JP2006278265A - Positive electrode plate for lithium secondary battery and manufacturing method thereof - Google Patents
Positive electrode plate for lithium secondary battery and manufacturing method thereof Download PDFInfo
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本発明は、リチウム二次電池用正極の改良に関し、特に正極活物質の充填状態を改良したリチウム二次電池用正極板に関する。 The present invention relates to an improvement in a positive electrode for a lithium secondary battery, and more particularly to a positive electrode plate for a lithium secondary battery in which a filling state of a positive electrode active material is improved.
携帯電話やノートパソコン等の移動情報端末の小型・軽量化の急速な進展に伴って、軽量かつ高容量のリチウム二次電池の利用が拡大している。リチウム二次電池は、正負極間でのリチウムの移動により充放電を行う電池であり、その正極板には活物質としてコバルト酸リチウムやニッケル酸リチウム等のリチウム複合酸化物が使用されている。 With the rapid progress of miniaturization and weight reduction of mobile information terminals such as mobile phones and laptop computers, the use of lightweight and high-capacity lithium secondary batteries is expanding. A lithium secondary battery is a battery that charges and discharges by movement of lithium between positive and negative electrodes, and a lithium composite oxide such as lithium cobaltate or lithium nickelate is used as an active material for the positive electrode plate.
このようなリチウム二次電池用正極板は、導電剤や結着剤等を配合した正極合剤スラリーを集電体表面に塗着し、乾燥した後、圧縮する方法により作製されており、圧縮時における加圧力を調整することにより所望の充填密度の正極板が作製される。この圧縮法においては、一般に、剛性が高い材質の大径ロールを使用し、より高い圧力で圧縮することにより、電極中の活物質充填密度を高めることができる。しかし、或る段階を超えると加圧力を増しても、電極板最表層の充填密度のみが高まり、その内部の充填密度が高まらないという現象が起きる。このような現象が起きた正極板は、合剤層内部の力学的構造が均一でなく、活物質充填密度が不均一になっているので、機械的強度や電気化学的特性に問題を有する。 Such a positive electrode plate for a lithium secondary battery is produced by a method in which a positive electrode mixture slurry containing a conductive agent, a binder, or the like is applied to the surface of a current collector, dried, and then compressed. A positive electrode plate having a desired packing density is produced by adjusting the pressure applied at the time. In this compression method, in general, the active material filling density in the electrode can be increased by using a large-diameter roll made of a material having high rigidity and compressing at a higher pressure. However, if the pressure is increased beyond a certain level, only the filling density of the outermost layer of the electrode plate increases, and the inside packing density does not increase. The positive electrode plate in which such a phenomenon occurs has a problem in mechanical strength and electrochemical characteristics because the mechanical structure inside the mixture layer is not uniform and the active material filling density is not uniform.
特に、正極活物質であるリチウム複合酸化物は、無機物で硬度が大きく、かつ流動性が良くないために、加圧力を高めても高充填密度の電極が得られ難いとともに、加圧力を高め過ぎると、リチウム複合酸化物の結晶構造が破壊され、リチウムイオンの挿入離脱性能が低下するという問題がある。 In particular, the lithium composite oxide, which is a positive electrode active material, is an inorganic material with high hardness and poor fluidity. Therefore, it is difficult to obtain an electrode with a high packing density even if the applied pressure is increased, and the applied pressure is increased too much. Then, there is a problem that the crystal structure of the lithium composite oxide is destroyed and the lithium ion insertion / extraction performance deteriorates.
他方、圧縮を複数回行うことにより徐徐に充填密度を高める方法もあるが、この方法によると圧縮に時間がかかるため生産性が低下するとともに、集電体が過剰に延伸して破断したり、湾曲が生じたりするなどの問題がある。 On the other hand, there is also a method of gradually increasing the packing density by performing compression several times, but this method takes time to compress and decreases productivity, and the current collector is excessively stretched and broken, There are problems such as bending.
ところで、電極充填密度に関する先行技術文献情報としては下記があり、このうち特許文献１には、集電体近傍の合剤密度を極板表面近傍の合剤密度に比べ大きくすることにより、電極上にリチウムが析出することを防止する技術が記載されている。しかし、特許文献１の技術は、上記した従来技術にかかる圧縮法の問題点を解決するものではない。よって、この技術により、極板表面近傍の合剤密度を十分に高め、かつ集電体近傍の合剤密度を前記極板表面近傍以上に高めることはできない。
By the way, as prior art document information regarding the electrode packing density, there is the following, among them,
本発明は、従来技術にかかる圧縮法における問題点を解消することを目的とするものであり、集電体近傍と電極板表層との充填密度の均一化が図れ、かつ正極板全体の単位当たりの充填密度を大幅に高めることのできるリチウム二次電池用正極板板の製造方法を提供するとともに、そのような製造方法により、発電性能や機械的強度に優れたリチウム二次電池用正極板を実現することを目的とする。 The present invention aims to eliminate the problems in the compression method according to the prior art, can achieve a uniform packing density in the vicinity of the current collector and the surface layer of the electrode plate, and per unit of the entire positive electrode plate. In addition to providing a method for producing a positive electrode plate for a lithium secondary battery capable of significantly increasing the packing density of the lithium secondary battery, a positive electrode plate for a lithium secondary battery having excellent power generation performance and mechanical strength can be obtained by such a production method. It aims to be realized.
上記課題は次の構成により達成できる。
〈第１の発明〉
リチウムイオンを吸蔵・放出するリチウム複合酸化物を主体とする正極活物質と、導電剤と、結着剤と、を含有する正極合剤スラリーを金属箔からなる集電体の両面に塗布し乾燥することにより、正極合剤の塗着された正極板前駆体を作製する正極板前駆体作製工程と、前記正極板前駆体を加圧ローラーにより加圧して、正極板前駆体の合剤層を所定の厚みにまで圧縮し正極板となす加圧工程と、を備え、
前記正極板前駆体作製工程においては、平均粒子径が１０μm〜２０μmであり、ＢＥＴ比表面積が０．２５m2／g〜０．７０m2／ｇである正極活物質粒子を用い、前記加圧工程においては、ロール径が１５０mm以上３６０mm以下の加圧ローラーを用い、かつ前記加圧ローラーの加圧力を４５/mm2以上１９０kg/mm2以下に制御することにより、活物質充填密度が３．６３g/cm3以上３．９５/cm3以下であり、活物質密度比ｄ1／ｄ8が数１の範囲内である正極板を作製することを特徴とするリチウム二次電池用正極板の製造方法。
The above problem can be achieved by the following configuration.
<First invention>
A cathode mixture slurry containing a cathode active material mainly composed of a lithium composite oxide that absorbs and releases lithium ions, a conductive agent, and a binder is applied to both sides of a current collector made of metal foil and dried. A positive electrode plate precursor preparation step for preparing a positive electrode plate precursor coated with a positive electrode mixture, and pressurizing the positive electrode plate precursor with a pressure roller to form a positive electrode plate precursor mixture layer. A pressing step of compressing to a predetermined thickness and forming a positive electrode plate,
Wherein the positive electrode plate precursor preparation step, an average particle diameter of 10 m to 20 m, BET specific surface area using the positive electrode active material particles is 0.25m 2 /g~0.70m 2 / g, the pressurizing step , The pressure density of the active material is 3.63 g by using a pressure roller having a roll diameter of 150 mm or more and 360 mm or less and controlling the pressure of the pressure roller to 45 / mm 2 or more and 190 kg / mm 2 or less. / cm 3 or more 3.95 / cm 3 or less, the manufacturing method of the positive electrode plate for a lithium secondary battery, characterized in that the active material density ratio d1 / d8 to prepare a positive electrode plate in the range of 1.
（数１）
０．９０≦ｄ1／ｄ8≦１．０５
但し、圧縮後の正極合剤層を厚み方向に均等に８分割した場合における電極表面側の最表層の活物質密度をｄ1とし、集電体に接する集電体近傍層の活物質密度をｄ8とする。
(Equation 1)
0.90 ≦ d1 / d8 ≦ 1.05
However, when the positive electrode mixture layer after compression is equally divided into eight in the thickness direction, the active material density of the outermost layer on the electrode surface side is d1, and the active material density of the near-current collector layer in contact with the current collector is d8. And
上記構成では、平均粒子径が１０μm〜２０μmであり、ＢＥＴ比表面積が０．２５m2／g〜０．７０m2／ｇである正極活物質粒子を用い、かつ加圧ロール径が１５０mm以上３６０mm以下の加圧ローラーで加圧力を４５g/mm2以上１９０kg/mm2以下として加圧圧縮するが、この条件であると、電極板の最表層のみが加圧され、内部層が殆ど圧縮されないという問題が発生しない。よって、活物質充填密度が３．６３g/cm3以上３．９５/cm3以下、活物質密度比ｄ1／ｄ8が数１の範囲内である正極板を作製することができる。この製造方法で作製された正極板は、合剤層全体に圧縮力が均一に及び、活物質密度の均一性がよいので、電気化学的特性や機械的強度に優れる。 In the above configuration, the average is a particle diameter of 10 m to 20 m, BET specific surface area using the positive electrode active material particles is 0.25m 2 /g~0.70m 2 / g, and the pressure roll diameter 150mm or 360mm or less of it under pressure compresses the pressure with a pressure roller as a 45 g / mm 2 or more 190 kg / mm 2 or less, with this condition, only the outermost layer of the electrode plate is pressurized, a problem that the inner layer is hardly compressed Does not occur. Therefore, a positive electrode plate having an active material packing density of 3.63 g / cm 3 or more and 3.95 / cm 3 or less and an active material density ratio d1 / d8 within the range of Formula 1 can be manufactured. The positive electrode plate produced by this production method is excellent in electrochemical characteristics and mechanical strength because the entire mixture layer has a uniform compressive force and good uniformity of the active material density.
上記第１の発明においては、前記正極板中の正極活物質の平均粒子径を、前記正極板前駆体作製工程で使用した正極活物質の平均粒子径の７５％以上に加圧圧縮するのがよい。上記構成の正極板の製造方法を用いると、無用に加圧力を高めなくとも、合剤層の活物質密度を十分に高めることができるので、上記条件の範囲内で加圧力やローラーの回転速度等を調整して、正極活物質粒子の平均粒子径を加圧前の７５％以上に止まるようにするのがよい。加圧前後における正極活物質の平均粒子径の減少（粒子の潰れ）が２５％以内であれば、正極活物質の結晶構造の破壊に起因する電気化学的特性の減少よりも、本発明方法による充填密度の向上に伴う効果（２Ｃ放電容量維持率等の向上）の方が優位になるからである。 In the first invention, the average particle diameter of the positive electrode active material in the positive electrode plate is pressure-compressed to 75% or more of the average particle diameter of the positive electrode active material used in the positive electrode plate precursor preparation step. Good. If the positive electrode plate manufacturing method of the above configuration is used, the active material density of the mixture layer can be sufficiently increased without unnecessarily increasing the pressing force, so that the pressing force and the rotation speed of the roller are within the range of the above conditions. It is preferable to adjust the average particle diameter of the positive electrode active material particles to 75% or more before pressurization. If the decrease in the average particle size of the positive electrode active material before and after pressurization (particle collapse) is within 25%, the method according to the present invention is more effective than the decrease in electrochemical properties due to the destruction of the crystal structure of the positive electrode active material. This is because the effect (improvement of the 2C discharge capacity retention rate, etc.) associated with the improvement of the packing density is more dominant.
更に上記第１の発明においては、前記加圧工程における加圧ローラーによる加圧を１回のみとすることができる。
加圧圧縮回数を１回とすることにより、電極板の無用な延伸を抑制でき、集電体の破断や電極板の湾曲を抑制できる。よって、この構成によると、高充填密度で高品質のリチウム二次電池用正極板を製造することができる。
Furthermore, in the said 1st invention, the pressurization by the pressurization roller in the said pressurization process can be made only once.
By setting the number of pressurization and compression times to one, unnecessary stretching of the electrode plate can be suppressed, and breakage of the current collector and bending of the electrode plate can be suppressed. Therefore, according to this configuration, a high-quality positive electrode plate for a lithium secondary battery with a high packing density can be manufactured.
〈第２の発明〉
リチウムイオンを吸蔵・放出するリチウム複合酸化物を主体とする正極活物質と、導電剤と、結着剤と、を含有する正極合剤が集電体表面に圧縮形成されてなる正極合剤層を備えたリチウム二次電池用正極板において、前記正極合剤層中の正極活物質は、平均粒子径が７．５μm〜２０μmで、ＢＥＴ比表面積が０．２５m2／g〜０．７０m2／gであり、前記活物質層の活物質充填密度が、３．６３ｇ／cm3 〜 ３．９５ｇ／cm3であり、
前記活物質層を厚み方向に均等に８分割した場合における電極表面側の最表層の活物質密度をｄ1とし、集電体に接する集電体近傍層の活物質密度をｄ8とするとき、活物質密度比ｄ1／ｄ8が０．９０〜１．０５であることを特徴とするリチウム二次電池用正極板。
<Second invention>
Positive electrode mixture layer formed by compressing and forming a positive electrode mixture containing a positive electrode active material mainly composed of a lithium composite oxide that absorbs and releases lithium ions, a conductive agent, and a binder on the surface of the current collector in the positive electrode plate for a lithium secondary battery including a positive electrode active material of the positive electrode mixture layer has an average particle diameter of 7.5Myuemu～20myuemu, BET specific surface area of 0.25m 2 /g~0.70m 2 / G, and the active material packing density of the active material layer is 3.63 g / cm 3 to 3.95 g /
When the active material density of the outermost layer on the electrode surface side when the active material layer is equally divided into eight in the thickness direction is d1, and the active material density of the current collector adjacent layer in contact with the current collector is d8, A positive electrode plate for a lithium secondary battery, wherein the material density ratio d1 / d8 is 0.90 to 1.05.
この構成のリチウム二次電池用正極板は、単位体積当たりの発電容量が大きく、しかも２Ｃ放電容量維持率やサイクル容量維持率に優れる。 The positive electrode plate for a lithium secondary battery having this configuration has a large power generation capacity per unit volume and is excellent in a 2C discharge capacity maintenance ratio and a cycle capacity maintenance ratio.
本発明によると、集電体近傍と電極板表層との充填密度の均一化が図れ、かつ正極板全体の単位当たりの活物質充填密度を大幅に高めたリチウム二次電池用正極板を実現することができ、この正極板は単位体積当たりの発電容量が大きく、しかも２Ｃ放電容量維持率やサイクル容量維持率に優れる。 According to the present invention, a positive electrode plate for a lithium secondary battery can be realized in which the packing density in the vicinity of the current collector and the electrode plate surface layer can be made uniform, and the active material packing density per unit of the entire positive electrode plate can be greatly increased. This positive electrode plate has a large power generation capacity per unit volume and is excellent in 2C discharge capacity maintenance rate and cycle capacity maintenance rate.
本発明を実施するための最良の形態を、実施例に基づいて説明する。 The best mode for carrying out the present invention will be described based on examples.
（実施例１）
[正極板の作製]
平均粒径１６μｍ、ＢＥＴ比表面積０．２６ｍ2／ｇのコバルト酸リチウム９４重量部とアセチレンブラック３重量部とポリフッ化ビニリデン(PVdF)３重量部とをN-メチルピロリドン液で攪拌して正極合剤スラリー作製し、これを厚さ１５μmのアルミニウムからなる集電体（芯体）の両面に塗布し乾燥した。乾燥後の正極合剤層の厚み０．２６０mmであり、幅は１２０mmであった。このものを、直径２６０mmの金属ロールを用い、圧縮圧力４５kg／mm2で１回ロールプレスして正極合剤層厚みが０．１６０mmの正極板を作製した。
Example 1
[Preparation of positive electrode plate]
94 parts by weight of lithium cobaltate having an average particle diameter of 16 μm and a BET specific surface area of 0.26 m 2 / g, 3 parts by weight of acetylene black, and 3 parts by weight of polyvinylidene fluoride (PVdF) are stirred with an N-methylpyrrolidone solution. An agent slurry was prepared and applied to both sides of a current collector (core body) made of aluminum having a thickness of 15 μm and dried. The thickness of the positive electrode mixture layer after drying was 0.260 mm and the width was 120 mm. This was roll-pressed once using a metal roll having a diameter of 260 mm at a compression pressure of 45 kg / mm 2 to prepare a positive electrode plate having a positive electrode mixture layer thickness of 0.160 mm.
ここで上記コバルト酸リチウムの平均粒径は、レーザー回折式粒度分布測定装置で測定した値であり、ＢＥＴ比表面積とは、Ｎ2ガスを用いＢＥＴ吸着等温式に基づいて算出した値である。 Here, the average particle diameter of the lithium cobalt oxide is a value measured with a laser diffraction particle size distribution analyzer, and the BET specific surface area is a value calculated based on the BET adsorption isotherm using N 2 gas.
[負極及び電解液の作製]
リチウムイオンを吸蔵離脱させることのできるグラファイトを結着剤を使用して銅箔からなる集電体両面に塗着させた。これを負極板とした。電解液は、エチレンカーボネートとジエチルカーボネートとを等体積（２５℃）で混合した混合溶媒にLiPF6を1mol／L溶解して作製した。
[Preparation of negative electrode and electrolyte]
Graphite capable of occluding and releasing lithium ions was applied to both sides of a current collector made of copper foil using a binder. This was used as a negative electrode plate. The electrolyte was prepared by dissolving 1 mol / L of LiPF6 in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at an equal volume (25 ° C.).
[電池組み立て]
上記正極板及び負極板を所定寸法に切断した一対の電極にポリプロピレン製の微多孔膜からなるセパレータを介し巻回して巻回型電極体となし、これを円筒型外装缶内に挿入し、電解液を注液した後、外装缶の開口部をカシメ封口することにより、円筒型リチウム二次電池(電池設計容量１５００ｍＡ)を作製した。
[Battery assembly]
A pair of electrodes obtained by cutting the positive electrode plate and the negative electrode plate to a predetermined size is wound through a separator made of a polypropylene microporous film to form a wound electrode body, which is inserted into a cylindrical outer can and electrolyzed. After injecting the liquid, a cylindrical lithium secondary battery (battery design capacity 1500 mA) was produced by caulking and sealing the opening of the outer can.
（実施例２）
正極板の圧縮に際し、直径３６０mmの金属ロールを使用し、圧縮圧力を５０kg／mm2として正極板を作製したこと以外は上記実施例１と同様にして実施例２にかかるリチウム二次電池を作製した。
(Example 2)
A lithium secondary battery according to Example 2 was produced in the same manner as in Example 1 except that a metal roll having a diameter of 360 mm was used for compression of the positive electrode plate and the positive electrode plate was produced at a compression pressure of 50 kg / mm 2. did.
（実施例３）
正極板の圧縮に際し、直径１５０mmの金属ロールを使用し、圧縮圧力を４６kg／mm2として正極板を作製したこと以外は上記実施例１と同様にして実施例３にかかるリチウム二次電池を作製した。
(Example 3)
A lithium secondary battery according to Example 3 was prepared in the same manner as in Example 1 except that a metal roll having a diameter of 150 mm was used to compress the positive electrode plate, and the positive electrode plate was prepared at a compression pressure of 46 kg / mm 2. did.
（実施例４）
正極板の圧縮に際し、直径１９０mmの金属ロールを使用し圧縮圧力は実施例１と同じとして正極板を作製したこと以外は上記実施例１と同様にして実施例４にかかるリチウム二次電池を作製した。
Example 4
When the positive electrode plate was compressed, a lithium secondary battery according to Example 4 was prepared in the same manner as in Example 1 except that a metal roll having a diameter of 190 mm was used and the compression pressure was the same as in Example 1, and the positive electrode plate was prepared. did.
（比較例１）
正極板の圧縮に際し、直径１３０mmの金属ロールを使用し、圧縮圧力を４６kg／mm2として正極板を作製したこと以外は上記実施例１と同様にして比較例１にかかるリチウム二次電池を作製した。
(Comparative Example 1)
A lithium secondary battery according to Comparative Example 1 was produced in the same manner as in Example 1 except that a positive electrode plate was produced using a metal roll having a diameter of 130 mm and a compression pressure of 46 kg / mm 2 when the positive electrode plate was compressed. did.
（比較例２）
正極板の圧縮に際し、直径４５０mmの金属ロールを使用し、圧縮圧力を５７kg／mm2として正極板を作製したこと以外は上記実施例１と同様にして比較例２にかかるリチウム二次電池を作製した。
(Comparative Example 2)
A lithium secondary battery according to Comparative Example 2 was produced in the same manner as in Example 1 above, except that a metal roll having a diameter of 450 mm was used for compression of the positive electrode plate and the positive electrode plate was produced at a compression pressure of 57 kg / mm 2. did.
（比較例３）
正極板の圧縮に際し、実施例１と同様の直径の金属ロールを用い、圧縮圧力を４０kg／mm2として正極板を作製したこと以外は上記実施例１と同様にして比較例３にかかるリチウム二次電池を作製した。
(Comparative Example 3)
When the positive electrode plate was compressed, a metal roll having the same diameter as in Example 1 was used, and the positive electrode plate was produced at a compression pressure of 40 kg / mm 2. A secondary battery was produced.
（比較例４）
正極板の圧縮に際し、実施例１と同様の直径の金属ロールを用い、圧縮圧力を２５０kg／mm2として正極板を作製したこと以外は上記実施例１と同様にして比較例４にかかるリチウム二次電池を作製した。
(Comparative Example 4)
When the positive electrode plate was compressed, a metal roll having the same diameter as in Example 1 was used, and the positive electrode plate was produced at a compression pressure of 250 kg / mm 2. A secondary battery was produced.
以下の実施例５、比較例５，６は、圧縮回数の影響を調べるためのものである。
（実施例５）
コバルト酸リチウム９４重量部とアセチレンブラック３重量部とポリフッ化ビニリデン３重量部とN-メチルピロリドン液とを攪拌して正極合剤スラリーを作製し、これを厚さ１５μmのアルミニウム集電体の両面に塗布し、乾燥した後、正極活物質密度が概ね３．７０ｇ／ｃｍ3になるように、直径２５０mmの金属ロールを使用し、圧縮圧力６０ｋｇ／mm2、圧縮回数1回でロールプレスを行い、正極板を作製した。
Example 5 and Comparative Examples 5 and 6 below are for examining the influence of the number of compressions.
(Example 5)
94 parts by weight of lithium cobaltate, 3 parts by weight of acetylene black, 3 parts by weight of polyvinylidene fluoride, and N-methylpyrrolidone solution were stirred to prepare a positive electrode mixture slurry, which was formed on both sides of a 15 μm thick aluminum current collector. After being applied to the substrate and dried, a metal roll having a diameter of 250 mm is used so that the positive electrode active material density is approximately 3.70 g / cm 3 , and a roll press is performed at a compression pressure of 60 kg / mm 2 and a single compression. A positive electrode plate was prepared.
（比較例５）
圧縮圧力４０ｋｇ／ｍｍ2、圧縮回数を2回としたこと以外は、上記実施例５と同様にして比較例５にかかる正極板を作製した。
(Comparative Example 5)
A positive electrode plate according to Comparative Example 5 was produced in the same manner as in Example 5 except that the compression pressure was 40 kg / mm 2 and the number of compressions was two.
（比較例６）
圧縮圧力３０ｋｇ／ｍｍ2、圧縮回数を３回としたこと以外は、上記実施例５と同様にして比較例６にかかる正極板を作製した。
(Comparative Example 6)
A positive electrode plate according to Comparative Example 6 was produced in the same manner as in Example 5 except that the compression pressure was 30 kg / mm 2 and the number of compressions was three.
以上で作製した各種正極板の特性を調べた。詳しくは、正極合剤層の断面形状を走査型電子顕微鏡（ＳＥＭ）で観察すると共に、正極合剤層のＳＥＭ拡大画像を用いて活物質密度比の評価を行った。また、上記各電池について、２Ｃ放電容量維持率の測定を行った。また、圧縮回数と電極板の延びの関係を調べた。これらの条件とその結果を順次説明する。 The characteristics of the various positive electrode plates produced above were examined. Specifically, the cross-sectional shape of the positive electrode mixture layer was observed with a scanning electron microscope (SEM), and the active material density ratio was evaluated using the SEM enlarged image of the positive electrode mixture layer. Moreover, about the said each battery, the 2C discharge capacity maintenance factor was measured. Further, the relationship between the number of compressions and the extension of the electrode plate was examined. These conditions and the results will be described sequentially.
〈ＳＥＭ拡大画像作成条件〉。
正極板を1cm×1cmに切り、シリコンウエハ面に接着し固定し、その表面を熱硬化性樹脂で覆った後、クロスセクションポリシャ法を用いて断面加工を行った。次いで、ＳＥＭを介して電極表面側の正極合剤層および集電体近傍の正極合剤層の断面状態を観察すると共に、これらについて写真撮影した。活物質密度比の評価用の写真撮影は拡大倍率９００倍、２５００倍で行った。
<SEM enlarged image creation conditions>.
The positive electrode plate was cut into 1 cm × 1 cm, adhered and fixed to the silicon wafer surface, the surface was covered with a thermosetting resin, and then the cross section was processed using a cross section polisher method. Next, the cross-sectional state of the positive electrode mixture layer on the electrode surface side and the positive electrode mixture layer in the vicinity of the current collector was observed through SEM, and photographs of these were taken. Photography for evaluation of the active material density ratio was performed at a magnification of 900 times and 2500 times.
〈活物質密度比の測定条件〉
画像処理ソフトを使用し上記で撮影した画像における正極合剤層の厚み方向の全厚を８個の層に均等分割し、電極最表層を第1層とし、集電体面に接する集電体近傍を第８層とし、その中間をｄn（n＝２〜７）とした。また、正極合剤層中の活物質粒子を白色、活物質以外を黒色にする２値化処理を行った。そして、正極合剤層の全厚の1/8を縦長とし、横長(集電体に平行な方向）を０．０３mmとする区画を一区画とし、この区画内における白色面積を測定する方法により第１層から第８層までの活物質密度を測定した。
<Measurement conditions of active material density ratio>
In the image taken above using image processing software, the total thickness of the positive electrode mixture layer in the thickness direction is equally divided into 8 layers, the outermost electrode layer is the first layer, and the vicinity of the current collector in contact with the current collector surface Was the eighth layer, and its middle was dn (n = 2 to 7). Moreover, the binarization process which makes active material particle | grains in a positive mix layer white and black except active material was performed. Then, a method in which 1/8 of the total thickness of the positive electrode mixture layer is vertically long and a horizontally long (direction parallel to the current collector) is 0.03 mm is defined as one section, and the white area in this section is measured. The active material density from the first layer to the eighth layer was measured.
電極表面の第1層の活物質密度をｄ１、集電体面に接する集電体近傍層の活物質密度をｄ8として、ｄ１／ｄ8を求め、これを活物質密度比とした。表１には、ｄ１／ｄ8の結果を示し、ｄ１／ｄ8活物質密度比が０．９０＜ｄ１／ｄ8＜１．０５の範囲内にある場合を良（○）とした。活物質密度比がこの範囲内にあれば、正極合剤層全体が十分に均一であると言えるからである。 The active material density of the first layer on the electrode surface was d1, and the active material density of the near-current collector layer in contact with the current collector surface was d8, so that d1 / d8 was obtained and used as the active material density ratio. Table 1 shows the result of d1 / d8, and the case where the d1 / d8 active material density ratio is in the range of 0.90 <d1 / d8 <1.05 was evaluated as good (◯). This is because if the active material density ratio is within this range, it can be said that the entire positive electrode mixture layer is sufficiently uniform.
〈粒子の潰れの評価〉
圧縮前の正極活物質の粒度分布を測定しこの平均粒子径をｒ1とし、圧縮後の正極板から回収した活物質を約４００℃で１時間加熱し、バインダーを分解させてとり除いた後、粒度分布を測定し、この平均粒子径をｒ2とした。各々の正極板におけるｒ2／ｒ1を求め、この百分率を形状維持率％とし、〔ｒ2／ｒ1〕×１００ ＞ ７５である場合を良（○）とした。なお、活物質粒子の潰れがない場合は、形状維持率が１００となる。
<Evaluation of particle collapse>
After measuring the particle size distribution of the positive electrode active material before compression and setting this average particle size to r1, the active material recovered from the positive electrode plate after compression was heated at about 400 ° C. for 1 hour to decompose and remove the binder, The particle size distribution was measured, and this average particle size was defined as r2. The ratio r2 / r1 of each positive electrode plate was determined, and the percentage was defined as the shape retention ratio%, and the case of [r2 / r1] × 100> 75 was evaluated as good (◯). When the active material particles are not crushed, the shape maintenance ratio is 100.
〈２Ｃ放電容量維持率の測定〉
各電池について、２５℃において電流１５００ｍＡ、終止電圧４．２Ｖの定電流充電を行い、続いて電圧４．２Ｖ、終止電流３０ｍＡの定電圧充電を行った後、電流値１５００ｍＡで２．７５Ｖまで放電しこの時の放電容量を測定した。これを基準放電容量とした。他方、同様に充電した後、今度は電流値３０００ｍＡで２．７５Ｖまで放電してこの時の放電容量を測定し、これを２Ｃ放電容量とした。上記基準放電容量に対する２Ｃ放電容量の百分率を２Ｃ容量維持率（％）とした。
<Measurement of 2C discharge capacity retention rate>
Each battery was charged at a constant current of 1500 mA and a final voltage of 4.2 V at 25 ° C., followed by a constant voltage of 4.2 V and a final current of 30 mA, and then discharged to 2.75 V at a current value of 1500 mA. The discharge capacity at this time was measured. This was defined as a reference discharge capacity. On the other hand, after charging in the same manner, the battery was discharged to 2.75 V at a current value of 3000 mA, the discharge capacity at this time was measured, and this was defined as 2C discharge capacity. The percentage of 2C discharge capacity with respect to the reference discharge capacity was defined as 2C capacity maintenance rate (%).
〈２５℃サイクル容量維持率の測定〉
上記と同様、２５℃において、定電流充電(電流１５００ｍＡ、終止電圧４．２Ｖ) − 定電圧充電(電圧４．２Ｖ、終止電流３０ｍＡ)を行い、電流値１５００ｍＡで２．７５Ｖまで放電する充放電を１サイクルとし、これを５００サイクル繰り返した。各電池について、１サイクル目と５００サイクル目における放電容量を測定し、１サイクル目の放電容量に対する５００サイクル目の放電容量の百分率を２５℃サイクル容量維持率（％）とした。
<Measurement of cycle capacity maintenance rate at 25 ° C.>
Similarly to the above, constant current charging (current 1500 mA, final voltage 4.2 V) -constant voltage charging (voltage 4.2 V, final current 30 mA) at 25 ° C., charging / discharging to 2.75 V at a current value of 1500 mA Was one cycle and this was repeated 500 cycles. About each battery, the discharge capacity in the 1st cycle and the 500th cycle was measured, and the percentage of the discharge capacity of the 500th cycle to the discharge capacity of the 1st cycle was made into 25 ° C cycle capacity maintenance rate (%).
（結果）
実施例１〜４および比較例１〜３における各種条件と評価結果を表１に一覧表示する。また、実施例１、比較例３にかかる正極板の正極合剤層のＳＥＭ写真に基づく概念図をそれぞれ図１図２に示し、図３に圧縮回数と電極板の延びとの関係を示す。図１における符号１は電極表面側の正極合剤最表層であり、符号２は活物質粒子、符号３は集電体である。
(result)
Various conditions and evaluation results in Examples 1 to 4 and Comparative Examples 1 to 3 are listed in Table 1. Moreover, the conceptual diagram based on the SEM photograph of the positive mix layer of the positive electrode plate concerning Example 1 and the comparative example 3 is shown in FIG. 1, FIG. 2, respectively, The relationship between the frequency | count of compression and the extension of an electrode plate is shown in FIG. In FIG. 1,
表１において、ロール径が１５０mmから３６０mmであり、加圧力が４５ｋｇ／mm2から１９０ｋｇ／mm2であり、活物質充填密度が３．６３ｇ／cm3 〜３．９５ｇ／cm3である実施例１〜４の正極板は、活物質密度比ｄ１/ｄ8が０．９０〜１．０５と顕著に小さかった。そして、この正極板を用いてなる実施例１〜４にかかるリチウム二次電池は、２Ｃ放電容量維持率が８２〜８７％であり、２５℃５００サイクルにおける容量維持率が８５〜９０％と優れた電池性能を示した。
In Table 1, Examples in which the roll diameter is 150 mm to 360 mm, the applied pressure is 45 kg / mm 2 to 190 kg / mm 2 , and the active material packing density is 3.63 g / cm 3 to 3.95 g / cm 3. In the
これに対して、ロール径または加圧力の何れかが上記範囲内にない比較例１〜４は、上記実施例１〜４に比較して活物質密度比ｄ１/ｄ8値が１より大きく離れており、２Ｃ放電容量維持率、２５℃５００サイクル容量維持率が共に大きく低下していた。 In contrast, Comparative Examples 1 to 4 in which either the roll diameter or the applied pressure is not within the above range has an active material density ratio d1 / d8 value that is larger than 1 compared to Examples 1 to 4 above. Both the 2C discharge capacity retention rate and the 25 ° C. 500 cycle capacity retention rate were significantly reduced.
また、表１において、活物質粒子の形状維持率（％)について見ると、例えば実施例１の形状維持率は９０％であり、比較例２のそれは９８％であったが、２Ｃ放電容量維持率、２５℃５００サイクル容量維持率とも実施例１の方が顕著に優れていた。この理由としては、図１、２に示すように、実施例１の正極板では極板全体が均一に圧縮され活物質密度が均一であるのに対し（図１）、比較例２は極板表面近傍のみが高密度に圧縮され、中間層や集電体近傍の圧縮密度が小さくなった不均一構造が形成（図２）されているためと考えられる。 Further, in Table 1, when looking at the shape retention rate (%) of the active material particles, for example, the shape retention rate of Example 1 was 90% and that of Comparative Example 2 was 98%, but the 2C discharge capacity was maintained. In Example 1, both the rate and the cycle capacity maintenance rate at 25 ° C. were significantly superior. The reason for this is that, as shown in FIGS. 1 and 2, in the positive electrode plate of Example 1, the entire electrode plate is uniformly compressed and the active material density is uniform (FIG. 1), whereas in Comparative Example 2, the electrode plate is This is probably because only the vicinity of the surface is compressed to a high density, and a non-uniform structure is formed (FIG. 2) in which the compression density in the vicinity of the intermediate layer and current collector is reduced.
また、実施例３とその他の実施例や比較例との比較から、活物質粒子の潰れの程度は電池性能の差に直結するのではなく、活物質密度比との関連において電池性能に影響を与えることが判る。つまり、活物質密度比ｄ１/ｄ8が０．９０〜１．０５の範囲内にある場合には、活物質粒子の形状維持率が７５％（実施例３）以上であれば十分な電池性能が担保できることが判る。これは、正極活物質の結晶構造の破壊に起因する電気化学的特性の減少よりも、正極板全体の活物質密度の均一化によるよる効果（２Ｃ放電容量維持率等の向上）の方が優位になるからであると考えられる。 Moreover, from the comparison between Example 3 and other examples and comparative examples, the degree of crushing of the active material particles does not directly affect the difference in battery performance, but affects the battery performance in relation to the active material density ratio. I can give it. That is, when the active material density ratio d1 / d8 is in the range of 0.90 to 1.05, sufficient battery performance is obtained if the shape retention rate of the active material particles is 75% (Example 3) or more. It can be seen that it can be secured. This is superior to the effect (improvement of 2C discharge capacity maintenance ratio, etc.) due to the uniformity of the active material density of the entire positive electrode plate, rather than the decrease in electrochemical characteristics due to the destruction of the crystal structure of the positive electrode active material. This is considered to be.
図３に圧縮回数（加圧圧縮回数）と正極板の延びとの関係を示すが、図３から明らかなように、圧縮回数が増えると直線的に電極板が延びる傾向が認められる。このことは、圧縮回数を増やすことにより合剤の充填密度を高める方法によると、集電体の破損等が生じ易くなることを意味する。よって、好ましくは１回の圧縮で所望の活物質密度の正極板を得ることのできる製造方法がよい。 FIG. 3 shows the relationship between the number of compressions (the number of pressure compressions) and the extension of the positive electrode plate. As is clear from FIG. 3, as the number of compressions increases, there is a tendency for the electrode plate to extend linearly. This means that, according to the method of increasing the packing density of the mixture by increasing the number of compressions, the current collector is easily damaged. Therefore, it is preferable to use a manufacturing method that can obtain a positive electrode plate having a desired active material density by one compression.
（その他の事項）
上記実施例では、正極活物質として平均粒径１６μｍ、ＢＥＴ比表面積０．２６ｍ2／ｇのコバルト酸リチウムを用いたが、正極活物質は、平均粒子径が１０μm〜２０μmであり、ＢＥＴ比表面積が０．２５m2／g〜０．７０m2／ｇのものであればよい。この範囲内であれば、活物質の硬度が硬くなり、本発明で圧縮した場合においても結晶構造の破壊が少なく粒子形状がほとんど変化しないためである。
(Other matters)
In the above examples, lithium cobaltate having an average particle diameter of 16 μm and a BET specific surface area of 0.26 m 2 / g was used as the positive electrode active material. The positive electrode active material has an average particle diameter of 10 μm to 20 μm and a BET specific surface area. There may be those of 0.25m 2 /g~0.70m 2 / g. Within this range, the hardness of the active material becomes hard, and even when compressed according to the present invention, the crystal structure is hardly broken and the particle shape hardly changes.
また、上記実施例では、正極活物質としてコバルト酸リチウムを用いたが、本発明は、結晶が硬く、粒子流動性が悪く、かつ過大な圧力が加わると、結晶構造が破壊されるという特性を有するリチウム複合酸化物全般に適用できる。コバルト酸リチウム以外のリチウム複合酸化物としては、例えばマンガン酸リチウム、ニッケル酸リチウム、リチウムチタン酸化物、オリビン型燐酸鉄リチウムなどが挙げられる。 Further, in the above examples, lithium cobaltate was used as the positive electrode active material, but the present invention has the characteristics that the crystal is hard, the particle fluidity is poor, and the crystal structure is destroyed when an excessive pressure is applied. Applicable to all lithium composite oxides. Examples of lithium composite oxides other than lithium cobaltate include lithium manganate, lithium nickelate, lithium titanium oxide, and olivine type lithium iron phosphate.
本発明は、圧縮方法を工夫して集電体近傍と電極板表層との充填密度の均一化を図ることにより、単位体積当たりの発電容量が大きく、２Ｃ放電容量維持率やサイクル容量維持率に優れたリチウム二次電池用正極板を提供する。この正極板はリチウム二次電池の電池性能を顕著に高めることができるので、その産業上の利用可能性は大きい。 In the present invention, the power generation capacity per unit volume is large by devising the compression method and making the packing density in the vicinity of the current collector and the electrode plate surface layer uniform, and the 2C discharge capacity maintenance rate and cycle capacity maintenance rate are increased. An excellent positive electrode plate for a lithium secondary battery is provided. Since this positive electrode plate can remarkably improve the battery performance of the lithium secondary battery, its industrial applicability is great.
１ 正極合剤最表層
２ 正極活物質
３ 集電体
DESCRIPTION OF
Claims (4)
前記正極板前駆体を加圧ローラーにより加圧して、正極板前駆体の合剤層を所定の厚みにまで圧縮し正極板となす加圧工程と、
を備え、
前記正極板前駆体作製工程においては、平均粒子径が１０μm〜２０μmであり、ＢＥＴ比表面積が０．２５m2／g〜０．７０m2／ｇである正極活物質粒子を用い、
前記加圧工程においては、ロール径が１５０mm以上３６０mm以下の加圧ローラーを用い、かつ前記加圧ローラーの加圧力を４５/mm2以上１９０kg/mm2以下に制御することにより、活物質充填密度が３．６３g/cm3以上３．９５/cm3以下であり、活物質密度比ｄ1／ｄ8が数１の範囲内である正極板を作製する
ことを特徴とするリチウム二次電池用正極板の製造方法。
（数１）
０．９０≦ｄ1／ｄ8≦１．０５
但し、圧縮後の正極合剤層を厚み方向に均等に８分割した場合における電極表面側の最表層の活物質密度をｄ1とし、集電体に接する集電体近傍層の活物質密度をｄ8とする。
A cathode mixture slurry containing a cathode active material mainly composed of a lithium composite oxide that absorbs and releases lithium ions, a conductive agent, and a binder is applied to both sides of a current collector made of metal foil and dried. A positive electrode plate precursor preparation step of preparing a positive electrode plate precursor coated with a positive electrode mixture,
Pressurizing the positive electrode plate precursor with a pressure roller, compressing the mixture layer of the positive electrode plate precursor to a predetermined thickness and forming a positive electrode plate;
With
Wherein the positive electrode plate precursor preparation step, an average particle diameter of 10 m to 20 m, BET specific surface area using the positive electrode active material particles is 0.25m 2 /g~0.70m 2 / g,
In the pressurizing step, an active material filling density is achieved by using a pressure roller having a roll diameter of 150 mm or more and 360 mm or less and controlling the pressing force of the pressure roller to 45 / mm 2 or more and 190 kg / mm 2 or less. A positive electrode plate for a lithium secondary battery, characterized in that a positive electrode plate having an active material density ratio d 1 / d 8 within the range of Formula 1 is produced by the process of 3.63 g / cm 3 to 3.95 / cm 3 Manufacturing method.
(Equation 1)
0.90 ≦ d1 / d8 ≦ 1.05
However, when the positive electrode mixture layer after compression is equally divided into eight in the thickness direction, the active material density of the outermost layer on the electrode surface side is d1, and the active material density of the near-current collector layer in contact with the current collector is d8. And
前記正極板中の正極活物質の平均粒子径が、前記正極板前駆体作製工程で使用した正極活物質の平均粒子径の７５％以上である
ことを特徴とするリチウム二次電池用正極板の製造方法。 In the manufacturing method of the positive electrode plate for lithium secondary batteries of Claim 1,
An average particle size of the positive electrode active material in the positive electrode plate is 75% or more of an average particle size of the positive electrode active material used in the positive electrode plate precursor preparation step. Production method.
前記加圧工程における加圧ローラーによる加圧が１回のみである
ことを特徴とするリチウム二次電池用正極板の製造方法。 In the manufacturing method of the positive electrode plate for lithium secondary batteries of Claim 1 or 2,
The method for producing a positive electrode plate for a lithium secondary battery, characterized in that the pressing by the pressing roller in the pressing step is only once.
前記正極活物質は、平均粒子径が７．５μm〜２０μmで、ＢＥＴ比表面積が０．２５m2／g〜０．７０m2／ｇであり、
前記正極合剤層の正極活物質充填密度が、３．６３ｇ／cm3 〜 ３．９５ｇ／cm3であり、
前記活物質層を厚み方向に均等に８分割した場合における電極表面側の最表層の活物質密度をｄ1とし、集電体に接する集電体近傍層の活物質密度をｄ8とするとき、活物質密度比ｄ1／ｄ8が０．９０〜１．０５である、
ことを特徴とするリチウム二次電池用正極板。
Positive electrode mixture layer formed by compressing and forming a positive electrode mixture containing a positive electrode active material mainly composed of a lithium composite oxide that absorbs and releases lithium ions, a conductive agent, and a binder on the surface of the current collector In a positive electrode plate for a lithium secondary battery comprising:
The positive active material has an average particle diameter of 7.5Myuemu～20myuemu, BET specific surface area of 0.25m 2 /g~0.70m 2 / g,
The positive electrode active material filling density of the positive electrode mixture layer is a 3.63g / cm 3 ~ 3.95g / cm 3,
When the active material density of the outermost layer on the electrode surface side when the active material layer is equally divided into eight in the thickness direction is d1, and the active material density of the current collector adjacent layer in contact with the current collector is d8, The material density ratio d1 / d8 is 0.90 to 1.05.
The positive electrode plate for lithium secondary batteries characterized by the above-mentioned.
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| JP2008159410A (en) * | 2006-12-25 | 2008-07-10 | Matsushita Electric Ind Co Ltd | Cathode plate for nonaqueous secondary battery, and nonaqueous secondary battery using this |
| JP2014102896A (en) * | 2012-11-16 | 2014-06-05 | Toyota Industries Corp | Power storage device, secondary battery, and electrode manufacturing method |
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