＣＭＣの吸着サイトが多いため、負極活物質の表面がＣＭＣに多く覆われた状態となっており、リチウムイオン二次電池の初期反応抵抗が２９００ｍΩを越える大きな値となっている。 In Comparative Example 4, since the amount of oil absorption of the negative electrode active material is large and the number of CMC adsorption sites is large, the surface of the negative electrode active material is covered with CMC, and the initial reaction resistance of the lithium ion secondary battery is low. It is a large value exceeding 2900 mΩ.
比較例５については、水分が多い状態で固練りすることで、比較例１に比べて黒色度が低くなっているが、負極合材ペーストの固形分率が低いため、負極板作製時の負極合材ペーストの乾燥時間が長くなり、負極板の生産性が低くなっている。 About Comparative Example 5, the blackness is lower than that of Comparative Example 1 by kneading in a state where there is a lot of moisture, but the solid content rate of the negative electrode mixture paste is low, so the negative electrode during the preparation of the negative electrode plate The drying time of the composite paste is prolonged, and the productivity of the negative electrode plate is lowered.
以上のごとく、比較例に示したように、負極合材材料を造粒する湿潤工程を行わなくても、負極合材ペーストの固形分率を低下させれば、負極活物質の割れや欠けを抑制することができるが、負極合材ペーストの乾燥に多くの時間を要し、負極板の生産性が悪化することとなる。
これに対して、本願発明に係る実施例においては、負極合材ペーストの作製時に、高速かつ安価に実施できる湿潤工程を付加することにより、負極合材ペーストの固形分率が高くても負極活物質の割れや欠けを抑制することができ、リチウムイオン二次電池の電池特性を向上するとともに、生産性の高い負極板を構成することが可能となっている。
As described above, as shown in the comparative example, cracking and chipping of the negative electrode active material can be achieved by reducing the solid content rate of the negative electrode mixture paste without performing the wetting step of granulating the negative electrode mixture material. Although it can be suppressed, it takes a lot of time to dry the negative electrode mixture paste, and the productivity of the negative electrode plate is deteriorated.
On the other hand, in the embodiment according to the present invention, a negative electrode active paste is produced even when the negative electrode mixture paste has a high solid content by adding a wetting process that can be performed at a high speed and at a low cost when the negative electrode composite paste is produced. It is possible to suppress cracking and chipping of the material, improve the battery characteristics of the lithium ion secondary battery, and configure a highly productive negative electrode plate.
Ｓ１ 湿潤工程
Ｓ２ 混練工程
Ｓ２１ 固練り工程
Ｓ２２ 希釈工程
S1 Wetting process S2 Kneading process S21 Kneading process S22 Dilution process
Claims (2)
前記造粒体を混練機に投入して固練りする固練り工程と、
前記固練り工程にて固練りした混練物に溶媒を添加して希釈する希釈工程とを有する、
リチウムイオン二次電池用負極の製造方法であって、
前記負極活物質の亜麻仁油吸油量が、３５ｍｌ／１００ｇ以上である、
ことを特徴とするリチウムイオン二次電池用負極の製造方法。 A wetting step of obtaining a granulated body by mixing a negative electrode active material, a thickener, and a solvent;
A kneading step in which the granulated body is charged into a kneader and kneaded;
A dilution step of adding a solvent to the kneaded product kneaded in the kneading step and diluting it,
A method for producing a negative electrode for a lithium ion secondary battery, comprising:
The linseed oil absorption of the negative electrode active material is 35 ml / 100 g or more,
The manufacturing method of the negative electrode for lithium ion secondary batteries characterized by the above-mentioned.
ことを特徴とする請求項１に記載のリチウムイオン二次電池用負極の製造方法。 The linseed oil absorption of the negative electrode active material is 65 ml / 100 g or less,
The manufacturing method of the negative electrode for lithium ion secondary batteries of Claim 1 characterized by the above-mentioned.
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