JP6569548B2 - Method for producing carbon black dispersion for lithium ion secondary battery - Google Patents
Method for producing carbon black dispersion for lithium ion secondary battery Download PDFInfo
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- JP6569548B2 JP6569548B2 JP2016015879A JP2016015879A JP6569548B2 JP 6569548 B2 JP6569548 B2 JP 6569548B2 JP 2016015879 A JP2016015879 A JP 2016015879A JP 2016015879 A JP2016015879 A JP 2016015879A JP 6569548 B2 JP6569548 B2 JP 6569548B2
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- carbon black
- dispersion
- mass
- battery
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、リチウムイオン二次電池用カーボンブラック分散液の製造方法に関する。 The present invention relates to a method for producing a carbon black dispersion for a lithium ion secondary battery.
近年、モバイル端末や電気自動車、ハイブリッド自動車の高性能化と普及に伴い、これらの電源として好ましく用いられるリチウムイオン二次電池も益々出力や量産性、さらには安全性の向上が求められるようになっている。 In recent years, as mobile terminals, electric vehicles, and hybrid vehicles have become more sophisticated and popular, lithium ion secondary batteries that are preferably used as power sources have been increasingly required to improve output, mass productivity, and safety. ing.
リチウムイオン二次電池の正極および負極は、電気を蓄える役割を果たす活物質と、導電性を付与する導電材、これらを結着させるバインダー、および分散媒から成るスラリー状の混合物を塗工、乾燥させて得られる。導電材としては、工業的に量産しやすく安価なカーボンブラックが主として用いられる他、カーボンナノチューブやカーボンファイバー、黒鉛、グラフェン等の導電性炭素材料が広く使用されている。バインダーとしては、電池セル内の電気的、熱的に過酷な環境下に対しても耐性が高いポリフッ化ビニリデン系ポリマーが主として用いられ、分散媒にはこの良溶媒であるＮ−メチル−２−ピロリドンが用いられる。 A positive electrode and a negative electrode of a lithium ion secondary battery are coated and dried with a slurry-like mixture comprising an active material that stores electricity, a conductive material that imparts conductivity, a binder that binds these materials, and a dispersion medium Can be obtained. As the conductive material, carbon black that is easily mass-produced industrially and is inexpensive is mainly used, and conductive carbon materials such as carbon nanotubes, carbon fibers, graphite, and graphene are widely used. As the binder, a polyvinylidene fluoride-based polymer having high resistance to an electrically and thermally harsh environment in the battery cell is mainly used, and N-methyl-2-2, which is a good solvent, is used as a dispersion medium. Pyrrolidone is used.
電池の出力は電池セル内における電子抵抗、リチウムイオンの拡散抵抗、リチウムイオンと活物質の反応抵抗をそれぞれ低減させることで向上し、これらの低減にはカーボンブラックの分散状態を適切にコントロールすることが効果的である。 The output of the battery is improved by reducing the electronic resistance in the battery cell, the diffusion resistance of lithium ions, and the reaction resistance of lithium ions and the active material, respectively. To reduce these, appropriately control the dispersion state of carbon black. Is effective.
カーボンブラックは微細な粒子であるため凝集力が強いが、凝集が多い状態では効率的なネットワーク状の導電パスを形成することができないため電子抵抗が増大してしまう。しかし、凝集を解そうとして強力な外力をかけると、アグリゲートと言われる最小単位構造が破壊されて、かえって導電パスを途切れさせてしまう。 Since carbon black is a fine particle and has a strong cohesive force, an electronic network increases because an efficient network-like conductive path cannot be formed in a state where the cohesion is large. However, if a strong external force is applied to solve the aggregation, the minimum unit structure called an aggregate is destroyed and the conductive path is interrupted.
アグリゲートは球状の粒子が数珠つなぎになった嵩高い形状をしており、適度に分散させると粒子間に空間を形成し、これがリチウムイオンの良好な拡散経路となって拡散抵抗を低減させる。さらに活物質に接触しながらも表面近傍に適度な空間が形成されるため、リチウムとの反応抵抗も低減される。逆に、アグリゲートが破壊されるほど過分散にしてしまうとカーボンブラックが密に充填され空間を塞ぐため、これらの抵抗が増大する。 The aggregate has a bulky shape in which spherical particles are connected in a daisy chain. When moderately dispersed, a space is formed between the particles, which becomes a good diffusion path for lithium ions and reduces diffusion resistance. Furthermore, since an appropriate space is formed near the surface while being in contact with the active material, reaction resistance with lithium is also reduced. On the contrary, if the dispersion is excessively dispersed so that the aggregate is destroyed, carbon black is densely filled to close the space, and these resistances increase.
このようなカーボンブラックの分散状態をコントロールする方法として、予めカーボンブラックの分散液を製造して用いる方法が種々提案されている。 As a method for controlling the dispersion state of such carbon black, various methods for producing and using a carbon black dispersion in advance have been proposed.
特許文献１では、メディア型分散機を用いてせん断速度１００〜１０００／ｓに粘度の極小値を有するようにカーボンブラックの分散状態を制御することで、リチウムイオン二次電池の性能を向上させている。しかしながら、特許文献２でも述べられている通り、メディア型分散機を用いると、カーボンブラックと分散メディアとが激しく衝突して過分散になりベストな抵抗は得られない。 In Patent Document 1, the performance of the lithium ion secondary battery is improved by controlling the dispersion state of the carbon black so as to have a minimum viscosity at a shear rate of 100 to 1000 / s using a media type disperser. Yes. However, as described in Patent Document 2, when a media-type disperser is used, carbon black and the dispersive medium collide violently, resulting in overdispersion and the best resistance cannot be obtained.
適度に分散した高濃度のカーボンブラック分散液は、あるせん断速度で粘度の極小値を有するダイラタント流体として振る舞う。極小値のせん断速度は粒径が小さい程、すなわち分散度が高いほど大きくなる。 A moderately dispersed high concentration carbon black dispersion behaves as a dilatant fluid having a minimum viscosity at a certain shear rate. The minimum shear rate increases as the particle size decreases, that is, as the degree of dispersion increases.
また、リチウムイオン二次電池は内部に可燃性液体である電解液を使用しているため、過去に発火事故が複数報告されていることからもわかるように、本質的に火災のリスクを有している。火災が発生する原因の一つに、電池内に存在する金属微粒子の近傍で過充電が起こり、発熱して熱暴走に至る場合がある。特に自動車では命に係わる重大な事故となり得るため、リチウムイオン二次電池が身近になればなるほど、厳重に金属微粒子の混入を防ぐ、または排除する必要性が増していく。 In addition, since lithium ion secondary batteries use an electrolyte that is a flammable liquid, there is inherently a risk of fire, as can be seen from the fact that multiple accidents have been reported in the past. ing. One of the causes of the fire is that overcharging occurs in the vicinity of the metal fine particles present in the battery, generating heat and leading to thermal runaway. Especially in automobiles, it can be a serious life-threatening accident, so the closer you are to a lithium ion secondary battery, the greater the need to prevent or eliminate metal particulates.
カーボンブラックには製造工程や原料に由来する金属微粒子が元々含まれているが、粉末から除去するよりも分散液の状態でろ過する方が精度良く効率的に除去でき、また、分散工程でも混入の可能性があるため、カーボンブラックの分散工程に続いてろ過工程を行うのが安全上、およびコスト上最も良い。 Carbon black originally contains fine metal particles derived from the manufacturing process and raw materials, but it can be removed more accurately and efficiently by filtering in the state of dispersion than by removing it from the powder. Therefore, it is best in terms of safety and cost to perform a filtration step following the carbon black dispersion step.
しかし、特許文献１や特許文献２に記載のようなカーボンブラック分散液はダイラタント流体であるため、ろ過工程で圧力がかかった際に高いせん断力がかかり、フィルター上で固体のように振る舞って詰まりが発生するという問題があった。カーボンブラック濃度が１０質量部未満の場合はダイラタントにならず、ろ過詰まりは起こらないが、電極用スラリー組成物の濃度が低くなってしまい、分散媒の原料費や塗工乾燥にかかるコストが嵩むという別の問題が生じてしまう。 However, since carbon black dispersions as described in Patent Document 1 and Patent Document 2 are dilatant fluids, high shear force is applied when pressure is applied in the filtration process, and they act as solids on the filter and clog. There was a problem that occurred. When the carbon black concentration is less than 10 parts by mass, the dilatant does not become clogged and filtration clogging does not occur, but the concentration of the electrode slurry composition becomes low, and the raw material cost of the dispersion medium and the cost for coating drying increase. Another problem will arise.
さらに、前述のカーボンブラック分散液は粘性を付与するような樹脂成分を含まないため、貯蔵安定性が不十分であり、３か月程度保管するとカーボンブラックが凝集したり、ケーキ状の沈降が発生するという問題があった。 Furthermore, since the carbon black dispersion described above does not contain a resin component that imparts viscosity, the storage stability is insufficient, and when stored for about 3 months, carbon black aggregates or cake-like sedimentation occurs. There was a problem to do.
一方、特許文献３のようにバインダーを多く含む場合は、バインダー自体の粘性の影響を受けてダイラタント流体にはならないため、ろ過詰まりや貯蔵安定性に問題はない。しかし、デバイスやリチウムイオン二次電池の設計によって種々異なるカーボンブラック種、バインダー種、これらの混合比に対応する多数の製品をそれぞれ製造、保管する必要が生じるため、ハンドリングが悪くコストが高くなるという問題があった。 On the other hand, when many binders are included like patent document 3, since it does not become a dilatant fluid under the influence of the viscosity of the binder itself, there is no problem in filtration clogging and storage stability. However, depending on the device and the design of the lithium ion secondary battery, it is necessary to manufacture and store various products corresponding to different carbon black types, binder types, and mixing ratios thereof, so that handling is bad and cost is high. There was a problem.
ところで、特許文献４では、炭素ベースの導電性充填材に対し質量比が０．０４〜０．４のバインダーと混練し固形状のマスターバッチを経由して、希釈することで電池用スラリーを製造する方法が記述されている。しかし、固形状物質の混練工程は装置の摩耗が激しく、装置由来の金属微粒子の混入量が増えてしまう。また、希釈してからろ過をするとしても、工数が増えることによる混入リスクが高くなる。さらには、溶解、希釈工程に必要な製造コストと設備投資コストが増えるという問題がある。 By the way, in patent document 4, the slurry for batteries is manufactured by kneading with the binder of mass ratio 0.04-0.4 with respect to a carbon-based conductive filler, and diluting via a solid masterbatch. How to do is described. However, in the solid material kneading process, the apparatus is heavily worn, and the amount of metal fine particles derived from the apparatus increases. Moreover, even if it filters after diluting, the contamination risk by an increase in a man-hour increases. Furthermore, there is a problem that manufacturing costs and capital investment costs required for the dissolution and dilution processes increase.
以上の背景から、本発明では、量産性、貯蔵安定性を有しながら出力に優れるリチウムイオン二次電池用カーボンブラック分散液を提供することが課題である。 From the above background, it is an object of the present invention to provide a carbon black dispersion for a lithium ion secondary battery that is excellent in output while having mass productivity and storage stability.
本発明者らは、カーボンブラックの含有量が分散液１００質量部に対して１０〜３０質量部、分散剤の含有量がカーボンブラック１００質量部に対して１〜６質量部、ポリフッ化ビニリデン系ポリマーの含有量がカーボンブラック１００質量部に対して２０質量部以下、かつ、ｘ＝ａ／Ｍｗ（ただし、ａは、１１×１０5≦ａ≦２２×１０6の範囲内である数、Ｍｗはポリフッ化ビニリデン系ポリマーの重量平均分子量）であって、分散液の粘度がせん断速度１／ｓ以上１００／ｓ未満の範囲内で０．１〜３Ｐａ・ｓの粘度の極小値を示すようにせん断型分散機を用いて分散させることで、適度な分散度に制御しつつ、ダイラタントであってもポリフッ化ビニリデン系ポリマーがろ過材に対して潤滑剤として作用するためろ過詰まりを発生させず、さらに、ｘが２０以下であれば種々のデバイスやリチウムイオン二次電池に適応可能であることを見出した。 The inventors of the present invention have a carbon black content of 10 to 30 parts by mass with respect to 100 parts by mass of the dispersion, a dispersant content of 1 to 6 parts by mass with respect to 100 parts by mass of the carbon black, and a polyvinylidene fluoride system. The polymer content is 20 parts by mass or less with respect to 100 parts by mass of carbon black, and x = a / Mw (where a is a number within the range of 11 × 10 5 ≦ a ≦ 22 × 10 6 , Mw Is the weight average molecular weight of the polyvinylidene fluoride polymer), and the viscosity of the dispersion exhibits a minimum viscosity of 0.1 to 3 Pa · s within the range of the shear rate of 1 / s or more and less than 100 / s. Dispersion using a shearing disperser causes control clogging because the polyvinylidene fluoride polymer acts as a lubricant for the filter medium, even with dilatant, while controlling to an appropriate degree of dispersion. Further found that x is adaptable to a variety of devices and the lithium ion secondary battery as long 20 or less.
即ち、本発明は、カーボンブラック、Ｎ−メチル−２−ピロリドン、ポリフッ化ビニリデン系ポリマーおよび分散剤を含んでなる電池用カーボンブラック分散液の製造方法であって、カーボンブラックの含有量が分散液１００質量部に対して１０〜３０質量部、分散剤の含有量がカーボンブラック１００質量部に対して１〜６質量部、ポリフッ化ビニリデン系ポリマーの含有量ｘが、カーボンブラック１００質量部に対して２０質量部以下、かつ、ｘ＝ａ／Ｍｗ（ただし、ａは、１１×１０5≦ａ≦２２×１０6の範囲内である数、Ｍｗはポリフッ化ビニリデン系ポリマーの重量平均分子量）であって、分散液の粘度がせん断速度１／ｓ以上１００／ｓ未満の範囲内で０．１〜３Ｐａ・ｓの粘度の極小値を示すようにせん断型分散機を用いて分散させる電池用カーボンブラック分散液の製造方法に関する。 That is, the present invention relates to a method for producing a carbon black dispersion for a battery comprising carbon black, N-methyl-2-pyrrolidone, a polyvinylidene fluoride polymer and a dispersant, wherein the carbon black content is a dispersion. 10 to 30 parts by mass with respect to 100 parts by mass, 1 to 6 parts by mass with respect to 100 parts by mass of carbon black, and x of the content of polyvinylidene fluoride polymer with respect to 100 parts by mass of carbon black 20 parts by mass or less and x = a / Mw (where a is a number within the range of 11 × 10 5 ≦ a ≦ 22 × 10 6 and Mw is the weight average molecular weight of the polyvinylidene fluoride polymer) Then, the dispersion liquid was separated using a shearing disperser so that the viscosity showed a minimum value of 0.1 to 3 Pa · s within the range of the shear rate of 1 / s or more and less than 100 / s. It relates to a method for producing a carbon black dispersion battery for.
また、本発明は、３３×１０5≦ａ≦１１×１０6である前記電池用カーボンブラック分散液の製造方法に関する。 The present invention also relates to a method for producing the carbon black dispersion for a battery, wherein 33 × 10 5 ≦ a ≦ 11 × 10 6 .
また、本発明は、分散剤が酸性官能基を有する有機色素誘導体、酸性官能基を有するトリアジン誘導体、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するトリアジン誘導体、ポリビニルアルコール、ポリビニルブチラール、ポリビニルピロリドン、変性ポリビニルアルコール、変性ポリビニルブチラールおよび変性ポリビニルピロリドンからなる群より選ばれる少なくともひとつである前記電池用カーボンブラック分散液の製造方法に関する。 The present invention also relates to an organic dye derivative having an acidic functional group, a triazine derivative having an acidic functional group, an organic dye derivative having a basic functional group, a triazine derivative having a basic functional group, polyvinyl alcohol, and polyvinyl butyral. And a method for producing a carbon black dispersion for a battery, which is at least one selected from the group consisting of polyvinyl pyrrolidone, modified polyvinyl alcohol, modified polyvinyl butyral, and modified polyvinyl pyrrolidone.
また、本発明は、動的光散乱法により測定した分散液のＤ５０値が３００〜８００ｎｍである前記電池用カーボンブラック分散液の製造方法に関する。 The present invention also relates to a method for producing a carbon black dispersion for a battery, wherein the D50 value of the dispersion measured by a dynamic light scattering method is 300 to 800 nm.
また、本発明は、カーボンブラックの比表面積が５〜３００ｍ2／ｇである請求項１〜４いずれかに記載の電池用カーボンブラック分散液の製造方法に関する。 Moreover, this invention relates to the manufacturing method of the carbon black dispersion liquid for batteries in any one of Claims 1-4 whose specific surface area of carbon black is 5-300 m < 2 > / g.
また、本発明は、前記方法により製造されたカーボンブラック分散液に、正極または負極活物質と、さらにポリフッ化ビニリデン系ポリマーおよび／またはＮ−メチル−２−ピロリドンと、を加えて混合する電池用スラリーの製造方法に関する。 The present invention also provides a battery for mixing a carbon black dispersion produced by the above method with a positive electrode or negative electrode active material, and further, a polyvinylidene fluoride polymer and / or N-methyl-2-pyrrolidone. The present invention relates to a method for producing a slurry.
また、本発明は、前記方法により製造された電池用スラリーを用いた電極の製造方法に関する。 Moreover, this invention relates to the manufacturing method of the electrode using the slurry for batteries manufactured by the said method.
また、本発明は、前記方法により製造された電極を用いたリチウムイオン二次電池の製造方法に関する。 Moreover, this invention relates to the manufacturing method of the lithium ion secondary battery using the electrode manufactured by the said method.
本発明により、出力、量産性、貯蔵安定性、ろ過性を向上させたリチウムイオン二次電池用カーボン分散液の提供が可能になる。 According to the present invention, it is possible to provide a carbon dispersion for a lithium ion secondary battery with improved output, mass productivity, storage stability, and filterability.
以下、本発明の詳細を説明する。尚、本明細書では、「ポリフッ化ビニリデン系ポリマー」をＰＶｄＦ、「Ｎ−メチル−２−ピロリドン」を「ＮＭＰ」、カーボンブラックを「ＣＢ」、「ポリビニルアルコール」をＰＶＡ、「ポリビニルブチラール」をＰＶＢ、「ポリビニルピロリドン」をＰＶＰ、「ＰＶＡ、ＰＶＢ、ＰＶＰと（メタ）アクリル酸および（メタ）アクリル酸エステルと共重合させたもの、または変性させたもの」を変性ＰＶＡ、変性ＰＶＢ、変性ＰＶＰと略記することがある。また、カーボンブラック分散液を単に「分散液」と略記することがある。 Details of the present invention will be described below. In this specification, “polyvinylidene fluoride polymer” is PVdF, “N-methyl-2-pyrrolidone” is “NMP”, carbon black is “CB”, “polyvinyl alcohol” is PVA, and “polyvinyl butyral” is PVB, "polyvinylpyrrolidone" PVP, "PVA, PVB, PVP copolymerized with (meth) acrylic acid and (meth) acrylic acid ester or modified" "modified PVA, modified PVB, modified PVP May be abbreviated. Further, the carbon black dispersion may be simply abbreviated as “dispersion”.
＜カーボンブラック＞
本発明に用いるカーボンブラックとしては、市販のアセチレンブラック、ファーネスブラック、中空カーボンブラック、チャンネルブラック、サーマルブラック、ケッチェンブラックなど各種のものを用いることができる。また、通常行われている酸化処理されたカーボンブラックや、黒鉛化処理されたカーボンブラック、カーボンナノチューブやカーボンナノファイバー、黒鉛や薄片状黒鉛、グラフェンなども使用できる。
<Carbon black>
As the carbon black used in the present invention, various types such as commercially available acetylene black, furnace black, hollow carbon black, channel black, thermal black, ketjen black and the like can be used. Ordinarily oxidized carbon black, graphitized carbon black, carbon nanotubes and carbon nanofibers, graphite, flaky graphite, graphene, and the like can also be used.
カーボンブラックの酸化処理は、カーボンブラックを空気中で高温処理したり、硝酸や二酸化窒素、オゾン等で二次的に処理したりすることによって、例えばフェノール基、キノン基、カルボキシル基、カルボニル基のような酸素含有極性官能基をカーボンブラック表面に直接導入（共有結合）する処理であり、カーボンブラックの分散性を向上させるために一般的に行われている。 The oxidation treatment of carbon black is performed by treating the carbon black at a high temperature in the air or by treating it with nitric acid, nitrogen dioxide, ozone, etc., for example, phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) such an oxygen-containing polar functional group to the surface of carbon black, and is generally performed to improve the dispersibility of carbon black.
分散液の製造に用いるカーボンブラックの平均一次粒子径としては、一般的な分散液や塗料に用いられるカーボンブラックの平均一次粒子径範囲と同様に０．０１〜１μｍが好ましく、特に、０．０１〜０．２μｍが好ましく、０．０１〜０．１μｍがさらに好ましい。ここでいう平均一次粒子径とは、電子顕微鏡で測定された算術平均粒子径を示し、この物性値は一般にカーボンブラックの物理的特性を表すのに用いられている。 The average primary particle size of the carbon black used for the production of the dispersion is preferably 0.01 to 1 μm, particularly the average primary particle size range of the carbon black used for general dispersions and paints. -0.2 micrometer is preferable and 0.01-0.1 micrometer is further more preferable. The average primary particle size referred to here indicates an arithmetic average particle size measured with an electron microscope, and this physical property value is generally used to represent the physical characteristics of carbon black.
カーボンブラックの物理的特性を表すその他の物性値としては、ＢＥＴ比表面積やｐＨが知られている。ＢＥＴ比表面積は、窒素吸着によりＢＥＴ法で測定された比表面積（以下、単に比表面積と記載）を指し、この比表面積はカーボンブラックの表面積に対応しており、比表面積が大きいほど分散剤を必要とする量も多くなる。ｐＨはカーボンブラック表面の官能基や含有不純物の影響を受けて変化する。 As other physical property values representing the physical characteristics of carbon black, BET specific surface area and pH are known. The BET specific surface area refers to a specific surface area (hereinafter simply referred to as a specific surface area) measured by the BET method by nitrogen adsorption, and this specific surface area corresponds to the surface area of carbon black. The amount you need also increases. The pH changes under the influence of functional groups on the carbon black surface and impurities contained therein.
本発明で用いるカーボンブラックは、ＢＥＴ比表面積が５〜３００ｍ2／ｇのものが好ましく、３０〜８０ｍ2／ｇのものが特に好ましい。 Carbon black used in the present invention, BET specific surface area is preferably a 5 to 300 m 2 / g, particularly preferably from 30~80m 2 / g.
本発明で用いるカーボンブラックは、特に限定されるものではないが、アセチレンブラックやファーネスブラックなど、高い導電性を有し、かつ工業的に生産されるカーボンブラックが好適に用いられる。 The carbon black used in the present invention is not particularly limited, but industrially produced carbon black such as acetylene black and furnace black is preferably used.
＜ポリフッ化ビニリデン系ポリマー＞
本発明で用いるポリフッ化ビニリデン系ポリマーＰＶｄＦは、重量平均分子量が大きい方が潤滑剤としての効果が高いため添加量を少なくでき、設計の自由度が上がる。また、重量平均分子量が小さくなると、バインダーの耐性や密着性が低下することがあり、分子量が大きくなると耐性や密着性は向上するものの、バインダー自体の粘度が高くなり作業性が低下するとともに、凝集剤として働く場合がある。したがって、重量平均分子量が２００，０００〜１，５００，０００が好ましく、５００，０００〜１，２００，０００がより好ましい。
<Polyvinylidene fluoride polymer>
The polyvinylidene fluoride polymer PVdF used in the present invention has a higher effect as a lubricant when the weight average molecular weight is larger, so that the amount added can be reduced and the degree of freedom in design is increased. In addition, when the weight average molecular weight decreases, the resistance and adhesion of the binder may decrease, and when the molecular weight increases, the resistance and adhesion improve, but the viscosity of the binder itself increases and workability decreases, and aggregation May work as an agent. Therefore, the weight average molecular weight is preferably 200,000 to 1,500,000, more preferably 500,000 to 1,200,000.
ＰＶｄＦは、高電位にさらされる電池内の過酷な環境下でも優れた耐性を有するが、接着性の弱い樹脂であるために、塗膜にした際の基材に対する密着性を高めるために酸性官能基を有する共重合体を用いることもある。本発明では、ＰＶｄＦはホモポリマーであっても、酸性官能基を有する共重合体であってもよい。 PVdF has excellent resistance even in a harsh environment in a battery exposed to a high potential, but since it is a resin with low adhesiveness, it has an acidic functionality in order to increase adhesion to a substrate when formed into a coating film. A copolymer having a group may be used. In the present invention, PVdF may be a homopolymer or a copolymer having an acidic functional group.
＜Ｎ−メチル−２−ピロリドン＞
ＮＭＰは、ＰＶｄＦの好適な良溶媒であることから、リチウムイオン二次電池の電極製造に用いられている。本発明では、他の溶剤を１種類以上併用しても良いが、電極製造時に発生したＮＭＰ蒸気を回収して再利用することが環境上、コスト上好ましく、再生時に分留が難しくなることから、ＮＭＰを単独で用いることが好ましい。
<N-methyl-2-pyrrolidone>
Since NMP is a suitable good solvent for PVdF, it is used for manufacturing electrodes of lithium ion secondary batteries. In the present invention, one or more kinds of other solvents may be used in combination. However, it is preferable from an environmental and cost viewpoint to recover and reuse NMP vapor generated at the time of electrode production because fractionation is difficult at the time of regeneration. , NMP is preferably used alone.
＜分散剤＞
本発明に用いる分散剤としては、カーボンブラックと活物質の一方または両方の分散性を向上させるものであれば、特に限定されるものではないが、例えば、特許４２４０１５７号公報に記載の酸性官能基を有する有機色素誘導体またはトリアジン誘導体、特許４４２０１２３号公報に記載の塩基性官能基を有する有機色素誘導体またはトリアジン誘導体、特許５４５４７２５号公報に記載のＰＶＡ、特許４２３５７８８号公報に記載のＰＶＰ、特開２０１１−１８４６６４に記載のＰＶＢを用いることができる。
<Dispersant>
The dispersant used in the present invention is not particularly limited as long as it improves the dispersibility of one or both of carbon black and active material. For example, the acidic functional group described in Japanese Patent No. 4240157 is disclosed. Organic dye derivatives or triazine derivatives having a basic functional group, organic dye derivatives or triazine derivatives having a basic functional group described in Japanese Patent No. 4420123, PVA described in Japanese Patent No. 5454725, PVP described in Japanese Patent No. 4235788, JP 2011 PVB described in 184664 can be used.
分散剤の具体例として、表１に示す分散剤Ａ：酸性官能基を有する有機色素誘導体、分散剤Ｂ、Ｃ：酸性官能基を有するトリアジン誘導体、分散剤Ｄ：塩基性官能基を有する有機色素誘導体、分散剤Ｅ：塩基性官能基を有するトリアジン誘導体や、樹脂型分散剤として、分散剤Ｆ：ゴーセノールＫＬ−０３（ＰＶＡ、日本合成化学社製、けん化度７８．５〜８２．０ｍｏｌ％、平均重合度５００以下）、分散剤Ｇ：ＫＬ−５０６（変性ＰＶＡ、クラレ社製、けん化度７４．０〜８０．０ｍｏｌ％、平均重合度約６００）、分散剤Ｈ：ＰＶＰ Ｋ３０（日本触媒社製、分子量約４万）、分散剤Ｉ：エスレックＢＬ−１（ＰＶＢ、積水化学社製、分子量約１．９万）が挙げられる。 Specific examples of the dispersant include, as shown in Table 1, dispersant A: an organic dye derivative having an acidic functional group, dispersant B, C: a triazine derivative having an acidic functional group, dispersant D: an organic dye having a basic functional group Derivative, Dispersant E: Triazine derivative having a basic functional group, and resin type dispersant, Dispersant F: Gohsenol KL-03 (PVA, Nippon Synthetic Chemical Co., Ltd., saponification degree 78.5-82.0 mol%, Dispersant G: KL-506 (modified PVA, manufactured by Kuraray Co., Ltd., saponification degree: 74.0-80.0 mol%, average polymerization degree: about 600), Dispersant H: PVP K30 (Nippon Shokubai Co., Ltd.) Manufactured, having a molecular weight of about 40,000), dispersant I: ESREC BL-1 (PVB, manufactured by Sekisui Chemical Co., Ltd., molecular weight of about 19 million).
上記分散剤の中でも、とりわけ下記一般式（１）で示されるトリアジン誘導体の使用が好ましい。 Among the above dispersants, the use of a triazine derivative represented by the following general formula (1) is particularly preferable.
一般式（１）
Ｘ1は−ＮＨ−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ2ＮＨ−、−ＣＨ2ＮＨ−、−ＣＨ2ＮＨＣＯＣＨ2ＮＨ−または−Ｘ3−Ｙ−Ｘ4−を表し、Ｘ2及びＸ4はそれぞれ独立に−ＮＨ−または−Ｏ−を表し、Ｘ3は−ＣＯＮＨ−、−ＳＯ2ＮＨ−、−ＣＨ2ＮＨ−、−ＮＨＣＯ−または−ＮＨＳＯ2−を表し、
Ｙは炭素数１〜２０で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または置換基を有してもよいアリーレン基を表し、
Ｚは−ＳＯ3Ｍまたは−ＣＯＯＭ、または−Ｐ（Ｏ）（−ＯＭ）2を表し、Ｍは１〜３価のカチオンの一当量を表し、
Ｒ1は有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基または下記一般式（２）で表される基を表し、
Ｑは−Ｏ−Ｒ2、−ＮＨ−Ｒ2、ハロゲン基、−Ｘ1−Ｒ1または−Ｘ2−Ｙ−Ｚを表し、Ｒ2は水素原子、置換基を有してもよいアルキル基または置換基を有してもよいアルケニル基を表す。
General formula (1)
X 1 is -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 3 -Y-X 4 - represents, X 2 and X 4 each independently represent a -NH- or -O-, X 3 is -CONH -, - SO 2 NH - , - CH 2 NH -, - NHCO- or -NHSO 2 - represents,
Y represents a C1-C20 alkylene group which may have a substituent, an alkenylene group which may have a substituent or an arylene group which may have a substituent,
Z represents —SO 3 M or —COOM, or —P (O) (— OM) 2 , M represents one equivalent of a monovalent to trivalent cation,
R 1 represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the following general formula (2). ,
Q represents —O—R 2 , —NH—R 2 , a halogen group, —X 1 —R 1 or —X 2 —YZ, and R 2 represents a hydrogen atom or an alkyl group which may have a substituent. Or the alkenyl group which may have a substituent is represented.
一般式（２）
Ｒ3及びＲ4はそれぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基または−Ｙ−Ｚを表し、Ｙ及びＺは一般式（１）と同じ意味を表す。
General formula (2)
R 3 and R 4 each independently represents an organic dye residue, an optionally substituted heterocyclic residue, an optionally substituted aromatic ring residue, or —YZ. , Y and Z represent the same meaning as in general formula (1).
一般式（１）の式中Ｍは、１〜３価のカチオンの一当量を表し、例えば、水素原子（プロトン）、金属カチオン、４級アンモニウムカチオンのいずれかを表す。また、分散剤構造中にＭを２つ以上有する場合、Ｍはプロトン、金属カチオン、４級アンモニウムカチオンのいずれかひとつのみでも良いし、これらの組み合わせでも良い。金属としては、リチウム、ナトリウム、カリウム、カルシウム、バリウム、マグネシウム、アルミニウム、ニッケル、コバルト等が挙げられる。 In the formula of the general formula (1), M represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation. Further, when two or more Ms are included in the dispersant structure, M may be only one of a proton, a metal cation, and a quaternary ammonium cation, or a combination thereof. Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.
４級アンモニウムカチオンとしては、一般式（３）で示される構造を有する単一化合物
または、混合物である。
The quaternary ammonium cation is a single compound having a structure represented by the general formula (3) or a mixture.
一般式（３）
一般式（３）のＲ5、Ｒ6、Ｒ7、Ｒ8は、それぞれ同一でもよいし、異なっていてもよい。また、Ｒ5、Ｒ6、Ｒ7、Ｒ8が炭素原子を有する場合、炭素数は１〜４０、好ましくは１〜３０、更に好ましくは１〜２０である。炭素数が４０を超えると電極の導電性が低下する場合がある。 R 5 , R 6 , R 7 and R 8 in the general formula (3) may be the same or different. Moreover, when R < 5 >, R < 6 >, R < 7 >, R < 8 > has a carbon atom, carbon number is 1-40, Preferably it is 1-30, More preferably, it is 1-20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.
４級アンモニウムの具体例としては、ジメチルアンモニウム、トリメチルアンモニウム、ジエチルアンモニウム、トリエチルアンモニウム、ヒドロキシエチルアンモニウム、ジヒドロキシエチルアンモニウム、２−エチルヘキシルアンモニウム、ジメチルアミノプロピルアンモニウム、オクチルアンモニウム、ラウリルアンモニウム、ステアリルアンモニウム等が挙げられるが、これらに限定されない。 Specific examples of quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, octylammonium, laurylammonium, stearylammonium and the like. However, it is not limited to these.
また、樹脂型分散剤の中では、ＰＶＡまたは変性ＰＶＡの使用が特に好ましい。ＰＶＡおよび変性ＰＶＡは、溶媒やカーボンブラックとの親和性の観点から、けん化度が５０〜９５ｍｏｌ％、平均重合度は２０００以下が好ましく、けん化度が７０〜８５ｍｏｌ％、平均重合度は１０００以下がより好ましい。変性ＰＶＡには4級アンモニウム塩を有するカチオン変性ＰＶＡ、スルホン酸基やスルホン酸金属塩、カルボキシル基、カルボン酸金属塩を有するアニオン変性ＰＶＡ等が使用できるが、特にカルボキシル基やカルボン酸金属塩を有する変性ＰＶＡが好ましい。 Among resin-type dispersants, the use of PVA or modified PVA is particularly preferable. PVA and modified PVA have a saponification degree of 50 to 95 mol% and an average polymerization degree of preferably 2000 or less, and a saponification degree of 70 to 85 mol% and an average polymerization degree of 1000 or less from the viewpoint of affinity with a solvent or carbon black. More preferred. As the modified PVA, a cation-modified PVA having a quaternary ammonium salt, an anion-modified PVA having a sulfonic acid group or a sulfonic acid metal salt, a carboxyl group, or a carboxylic acid metal salt can be used. The modified PVA having is preferable.
カーボンブラック１００質量部に対する分散剤の添加量は、１〜６質量部であり、２〜４質量部が好ましい。分散剤の最適添加量は作用するカーボンブラックの比表面積に相関があり、比表面積が大きいカーボンブラック程多く必要になる。また、酸化処理されたカーボンブラックは分散性が良いため、酸化処理されていない同じ比表面積のカーボンブラックよりも必要な分散剤量は少なくてよい。最適な分散剤添加量よりも少なすぎると、分散液の粘度が高くなる、もしくは、分散液の濃度が低くなってしまう。また、長期保管中に凝集や沈降が起こりやすいため、貯蔵安定性も悪くなる。分散剤添加量が多すぎると、電池内で抵抗成分となって出力低下を引き起こす。 The addition amount of the dispersant with respect to 100 parts by mass of carbon black is 1 to 6 parts by mass, and preferably 2 to 4 parts by mass. The optimum addition amount of the dispersant has a correlation with the specific surface area of the acting carbon black, and the more the carbon black with the larger specific surface area is required. In addition, since the oxidized carbon black has good dispersibility, a smaller amount of dispersant may be required than carbon black having the same specific surface area that has not been oxidized. When the amount is less than the optimum amount of the dispersant added, the viscosity of the dispersion becomes high or the concentration of the dispersion becomes low. Moreover, since aggregation and sedimentation are likely to occur during long-term storage, the storage stability also deteriorates. If the amount of the dispersant added is too large, it becomes a resistance component in the battery and causes a decrease in output.
＜カーボンブラック分散液の製造方法＞
本発明の分散液は、分散剤とともにカーボンブラックをＮＭＰ中に分散したものである。この場合、分散剤とカーボンブラックを同時、または順次添加し混合することで、分散剤をカーボンブラックに作用（吸着）させつつ分散する。ただし、分散剤をＮＭＰ中に溶解、膨潤、または分散させ、その後、液中にカーボンブラックを添加し混合した方が、分散液の製造をより容易に行うことができる。また、分散剤がカーボンブラックにより均一に作用できるため、貯蔵安定性が増す。ＰＶｄＦは粉末の状態で添加しても、予めＮＭＰに溶解してワニスの状態で添加しても良いし、他の材料の添加のタイミングに係わらずどのタイミングで添加しても良い。ただし、ＰＶｄＦは継粉になりやすく、一旦継粉になると溶解が非常に困難になるため、カーボンブラックと同時に粉末の状態で添加した方が容易に溶解でき、より好ましい。さらに、ＰＶｄＦを単独で溶解させるには多くのＮＭＰを要するため、カーボンブラックを分散させてからワニスを添加すると、電池用スラリーとして好適な濃度が達成できなくなる場合がある。
<Method for producing carbon black dispersion>
The dispersion of the present invention is obtained by dispersing carbon black in NMP together with a dispersant. In this case, the dispersing agent and carbon black are added simultaneously or sequentially and mixed to disperse the dispersing agent while acting (adsorbing) on the carbon black. However, the dispersion can be more easily produced by dissolving, swelling, or dispersing the dispersant in NMP and then adding and mixing the carbon black in the liquid. In addition, since the dispersant can act uniformly with carbon black, the storage stability is increased. PVdF may be added in the form of a powder, dissolved in NMP in advance and added in the form of a varnish, or may be added at any timing regardless of the timing of addition of other materials. However, PVdF tends to be a splint, and once it becomes a splint, it becomes very difficult to dissolve. Therefore, it is more preferable to add it in a powder state together with carbon black because it can be easily dissolved. Furthermore, since a large amount of NMP is required to dissolve PVdF alone, when varnish is added after carbon black is dispersed, a concentration suitable for battery slurry may not be achieved.
混合、分散を行う装置としては、顔料分散等に通常用いられているせん断型分散機を使用することができる。例えば、ディスパー、ホモミキサー、プラネタリーミキサー等のミキサー類、ホモジナイザー（エム・テクニック社製「クレアミックス」、ＰＲＩＭＩＸ社「フィルミックス」、「ハイシェアミキサー」等、シルバーソン社製「アブラミックス」、「ミキサー」等）類、ロールミル、等が挙げられるが、これらに限定されるものではない。 As a device for mixing and dispersing, a shearing disperser usually used for pigment dispersion or the like can be used. For example, mixers such as dispersers, homomixers, planetary mixers, homogenizers ("Claremix" manufactured by M Technique, PRIMIX "Fillmix", "High Share Mixer", etc.), "Abramix" manufactured by Silverson, "Mixer" and the like), roll mill, and the like, but are not limited thereto.
比較として用いるメディア型分散機としては、ペイントコンディショナー（レッドデビル社製）、コロイドミル（ＰＵＣ社製「ＰＵＣコロイドミル」、ＩＫＡ社製「コロイドミルＭＫ」）類、コーンミル（ＩＫＡ社製「コーンミルＭＫＯ」等）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル等のメディア型分散機が挙げられる。 Media type dispersers used for comparison include paint conditioners (manufactured by Red Devil), colloid mills ("PUC colloid mill" manufactured by PUC, "colloid mill MK" manufactured by IKA), and cone mills ("corn mill MKO manufactured by IKA"). Etc.), a ball mill, a sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), an attritor, a pearl mill (such as “DCP mill” manufactured by Eirich), and a coball mill.
カーボンブラック分散液中のカーボンブラック濃度は、１０〜３０質量部であり、１７〜２４質量部が好ましい。カーボンブラック濃度が低いと活物質を加えたスラリー濃度も低くなり、塗工に好適な濃度が得られない場合がある。逆に高すぎると流動性を失い、作業性が低下するだけでなく、カーボンブラックやＰＶｄＦの凝集が発生して粗大粒子が残ってしまう。 The carbon black concentration in the carbon black dispersion is 10 to 30 parts by mass, preferably 17 to 24 parts by mass. If the carbon black concentration is low, the concentration of the slurry added with the active material is also low, and a concentration suitable for coating may not be obtained. On the other hand, if it is too high, not only will fluidity be lost and workability will deteriorate, but also agglomeration of carbon black and PVdF will occur and coarse particles will remain.
前述の通り、カーボンブラックは分散度が高すぎても低すぎても抵抗を増大させる。分散度を評価するひとつの方法として、動的光散乱方式の粒度分布測定がある。これより求められる平均粒子径Ｄ５０は、抵抗低減のために、０．３〜０．８μｍが好ましく、０．４〜０．６がより好ましい。 As described above, carbon black increases resistance whether the degree of dispersion is too high or too low. One method for evaluating the degree of dispersion is a dynamic light scattering particle size distribution measurement. Average particle diameter D50 calculated | required from this is 0.3-0.8 micrometer for the resistance reduction, and 0.4-0.6 are more preferable.
分散液のレオロジーも分散度を評価する手法として用いられており、せん断速度１／ｓ以上１００／ｓ未満において極小値を有し、極小の粘度が０．１〜３Ｐａ・ｓとなるまでせん断型分散機により分散させると、抵抗が最も低くなる。 The rheology of the dispersion is also used as a method for evaluating the degree of dispersion. The shear type has a minimum value at a shear rate of 1 / s or more and less than 100 / s, and the minimum viscosity is 0.1 to 3 Pa · s. When dispersed by a disperser, the resistance is lowest.
＜活物質＞
本発明の分散液を電池電極に用いる場合は、さらに、正極活物質または負極活物質を含有させることができる。
<Active material>
When using the dispersion liquid of this invention for a battery electrode, a positive electrode active material or a negative electrode active material can be contained further.
リチウムイオン二次電池用の正極活物質としては、特に限定はされないが、リチウムイオンをドーピングまたはインターカレーション可能な金属酸化物、金属硫化物等の金属化合物、および導電性高分子等を使用することができる。
例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ等の遷移金属の酸化物、金属Ｌｉやリチウムとの複合酸化物、遷移金属硫化物等の無機化合物等が挙げられる。具体的には、ＭｎＯ、Ｖ2Ｏ5、Ｖ6Ｏ13、ＴｉＯ2等の遷移金属酸化物粉末、層状構造のニッケル酸リチウム、コバルト酸リチウム、マンガン酸リチウム、スピネル構造のマンガン酸リチウムなどのリチウムと遷移金属との複合酸化物粉末、オリビン構造のリン酸化合物であるリン酸鉄リチウム系材料、ＴｉＳ2、ＦｅＳなどの遷移金属硫化物粉末等が挙げられる。また、ポリアニリン、ポリアセチレン、ポリピロール、ポリチオフェン等の導電性高分子を使用することもできる。また、上記の無機化合物や有機化合物を混合して用いてもよい。
The positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to.
Examples include oxides of transition metals such as Fe, Co, Ni, and Mn, composite oxides with metals Li and lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc. Examples thereof include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, and transition metal sulfide powders such as TiS 2 and FeS. In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.
リチウムイオン二次電池用の負極活物質としては、リチウムイオンをドーピングまたはインターカレーション可能なものであれば特に限定されない。例えば、金属Ｌｉ、その合金であるスズ合金、シリコン合金、鉛合金等の合金系、ＬｉXＦｅ2Ｏ3、ＬｉXＦｅ3Ｏ4、ＬｉXＷＯ2（０＜ｘ＜２）、チタン酸リチウム、バナジウム酸リチウム、ケイ素酸リチウム等の金属酸化物系、ポリアセチレン、ポリ−ｐ−フェニレン等の導電性高分子系、ソフトカーボンやハードカーボンといった、アモルファス系炭素質材料や、高黒鉛化炭素材料等の人造黒鉛、あるいは天然黒鉛等の炭素質粉末、カーボンブラック、メソフェーズカーボンブラック、樹脂焼成炭素材料、気層成長炭素繊維、炭素繊維などの炭素系材料が挙げられる。これら負極活物質は、１種または複数を組み合わせて使用することもできる。 The negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metallic Li, alloys thereof such as tin alloys, silicon alloys, lead alloys, etc., Li x Fe 2 O 3 , Li x Fe 3 O 4 , Li x WO 2 (0 <x <2), titanic acid Metallic oxides such as lithium, lithium vanadate, and lithium siliconate, conductive polymer such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, and highly graphitized carbon materials And carbonaceous materials such as artificial graphite such as natural graphite, carbon black such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, vapor-grown carbon fiber, and carbon fiber. These negative electrode active materials can be used alone or in combination.
本発明で用いる電極活物質は、リチウムおよびリチウム以外の金属元素を主要構成成分として含有する活物質であることが好ましく、正極活物質であることがより好ましい。 The electrode active material used in the present invention is preferably an active material containing lithium and a metal element other than lithium as a main constituent, and more preferably a positive electrode active material.
本発明で用いる正極活物質は、Ａｌ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ等の遷移金属を含むリチウムとの複合酸化物であることが好ましく、Ａｌ、Ｃｏ、Ｎｉ、Ｍｎのうちいずれかを含むリチウムとの複合酸化物であることがより好ましく、Ｎｉ、Ｍｎを含むリチウムとの複合酸化物であることが特に好ましい。 The positive electrode active material used in the present invention is preferably a composite oxide with lithium containing a transition metal such as Al, Fe, Co, Ni, or Mn, and lithium containing any of Al, Co, Ni, and Mn. And a composite oxide with lithium containing Ni and Mn is particularly preferable.
これらの活物質は、ＢＥＴ比表面積が０．１〜３０ｍ2／ｇのものが好ましく、０．２〜１０ｍ2／ｇのものがより好ましく、０．２〜５ｍ2／ｇのものがさらに好ましい。 These active material preferably has a BET specific surface area of 0.1~30m 2 / g, more preferably a 0.2 to 10 m 2 / g, further preferably from 0.2~5m 2 / g .
これらの活物質は、平均粒子径が０．０５〜１００μｍの範囲内であることが好ましく、さらに好ましくは、０．１〜５０μｍの範囲内である。本明細書でいう活物質の平均粒子径とは、活物質を電子顕微鏡で観察した粒子径の平均値である。 These active materials preferably have an average particle diameter in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. The average particle diameter of the active material as used herein is an average value of particle diameters obtained by observing the active material with an electron microscope.
＜電池用スラリーの製造方法＞
本発明の分散液に、正極活物質または負極活物質を加えて電池用スラリーを作製することができる。電池用スラリーには、分散液に含有のＰＶｄＦと同一もしくは異なる種類のＰＶｄＦを加えても良いし、さらにＮＭＰを加えても良い。また、電池の耐久性を向上させる目的で、主要成分以外の公知の物質を添加して用いても良い。
<Method for producing slurry for battery>
A slurry for a battery can be produced by adding a positive electrode active material or a negative electrode active material to the dispersion of the present invention. To the battery slurry, PVdF of the same or different type from the PVdF contained in the dispersion may be added, or NMP may be further added. Moreover, you may add and use well-known substances other than a main component in order to improve durability of a battery.
電池用スラリーを分散、混合する装置としては、カーボンブラックの分散度を維持するために、前述の「カーボンブラック分散液の製造方法」に記載のせん断型分散機を用いるのが好ましい。この際、カーボンブラック分散液と活物質粉末を混合、分散させても良いし、予め分散させた活物質をカーボンブラック分散液と混合しても良い。 As a device for dispersing and mixing the battery slurry, it is preferable to use the shearing disperser described in the above-mentioned “Method for producing carbon black dispersion” in order to maintain the degree of dispersion of carbon black. At this time, the carbon black dispersion and the active material powder may be mixed and dispersed, or the previously dispersed active material may be mixed with the carbon black dispersion.
カーボンブラック分散液と活物質の粉末を混合、分散させる場合は、分散液に活物質粉末を加えても、活物質粉末に分散液を加えても良いが、分散液に活物質粉末を撹拌しながら少しずつ加えるのが特に好ましい。特に分散によってダメージを受けやすい活物質の場合は、ディスパー等の弱い分散機を用いて分散液に活物質粉末を撹拌しながら少しずつ加えることで、活物質本来の特性を引き出すことができる。 When mixing and dispersing the carbon black dispersion and the active material powder, the active material powder may be added to the dispersion, or the dispersion may be added to the active material powder, but the active material powder is stirred into the dispersion. It is particularly preferable to add little by little. In particular, in the case of an active material that is easily damaged by dispersion, the original characteristics of the active material can be brought out by adding the active material powder to the dispersion little by little using a weak disperser such as a disper.
予め分散させた活物質とカーボンブラック分散液を混合する場合は、どちらをどちらに加えても良いし、加えてから撹拌しても、撹拌しながら少しずつ加えても良い。２液の接触によっていずれかの分散状態が変化する場合には、撹拌しながら少しずつ加えるのが好ましい。また、活物質の分散に用いる分散機は、前述のせん断型分散機、メディア型分散機を用いることができるが、特に活物質同士の凝集や融着が激しい場合は、より強力なメディア型分散機を用いるのが好ましい。 When mixing the pre-dispersed active material and the carbon black dispersion, either may be added to either, and the mixture may be added after stirring, or may be added little by little while stirring. When any of the dispersed states changes due to the contact of the two liquids, it is preferably added little by little while stirring. In addition, as the disperser used for dispersing the active material, the above-mentioned shear type disperser and media type disperser can be used. It is preferable to use a machine.
ＰＶｄＦを加える場合は、いずれのタイミングで加えても良いが、比重の重い活物質の沈降を防ぐためには、活物質を添加する前または同時に加えるのが好ましい。ＰＶｄＦは粉末で添加してから溶解させても、予めＮＭＰに溶解させてから用いても良い。 When PVdF is added, it may be added at any timing. However, in order to prevent sedimentation of an active material having a high specific gravity, it is preferably added before or simultaneously with the addition of the active material. PVdF may be dissolved after being added as a powder, or may be used after being dissolved in NMP in advance.
異なる種類のＰＶｄＦを用いる場合は、主成分としたいＰＶｄＦ種の物性に一方のＰＶｄＦ種の物性が影響を受けて、所望の物性が得られないことがある。本発明では、カーボンブラック１００質量部に対して２０質量部以下、かつｘ＝ａ／Ｍｗ（ｘ：ＰＶｄＦのカーボンブラック１００質量部に対する質量部、Ｍｗ：ＰＶｄＦの重量平均分子量）においてａ≦２２×１０6とすることでこうした影響を抑えた。さらに、設計の自由度とハンドリングを上げるという観点から、ｘ≦１５、ａ≦１１×１０6がより好ましい。 When different types of PVdF are used, the physical properties of one PVdF species may be affected by the physical properties of the PVdF species desired to be the main component, and the desired physical properties may not be obtained. In the present invention, a ≦ 22 × in 20 parts by mass or less with respect to 100 parts by mass of carbon black and x = a / Mw (x: parts by mass of PVdF with respect to 100 parts by mass of carbon black, Mw: weight average molecular weight of PVdF). By setting it to 10 6 , this effect was suppressed. Furthermore, x ≦ 15 and a ≦ 11 × 10 6 are more preferable from the viewpoint of increasing the degree of design freedom and handling.
また、ａ≧１１×１０5のとき、ＰＶｄＦはろ過材に対して潤滑剤として作用し、ダイラタントな分散液がろ過詰まりを発生するのを防ぐことができる。ａ≧２２×１０5が好ましく、ａ≧３３×１０5がより好ましい。 Further, when a ≧ 11 × 10 5 , PVdF acts as a lubricant for the filter medium, and the dilatant dispersion can be prevented from clogging. a ≧ 22 × 10 5 is preferable, and a ≧ 33 × 10 5 is more preferable.
ＮＭＰを加える場合は、いずれのタイミングで加えても良いが、活物質やＰＶｄＦ等を加える工程の途中でＮＭＰが不足すると、分散したカーボンブラックや活物質の凝集が起きたり、溶解したＰＶｄＦの析出が生じることがあるため、適宜加えるのが好ましい。工程の途中でＮＭＰが多くなり粘度が低くなり過ぎる場合は、比重の重い活物質の沈降を防ぐために工程の最後に加えるのが好ましい。 When NMP is added, it may be added at any timing. However, if NMP is insufficient during the process of adding the active material, PVdF, etc., aggregation of dispersed carbon black or active material occurs or precipitation of dissolved PVdF occurs. Therefore, it is preferable to add as appropriate. When NMP increases during the process and the viscosity becomes too low, it is preferably added at the end of the process in order to prevent sedimentation of an active material having a high specific gravity.
＜電極＞
本発明の電池用スラリーを集電体上に塗工・乾燥することで、電極を得ることができる。
<Electrode>
An electrode can be obtained by coating and drying the battery slurry of the present invention on a current collector.
（集電体）
電極に使用する集電体の材質や形状は特に限定されず、各種二次電池にあったものを適宜選択することができる。例えば、集電体の材質としては、アルミニウム、銅、ニッケル、チタン、白金、又はステンレス等の金属や合金が挙げられる。また、形状としては、一般的には平板上の箔が用いられるが、表面を粗面化したものや、穴あき箔状のもの、及びメッシュ状の集電体も使用できる。また、集電体には導電性の下地層形成用組成物を用いた下地層を設けても良い。
(Current collector)
The material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various secondary batteries can be appropriately selected. For example, examples of the material for the current collector include metals and alloys such as aluminum, copper, nickel, titanium, platinum, and stainless steel. In general, a flat foil is used as the shape, but a roughened surface, a perforated foil, or a mesh current collector can also be used. Further, the current collector may be provided with a base layer using a conductive base layer forming composition.
集電体上に電池用スラリーや下地層形成用組成物を塗工する方法としては、特に制限はなく公知の方法を用いることができる。具体的には、ダイコーティング法、ディップコーティング法、ロールコーティング法、ドクターコーティング法、ナイフコーティング法、スプレーコティング法、グラビアコーティング法、スクリーン印刷法または静電塗装法等が挙げる事ができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できるが、特にこれらに限定されるものではない。 The method for applying the battery slurry or the underlayer forming composition on the current collector is not particularly limited, and a known method can be used. Specific examples include die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method, and the like. Examples of methods that can be used include standing drying, blower dryers, hot air dryers, infrared heaters, and far-infrared heaters, but are not particularly limited thereto.
また、塗布後に平版プレスやカレンダーロール等による圧延処理を行っても良い。電極合材層の厚みは、一般的には１μｍ以上、５００μｍ以下であり、好ましくは１０μｍ以上、３００μｍ以下である。 Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating. The thickness of the electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.
＜二次電池＞
正極もしくは負極の少なくとも一方に上記の電極を用い、二次電池を得ることができる。二次電池としては、リチウムイオン二次電池の他、ナトリウムイオン二次電池、マグネシウム二次電池、アルカリ二次電池、鉛蓄電池、ナトリウム硫黄二次電池、リチウム空気二次電池等が挙げられ、それぞれの二次電池において、従来から知られている電解液やセパレーター等を適宜用いることができる。また、電気二重層キャパシタやリチウムイオンキャパシタ、これらのハイブリッドキャパシタに用いても良い。
<Secondary battery>
A secondary battery can be obtained by using the above electrode for at least one of a positive electrode and a negative electrode. Secondary batteries include lithium ion secondary batteries, sodium ion secondary batteries, magnesium secondary batteries, alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, lithium air secondary batteries, etc. In the secondary battery, conventionally known electrolytes, separators, and the like can be used as appropriate. Moreover, you may use for an electric double layer capacitor, a lithium ion capacitor, and these hybrid capacitors.
（電解液）
リチウムイオン二次電池の場合を例にとって説明する。電解液としては、リチウムを含んだ電解質を非水系の溶媒に溶解したものを用いる。電解質としては、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、Ｌｉ（ＣＦ3ＳＯ2）2Ｎ、ＬｉＣ4Ｆ9ＳＯ3、Ｌｉ（ＣＦ3ＳＯ2）3Ｃ、ＬｉＩ、ＬｉＢｒ、ＬｉＣｌ、ＬｉＡｌＣｌ、ＬｉＨＦ2、ＬｉＳＣＮ、又はＬｉＢＰｈ4（ただし、Ｐｈはフェニル基を表す）等が挙げられるが、これらに限定されない。
(Electrolyte)
A case of a lithium ion secondary battery will be described as an example. As the electrolytic solution, an electrolyte containing lithium dissolved in a non-aqueous solvent is used. As electrolytes, LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, or LiBPh 4 (where Ph represents a phenyl group), but is not limited thereto.
非水系の溶媒としては、特に限定はされないが、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、及びジエチルカーボネート等のカーボネート類；γ−ブチロラクトン、γ−バレロラクトン、及びγ−オクタノイックラクトン等のラクトン類；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、１，２−メトキシエタン、１，２−エトキシエタン、及び１，２−ジブトキシエタン等のグライム類；メチルフォルメート、メチルアセテート、及びメチルプロピオネート等のエステル類；ジメチルスルホキシド、及びスルホラン等のスルホキシド類；並びに、アセトニトリル等のニトリル類等が挙げられる。これらの溶媒は、それぞれ単独で使用しても良いが、２種以上を混合して使用しても良い。 The non-aqueous solvent is not particularly limited. For example, carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1, Glymes such as 2-dibutoxyethane; esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. And the like. These solvents may be used alone or in combination of two or more.
（セパレーター）
セパレーターとしては、例えば、ポリエチレン不織布、ポリプロピレン不織布、ポリアミド不織布及びこれらに親水性処理を施したものが挙げられるが、特にこれらに限定されるものではない。
(separator)
Examples of the separator include, but are not limited to, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment.
（電池構造・構成）
本発明の組成物を用いたリチウムイオン二次電池の構造については特に限定されないが、通常、正極及び負極と、必要に応じて設けられるセパレーターとから構成され、ペーパー型、円筒型、ボタン型、積層型等、使用する目的に応じた種々の形状とすることができる。
(Battery structure / configuration)
The structure of the lithium ion secondary battery using the composition of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, a paper type, a cylindrical type, a button type, It can be made into various shapes according to the purpose of use, such as a laminated type.
本発明では、上記課題に支障を及ぼさない範囲で、塗膜物性等の調整等の目的で、従来公知の分散剤や樹脂、添加剤等を併用しても良い。
そのような分散剤としては、例えば、ポリビニルアルコール、ポリビニルアセタール樹脂やポリビニルピロリドン樹脂、従来公知の色素誘導体、低分子量の界面活性剤等が挙げられる。また樹脂としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリエチレン、ポリプロピレン、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、ポリアクリル酸、ポリアクリルアミド、ポリウレタン、ポリジメチルシロキサン、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、スチレンブタジエンゴムなどの各種ゴム、リグニン、ペクチン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、セルロース系樹脂、ポリアルキレンオキサイド、ポリビニルエーテル、キチン類、キトサン類、デンプン等が挙げられる。また添加剤としては、リン化合物、硫黄化合物、有機酸、アミン化合物やアミド化合物、有機エステル、各種シラン系やチタン系、アルミニウム系のカップリング剤等が挙げられる。これらの従来公知の分散剤や樹脂、添加剤等は、単独または２種類以上併用して用いることが出来る。
In the present invention, conventionally known dispersants, resins, additives and the like may be used in combination for the purpose of adjusting the physical properties of the coating film and the like as long as the above-described problems are not affected.
Examples of such a dispersant include polyvinyl alcohol, polyvinyl acetal resin, polyvinyl pyrrolidone resin, conventionally known pigment derivatives, low molecular weight surfactants, and the like. Examples of the resin include polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polyacrylamide, and polyurethane. , Polydimethylsiloxane, epoxy resin, acrylic resin, polyester resin, melamine resin, phenol resin, styrene butadiene rubber and other rubbers, lignin, pectin, gelatin, xanthan gum, welan gum, succinoglycan, cellulosic resin, polyalkylene oxide, Examples include polyvinyl ether, chitins, chitosans, starch and the like. Examples of the additive include phosphorus compounds, sulfur compounds, organic acids, amine compounds and amide compounds, organic esters, various silane-based, titanium-based, and aluminum-based coupling agents. These conventionally known dispersants, resins, additives and the like can be used alone or in combination of two or more.
実施例に基づき本発明を詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded.
＜カーボンブラック＞
・デンカブラック粒状品（電気化学工業社製）：アセチレンブラック、平均一次粒子径３５ｎｍ、比表面積６９ｍ2／ｇ、以下粒状品と略記する。
・デンカブラックＨＳ−１００（電気化学工業社製）：アセチレンブラック、平均一次粒子径４８ｎｍ、比表面積３９ｍ2／ｇ、以下ＨＳ−１００と略記する。
・ＦＸ−３５（電気化学工業社製）：アセチレンブラック、平均一次粒子径２３ｎｍ、比表面積１３３ｍ2／ｇ。
・＃３０（三菱化学社製）：ファーネスブラック、平均一次粒子径３０ｎｍ、比表面積７４ｍ2／ｇ。
・ＥＣ−２００Ｌ（ライオン社製）：ケッチェンブラック、比表面積３７７ｍ2／ｇ、中空の多孔質カーボン。
<Carbon black>
Denka black granular product (manufactured by Denki Kagaku Kogyo Co., Ltd.): Acetylene black, average primary particle size 35 nm, specific surface area 69 m 2 / g, hereinafter abbreviated as granular product.
Denka black HS-100 (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size 48 nm, specific surface area 39 m 2 / g, hereinafter abbreviated as HS-100.
FX-35 (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size of 23 nm, specific surface area of 133 m 2 / g.
# 30 (manufactured by Mitsubishi Chemical Corporation): furnace black, average primary particle size 30 nm, specific surface area 74 m 2 / g.
EC-200L (manufactured by Lion Corporation): Ketjen black, specific surface area of 377 m 2 / g, hollow porous carbon.
＜ポリフッ化ビニリデン系ポリマー＞
・Ｗ＃７３００（クレハ社製）：重量平均分子量 １００万、ホモポリマー
・Ｗ＃１７００（クレハ社製）：重量平均分子量 ５０万、ホモポリマー
・Ｗ＃１１００（クレハ社製）：重量平均分子量 ２８万、ホモポリマー
・ＨＳＶ９００（アルケマ社製）：重量平均分子量 ８０万、ホモポリマー
・Ｗ＃９３００（クレハ社製）：重量平均分子量 １００万、酸性官能基入りコポリマー
・ｓｏｌｅｆ＃５１３０（ソルベイ社製）：重量平均分子量 １００―１２０万、酸性官能基入りコポリマー、以下＃５１３０と略記する。
<Polyvinylidene fluoride polymer>
W # 7300 (manufactured by Kureha): weight average molecular weight 1 million, homopolymer W # 1700 (manufactured by Kureha): weight average molecular weight 500,000, homopolymer W # 1100 (manufactured by Kureha): weight average molecular weight 28 Homopolymer HSV900 (manufactured by Arkema): weight average molecular weight 800,000, homopolymer W # 9300 (manufactured by Kureha): weight average molecular weight 1 million, copolymer containing acidic functional groups, solef # 5130 (manufactured by Solvay) : Weight average molecular weight 1 million to 1,200,000, copolymer with acidic functional group, hereinafter abbreviated as # 5130.
ＰＶｄＦの分子量は、ＰＶｄＦ粉末を０．１質量％で溶解したＮＭＰ溶液について、ゲルパーミエーションクロマトグラフ（日本分光株式会社製；ＧＰＣ−９００、ｓｈｏｄｅｘ ＫＤ−８０６Ｍカラム、温度４０℃）を用いることにより測定し、ポリスチレン換算の重量平均分子量として算出した。 The molecular weight of PVdF is obtained by using a gel permeation chromatograph (manufactured by JASCO Corporation; GPC-900, shodex KD-806M column, temperature 40 ° C.) for an NMP solution in which PVdF powder is dissolved at 0.1% by mass. Measured and calculated as a weight average molecular weight in terms of polystyrene.
＜分散剤＞
前述に記載の分散剤Ａ〜Ｉを用いた。
<Dispersant>
Dispersants A to I described above were used.
＜活物質＞
正極活物質：
・ＬｉＮｉ0.33Ｍｎ0.33Ｃｏ0.33Ｏ2、平均粒子径４．５μｍ、比表面積１．５ｍ2／ｇ、以下ＮＭＣと略記する。
・ＬｉＦｅＰＯ4、平均粒子径８．０μｍ、比表面積１８．７ｍ2／ｇ、以下ＬＦＰと略記する。
負極活物質：
・人造黒鉛、平均粒子径１２μｍ、以下、黒鉛と略記する。
<Active material>
Positive electrode active material:
LiNi 0.33 Mn 0.33 Co 0.33 O 2 , average particle diameter 4.5 μm, specific surface area 1.5 m 2 / g, hereinafter abbreviated as NMC.
LiFePO 4 , average particle diameter 8.0 μm, specific surface area 18.7 m 2 / g, hereinafter abbreviated as LFP.
Negative electrode active material:
Artificial graphite, average particle size 12 μm, hereinafter abbreviated as graphite.
＜カーボンブラック分散液の評価＞
実施例、比較例で得られたカーボンブラック分散液の評価は、レオロジー（粘度）、ろ過性、平均粒子径、貯蔵安定性を評価することにより行った。
<Evaluation of carbon black dispersion>
The carbon black dispersions obtained in Examples and Comparative Examples were evaluated by evaluating rheology (viscosity), filterability, average particle diameter, and storage stability.
レオロジー（粘度）測定は、レオメーター（ＨＡＡＫＥ社製「ＲＳ６０００」）、直径３５ｍｍ、角度２°のコーンプレートを用いて、シェアレート（せん断速度）０．０１〜１０００／ｓにおける粘度を測定した。分散液温度および測定部の温度は２５℃とした。 The rheology (viscosity) measurement was carried out using a rheometer (HAAKE “RS6000”), a cone plate having a diameter of 35 mm and an angle of 2 °, and the viscosity at a shear rate (shear rate) of 0.01 to 1000 / s was measured. The dispersion temperature and the temperature of the measurement part were 25 ° C.
ろ過性評価は、減圧濾過用フィルターホルダーと濾過鐘（アドバンテック社製「ＫＧ−４７」）、目開き４８μｍのナイロンメッシュを用い、ダイアフラム型真空ポンプにより減圧して行った。１００ｍｌの分散液をフィルターホルダーに注ぎ、真空ポンプを稼働してから、全量ろ過できた場合を「〇」とし、ろ過詰まりが発生し全量ろ過できなかった場合を「×」と判定した。 The filterability was evaluated by reducing the pressure with a diaphragm type vacuum pump using a filter holder for vacuum filtration, a filter bell (“KG-47” manufactured by Advantech Co., Ltd.), and a nylon mesh with an opening of 48 μm. After pouring 100 ml of the dispersion into the filter holder and operating the vacuum pump, the case where the total amount was filtered was set as “◯”, and the case where the filter was clogged and the total amount could not be filtered was determined as “x”.
平均粒子径は、カーボンブラック分散液をＮＭＰにより適切な濃度に希釈した後に、超音波処理を施した液を測定サンプルとして用い、動的光散乱法方式の粒度分布計（マイクロトラック・ベル社製「ナノトラックＵＰＡ−ＥＸ」、光源波長７８０ｎｍ）を用いて平均粒子径（Ｄ５０値）を測定することにより行った。各種測定条件は、上記方法によりＮＭＰ希釈した分散液のローディングインデックス値を０．７以上１．３以下に、粒子条件を、吸収性粒子、粒子形状非球形、密度１．８０とし、溶媒条件を、溶媒屈折率１．４７、液温２０℃における溶媒粘度１．８０ｍＰａ・ｓ、液温２５℃における溶媒粘度１．６５ｍＰａ・ｓと設定し、得られたメジアン径をＤ５０値として表記した。測定結果は、液温２５℃のＮＭＰ溶剤についてバックグラウンド値を測定した後、上記方法にて調製した液温２５℃のサンプルを測定容器に充填し、上記測定条件にて測定を行うことにより得た。同じカーボンブラックを使用して同じ分散処理をした場合、Ｄ５０値が小さいほど分散性が良好であり、大きいほど分散性が不良であることを示す。 The average particle size was determined by diluting the carbon black dispersion to an appropriate concentration with NMP and then using the sonicated liquid as the measurement sample, and using a dynamic light scattering particle size distribution meter (manufactured by Microtrac Bell) The measurement was carried out by measuring the average particle diameter (D50 value) using “Nanotrack UPA-EX”, light source wavelength 780 nm). Various measurement conditions were such that the loading index value of the dispersion diluted with NMP by the above method was 0.7 or more and 1.3 or less, the particle conditions were absorbent particles, particle shape non-spherical, density 1.80, and the solvent conditions were The solvent refractive index was 1.47, the solvent viscosity was 1.80 mPa · s at a liquid temperature of 20 ° C., the solvent viscosity was 1.65 mPa · s at a liquid temperature of 25 ° C., and the obtained median diameter was expressed as a D50 value. The measurement result is obtained by measuring the background value of the NMP solvent at a liquid temperature of 25 ° C., filling a sample with the liquid temperature of 25 ° C. prepared by the above method into a measurement container, and performing the measurement under the above measurement conditions. It was. When the same dispersion treatment is performed using the same carbon black, the smaller the D50 value, the better the dispersibility, and the greater the value, the poorer the dispersibility.
貯蔵安定性の評価は、カーボンブラック分散液を５０℃にて7日間静置して保存した後の、液性状の変化から評価した。液性状の変化は、ヘラで撹拌した際の撹拌しやすさから判断し、○：問題なし（良好）、△：粘度は上昇しているがゲル化はしていない（可）、×：ゲル化しているまたは沈降がある（極めて不良）、とした。 The storage stability was evaluated from the change in liquid properties after the carbon black dispersion was stored at 50 ° C. for 7 days. The change in the liquid property was judged from the ease of stirring when stirring with a spatula: ◯: No problem (good), △: Viscosity increased but not gelled (possible), ×: Gel It was assumed that it had become sunk or settled (very poor).
＜カーボンブラック分散液の調製＞
［実施例１〜実施例８］
表２に示す組成に従い、３００ｍｌのポリプロピレン製カップにＮＭＰと分散剤Ａを入れて、ホモミキサーにより撹拌して分散剤を溶解させた。撹拌翼はディスパー用の直径４０ｍｍを用い、回転数は５００ｒｐｍとした。引き続き粒状品とＰＶｄＦの粉末を撹拌しながら同時に合計約７ｇ／分の速度で添加した後、せん断型分散機であるハイシェアミキサーを用いて１０ｍ／秒で分散させた。目視による粗大粒子がなくなったところで分散を続けながらレオロジー測定を行い、せん断速度１／ｓ以上１００／ｓ未満の範囲内において粘度の極小値を示し、極小の粘度が０．１〜３Ｐａ・ｓの範囲内となったところで分散を終了し、カーボンブラック分散液をそれぞれ得た。ここで、分散液の質量は合計２００ｇとした。
<Preparation of carbon black dispersion>
[Examples 1 to 8]
According to the composition shown in Table 2, NMP and Dispersant A were placed in a 300 ml polypropylene cup, and the dispersant was dissolved by stirring with a homomixer. The stirring blade had a diameter of 40 mm for disperser and the rotation speed was 500 rpm. Subsequently, the granular product and the PVdF powder were simultaneously added at a rate of about 7 g / min while stirring, and then dispersed at 10 m / sec using a high shear mixer which is a shear type disperser. Rheology measurement is performed while continuing to disperse when there are no coarse particles visually, showing a minimum value of the viscosity within the range of the shear rate of 1 / s or more and less than 100 / s, and the minimum viscosity is 0.1 to 3 Pa · s. Dispersion was terminated when it was within the range, and carbon black dispersions were obtained. Here, the total mass of the dispersion was 200 g.
［実施例９］
分散機をハイシェアミキサーの代わりにプラネタリーミキサーを用いた以外は、実施例１と同様にカーボンブラック分散液を作製した。プラネタリーミキサーは３５０ｍｌのベッセルを用い、８０ｒｐｍにて運転した。
[Example 9]
A carbon black dispersion was prepared in the same manner as in Example 1 except that a planetary mixer was used instead of the high shear mixer. The planetary mixer was operated at 80 rpm using a 350 ml vessel.
［実施例１０〜実施例１７］
分散剤Ａの代わりに表３に示す分散剤種を用いた以外は、実施例１と同様にしてカーボンブラック分散液をそれぞれ作製した。
[Examples 10 to 17]
Carbon black dispersions were prepared in the same manner as in Example 1 except that the dispersant types shown in Table 3 were used instead of the dispersant A.
［実施例１８〜実施例２１］
粒状品の代わりに表４に示すカーボンブラック種とカーボンブラック濃度、分散剤添加量とした以外は実施例１と同様にしてカーボンブラック分散液をそれぞれ作製した。
[Examples 18 to 21]
Carbon black dispersions were prepared in the same manner as in Example 1 except that the carbon black species, carbon black concentration, and dispersant addition amount shown in Table 4 were used instead of the granular products.
[比較例１〜比較例４]
表５に示すＰＶｄＦ種と添加量を用いた以外は、実施例１と同様にしてカーボンブラック分散液をそれぞれ作製した。
[Comparative Examples 1 to 4]
Carbon black dispersions were prepared in the same manner as in Example 1 except that the PVdF species and the addition amount shown in Table 5 were used.
[比較例５]
実施例１の組成に従い、３００ｍｌのガラス瓶に分散剤とNMPを仕込んで、実施例１と同様に分散剤を溶解させた。粒状品とＰＶｄＦの粉末、および直径１．２５ｍｍのジルコニアビーズを２００ｇ加え、ペイントコンディショナーにて分散させた。目視による粗大粒子がなくなるまでを終点として１０分間毎に観察し、合計３０分間分散させ、カーボンブラック分散液を得た。
[Comparative Example 5]
According to the composition of Example 1, the dispersant and NMP were charged into a 300 ml glass bottle, and the dispersant was dissolved in the same manner as in Example 1. 200 g of granular product, PVdF powder, and 1.25 mm diameter zirconia beads were added and dispersed with a paint conditioner. Observation was performed every 10 minutes until the coarse particles disappeared visually, and dispersed for a total of 30 minutes to obtain a carbon black dispersion.
[比較例６]
比較例５の分散時間を６０分に延長した以外は、比較例５と同様にしてカーボンブラック分散液を得た。
[Comparative Example 6]
A carbon black dispersion was obtained in the same manner as in Comparative Example 5 except that the dispersion time in Comparative Example 5 was extended to 60 minutes.
[比較例７]
ハイシェアミキサーの周速を３０m／ｓとし、実施例１と同じ分散時間に変更した以外は、実施例１と同様にしてカーボンブラック分散液を得た。
[Comparative Example 7]
A carbon black dispersion was obtained in the same manner as in Example 1, except that the peripheral speed of the high shear mixer was changed to 30 m / s and the dispersion time was changed to the same as in Example 1.
[比較例８]
ハイシェアミキサーの周速を５m／ｓとし、実施例１と同じ分散時間に変更した以外は、実施例１と同様にしてカーボンブラック分散液を得た。
[Comparative Example 8]
A carbon black dispersion was obtained in the same manner as in Example 1, except that the peripheral speed of the high shear mixer was changed to 5 m / s and the dispersion time was changed to the same as in Example 1.
＜カーボンブラック分散液の評価結果＞
各種カーボンブラック分散液の評価結果を表６に示す。実施例１〜実施例２１の分散液はいずれも１／ｓ以上１００／ｓ未満に極小値を有しており、極小における粘度は０．１〜３Pa・ｓであった。また、D５０は０．３〜０．８μｍの範囲で、すべてろ過性、貯蔵安定性が良好であった。一方、比較例１〜４も１／ｓ以上１００／ｓ未満に極小値を有しており、極小における粘度は０．１〜３Pa・ｓ、D５０は０．３〜０．８μｍの範囲であったが、ＰＶｄＦ添加量が低い比較例１、３ではろ過することが出来ず、さらに貯蔵安定性試験中に沈降が発生した。比較例２、４はろ過性に問題はなかったが、貯蔵安定性試験により増粘が起きた。
<Evaluation results of carbon black dispersion>
Table 6 shows the evaluation results of various carbon black dispersions. The dispersions of Examples 1 to 21 all had a minimum value of 1 / s or more and less than 100 / s, and the viscosity at the minimum was 0.1 to 3 Pa · s. Further, D50 was in the range of 0.3 to 0.8 μm and all had good filterability and storage stability. On the other hand, Comparative Examples 1 to 4 also have a minimum value of 1 / s or more and less than 100 / s, the viscosity at the minimum is 0.1 to 3 Pa · s, and D50 is in the range of 0.3 to 0.8 μm. However, in Comparative Examples 1 and 3 in which the amount of PVdF added was low, filtration could not be performed, and sedimentation occurred during the storage stability test. In Comparative Examples 2 and 4, there was no problem in filterability, but thickening occurred in the storage stability test.
ペイントコンディショナーにより分散した比較例５は１００／ｓ以上に極小値を有しており、極小値における粘度は０．２Ｐａ・ｓであった。これより分散時間が長い比較例６は、極小値を有していなかった。比較例５および比較例６の分散体のD５０は０．３μｍ以下であり、貯蔵安定性試験により沈降が発生した。比較例７は１／ｓ以上１００／ｓ未満に極小値を有していたが、極小における粘度は０．０９Ｐａ・ｓであった。比較例８も同じく１／ｓ以上１００／ｓ未満に極小値を有していたが、極小における粘度は３．１Ｐａ・ｓであった。比較例７、比較例８のD５０は０．３〜０．８μｍの範囲であったが、比較例７は貯蔵安定性試験により増粘が起き、比較例８は粗大な粒子の沈降が見られた。 Comparative Example 5 dispersed by the paint conditioner had a minimum value of 100 / s or more, and the viscosity at the minimum value was 0.2 Pa · s. Comparative Example 6 having a longer dispersion time did not have a minimum value. D50 of the dispersions of Comparative Example 5 and Comparative Example 6 was 0.3 μm or less, and sedimentation occurred in the storage stability test. Comparative Example 7 had a minimum value of 1 / s or more and less than 100 / s, but the viscosity at the minimum was 0.09 Pa · s. Comparative Example 8 also had a minimum value of 1 / s or more and less than 100 / s, but the viscosity at the minimum was 3.1 Pa · s. D50 of Comparative Example 7 and Comparative Example 8 was in the range of 0.3 to 0.8 μm, but in Comparative Example 7, thickening occurred in the storage stability test, and Comparative Example 8 showed sedimentation of coarse particles. It was.
＜電池用スラリーの調整＞ <Preparation of battery slurry>
［実施例１−１］
表７に示す組成に従い、２００ｍｌのポリプロピレン製カップに実施例１の分散液を入れて、ホモミキサーにより撹拌しながら予め５質量部に溶解しておいたW＃７３００（以下、溶解ワニスと略記することがある）を加えた。撹拌翼はディスパー用の直径４０ｍｍを用い、回転数は５００ｒｐｍとした。引き続きＮＭＣの粉末を撹拌しながら合計約１０ｇ／分の速度で添加した後、１５００ｒｐｍにて5分間撹拌し、均一な電池用スラリーを得た。ここで、電池用スラリーの質量は合計２００ｇとした。
[Example 1-1]
In accordance with the composition shown in Table 7, W # 7300 (hereinafter abbreviated as “dissolving varnish”) was prepared by adding the dispersion of Example 1 to a 200 ml polypropylene cup and dissolving it in 5 parts by mass while stirring with a homomixer. Added). The stirring blade had a diameter of 40 mm for disperser and the rotation speed was 500 rpm. Subsequently, NMC powder was added at a rate of about 10 g / min while stirring, and then stirred at 1500 rpm for 5 minutes to obtain a uniform battery slurry. Here, the total mass of the battery slurry was 200 g.
［実施例１−２］
Ｗ＃７３００の代わりに、予め５質量部に溶解しておいたＷ＃９３００を用いた以外は、実施例１−１と同様にして電池用スラリーを得た。
[Example 1-2]
A slurry for a battery was obtained in the same manner as in Example 1-1 except that W # 9300 previously dissolved in 5 parts by mass was used instead of W # 7300.
［実施例１−３］
表７に示す組成に従い、２００ｍｌのポリプロピレン製カップに実施例１の分散液を入れて、ホモミキサーにより撹拌しながらW＃７３００の粉末とＮＭＣの粉末を同時に合計約１１ｇ／分の速度で添加した。撹拌翼はディスパー用の直径４０ｍｍを用い、回転数は５００ｒｐｍとした。添加終了後、１５００ｒｐｍにて１０分間撹拌し、均一な電池用スラリーを得た。ここで、電池用スラリーの質量は合計２００ｇとした。
[Example 1-3]
According to the composition shown in Table 7, the dispersion liquid of Example 1 was put in a 200 ml polypropylene cup, and W # 7300 powder and NMC powder were simultaneously added at a rate of about 11 g / min while stirring with a homomixer. . The stirring blade had a diameter of 40 mm for disperser and the rotation speed was 500 rpm. After completion of the addition, the mixture was stirred at 1500 rpm for 10 minutes to obtain a uniform battery slurry. Here, the total mass of the battery slurry was 200 g.
［実施例１−４］
ＬＦＰ５０ｇ、ＮＭＰ５０ｇを３００ｍｌのガラス瓶に仕込み、直径１．２５ｍｍのジルコニアビーズを２００ｇ加え、ペイントコンディショナーにて１時間分散させた。続いて、このＬＦＰ／ＮＭＰ液とジルコニアビーズとを分離し、２００ｍｌのポリプロピレン製カップに所定量計り取った。ホモミキサーにより撹拌しながら、表７に示す組成に従い実施例１の分散液を滴下した後、W＃７３００の粉末を約１ｇ／分の速度で添加した。撹拌翼はディスパー用の直径４０ｍｍを用い、回転数は５００ｒｐｍとした。添加終了後、１５００ｒｐｍにて１０分間撹拌し、均一な電池用スラリーを得た。ここで、電池用スラリーの質量は合計２００ｇとした。
[Example 1-4]
LFP 50 g and NMP 50 g were charged into a 300 ml glass bottle, 200 g of 1.25 mm diameter zirconia beads were added, and the mixture was dispersed with a paint conditioner for 1 hour. Subsequently, the LFP / NMP solution and zirconia beads were separated and weighed into a 200 ml polypropylene cup. While stirring with a homomixer, the dispersion of Example 1 was dropped according to the composition shown in Table 7, and then a powder of W # 7300 was added at a rate of about 1 g / min. The stirring blade had a diameter of 40 mm for disperser and the rotation speed was 500 rpm. After completion of the addition, the mixture was stirred at 1500 rpm for 10 minutes to obtain a uniform battery slurry. Here, the total mass of the battery slurry was 200 g.
［実施例１−５］
表７に示す組成に従い、実施例１−１でＮＭＣの代わりに黒鉛を用いた以外は同様の手順で電池用スラリーを得た。
[Example 1-5]
According to the composition shown in Table 7, a battery slurry was obtained in the same procedure except that graphite was used instead of NMC in Example 1-1.
［比較例２−１］
比較例２の分散液を用いて、表７に示す組成に従い実施例１−２と同様にして電池用スラリーを得た。
[Comparative Example 2-1]
Using the dispersion liquid of Comparative Example 2, a battery slurry was obtained in the same manner as in Example 1-2 according to the composition shown in Table 7.
［比較例４−１］
比較例４の分散液を用いて、表７に示す組成に従い実施例１−１と同様にして電池用スラリーの作製を試みたが、比較例４の分散液には元々ＰＶｄＦがカーボンブラック１００質量部に対して８０質量部も含まれていたため、所望の組成であるカーボンブラック／ＰＶｄＦ＝７／２にすることができなかった。
[Comparative Example 4-1]
Using the dispersion liquid of Comparative Example 4, an attempt was made to prepare a battery slurry in the same manner as in Example 1-1 according to the composition shown in Table 7, but the PVdF originally contained 100 mass of carbon black in the dispersion liquid of Comparative Example 4. As a result, 80 parts by mass with respect to the part was included, so that the desired composition of carbon black / PVdF = 7/2 could not be obtained.
［比較例５−１、比較例７−１、比較例８−１］
比較例５、７、８の分散液を用いて、表７に示す組成に従い実施例１−１と同様にして電池用スラリーをそれぞれ得た。
[Comparative Example 5-1, Comparative Example 7-1, Comparative Example 8-1]
Using the dispersions of Comparative Examples 5, 7, and 8, battery slurries were obtained in the same manner as in Example 1-1 according to the compositions shown in Table 7.
［比較例５−２］
比較例５の分散液を用いて、表７に示す組成に従い実施例１−５と同様にして電池用スラリーを得た。
[Comparative Example 5-2]
Using the dispersion liquid of Comparative Example 5, a battery slurry was obtained in the same manner as in Example 1-5 according to the composition shown in Table 7.
＜二次電池用電極の作製＞
上記の各実施例、比較例で得られた電池用スラリーを、活物質がＮＭＣであれば厚さ２０μｍのアルミ箔上に、黒鉛であれば厚さ２０μｍの銅箔上にドクターブレードを用いて塗工した後、減圧化１２０℃で３０分間乾燥し、乾燥後膜厚１００μｍの電極を作製した。
<Preparation of secondary battery electrode>
Using the doctor blade, the battery slurry obtained in each of the above Examples and Comparative Examples was formed on an aluminum foil having a thickness of 20 μm if the active material was NMC, and on a copper foil having a thickness of 20 μm if the active material was graphite. After coating, it was dried at 120 ° C. under reduced pressure for 30 minutes, and after drying, an electrode having a thickness of 100 μm was produced.
得られた電極の密着性評価は、剥離強度試験により行った。なお、剥離強度の測定には卓上型引張試験機（東洋精機製作所製、ストログラフＥ３）を用い、１８０度剥離試験法により評価した。具体的には、１００ｍｍ×２０ｍｍサイズの両面テープ（Ｎｏ．５０００ＮＳ、ニトムズ社製）をアクリル板上に貼り付け、作製した電池電極合材層を両面テープのもう一方の面に密着させ、一定速度（５０ｍｍ／分）で上方に引っ張り、剥離する際のトルクを測定した。剥離強度試験の結果は、実施例１−１−１の実測値を１．０とし、それに対する比で表記した。 The adhesion of the obtained electrode was evaluated by a peel strength test. The peel strength was measured by a 180-degree peel test method using a desktop tensile tester (manufactured by Toyo Seiki Seisakusho, Strograph E3). Specifically, a 100 mm × 20 mm double-sided tape (No. 5000NS, manufactured by Nitoms Co., Ltd.) is attached on an acrylic plate, and the produced battery electrode mixture layer is brought into close contact with the other side of the double-sided tape. The torque at the time of pulling upward at (50 mm / min) and peeling was measured. The result of the peel strength test was expressed as a ratio with respect to 1.0, with the actually measured value of Example 1-1-1.
［実施例１−１−１、実施例１−２−１］［比較例２−１−１］
実施例１−１、１−２、比較例２−１で得られた電池用スラリーを用いて電極をそれぞれ作製し、剥離強度試験を行った。結果を表８に示す。Ｗ＃９３００は密着性向上効果がある酸性官能基を含む共重合体であるため、実施例１−２−１はＷ＃７３００単独の実施例１−１−１よりも剥離強度が高くなった。しかし、比較例２−１−１はカーボンブラック分散液としてＷ＃７３００を多く含む分、Ｗ＃９３００の量が少なくなったことにより、密着性向上効果が十分得られなかった。
[Example 1-1-1, Example 1-2-1] [Comparative Example 2-1-1]
Electrodes were produced using the battery slurries obtained in Examples 1-1 and 1-2 and Comparative Example 2-1, respectively, and a peel strength test was performed. The results are shown in Table 8. Since W # 9300 is a copolymer containing an acidic functional group that has an effect of improving adhesion, Example 1-2-1 has higher peel strength than Example 1-1-1 of W # 7300 alone. . However, since Comparative Example 2-1-1 contained a large amount of W # 7300 as a carbon black dispersion, the amount of W # 9300 was reduced, so that the effect of improving adhesion was not sufficiently obtained.
実施例１のように分散液に含まれるＰＶｄＦが少ない場合、電池用スラリー作製の際に添加するＰＶｄＦ種および量が任意に設定できるため、所望の電極特性に必要な組成設計の自由度が高くなる。一方、比較例２のように分散液に多くのＰＶｄＦを含む場合、電池用スラリーの組成設計における自由度が少ないため、所望の電極特性の達成が困難となる。したがって、比較例２のようなＰＶｄＦを多く含む分散液を用いて所望の電極特性を達成するには、ＰＶｄＦ種および量の異なる分散液を各種製造する必要が生じる。 When PVdF contained in the dispersion is small as in Example 1, the PVdF species and amount to be added at the time of battery slurry preparation can be arbitrarily set, so the degree of freedom in composition design necessary for desired electrode characteristics is high. Become. On the other hand, when a large amount of PVdF is included in the dispersion liquid as in Comparative Example 2, it is difficult to achieve desired electrode characteristics because the degree of freedom in the composition design of the battery slurry is small. Therefore, in order to achieve desired electrode characteristics using a dispersion containing a large amount of PVdF as in Comparative Example 2, it is necessary to produce various dispersions having different PVdF species and amounts.
［実施例１−３−１、１−５−１］
［比較例５−１−１、５−２−１、７−１−１、８−１−１］
実施例１−３、１−５、比較例５−１、５−２、７−１、８−１で得られた電池用スラリーを用いてそれぞれ電極を作製した。
[Examples 1-3-1, 1-5-1]
[Comparative Examples 5-1-1, 5-2-1, 7-1-1, 8-1-1]
Electrodes were produced using the battery slurries obtained in Examples 1-3 and 1-5 and Comparative Examples 5-1, 5-2, 7-1 and 8-1.
＜リチウムイオン二次電池評価用セルの組み立て＞
先に作製した電極を、ローラープレス機にて厚さ７０μｍとなるように圧延処理した。これを直径１６mｍに打ち抜き作用極とし、金属リチウム箔（厚さ０．１５ｍｍ）を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター（膜厚２５μｍ、空孔率が５０％、平均孔径３０ｎｍ）を挿入積層し、電解液（エチレンカーボネートとジエチルカーボネートを体積比１:１で混合した混合溶媒にＬｉＰＦ6を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝泉社製ＨＳフラットセル）を組み立てた。セルの組み立ては、アルゴンガス置換したグローブボックス内で行った。活物質がＮＭＣの場合は正極評価、活物質が黒鉛の場合は負極評価を行った。
<Assembly of lithium ion secondary battery evaluation cell>
The electrode produced previously was rolled with a roller press so as to have a thickness of 70 μm. This is a punching working electrode with a diameter of 16 mm, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator made of a porous polypropylene film between the working electrode and the counter electrode (film thickness 25 μm, porosity is 50%, Inserted and laminated with an average pore diameter of 30 nm, filled with electrolyte (nonaqueous electrolyte in which LiPF 6 was dissolved at a concentration of 1 M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1) and sealed in two poles A metal cell (HS flat cell manufactured by Hosen Co., Ltd.) was assembled. The cell was assembled in a glove box substituted with argon gas. When the active material was NMC, positive electrode evaluation was performed, and when the active material was graphite, negative electrode evaluation was performed.
＜リチウムイオン二次電池正極評価＞
測定の前に、作製したセルを２５℃で２４時間放置した。充放電試験には充放電装置（北斗電工社製ＳＭ−８）を使用した。充電レート０．２Ｃの定電流定電圧充電（上限電圧４．２Ｖ、下限電流０．０２Ｃ）で満充電とし、１０分間の休止時間を挟んで、放電レート０．２Ｃの定電流放電（下限電圧３．０Ｖ）を行う充放電を１サイクルとし、５サイクル繰り返した後、６サイクル目の放電レートを５Ｃとして、１〜５サイクル目と同様にして充放電した。１サイクル目の充電容量に対する５サイクル目の放電容量の比から「初期効率」を求めた。５サイクル目の放電容量に対する６サイクル目の放電容量の比から「レート特性」を求めた。
<Evaluation of positive electrode for lithium ion secondary battery>
Before the measurement, the produced cell was left at 25 ° C. for 24 hours. A charge / discharge device (SM-8 manufactured by Hokuto Denko) was used for the charge / discharge test. A constant current and constant voltage charge with a charge rate of 0.2 C (upper limit voltage of 4.2 V, lower limit current of 0.02 C) is fully charged, and a constant current discharge with a discharge rate of 0.2 C (lower limit voltage) with a 10-minute rest period. The charging / discharging for 3.0V) was set to 1 cycle, and after repeating 5 cycles, the discharging rate of the 6th cycle was set to 5C, and charging / discharging was performed in the same manner as the 1st to 5th cycles. The “initial efficiency” was determined from the ratio of the discharge capacity at the fifth cycle to the charge capacity at the first cycle. The “rate characteristic” was determined from the ratio of the discharge capacity at the sixth cycle to the discharge capacity at the fifth cycle.
＜リチウムイオン二次電池負極評価＞
下限電圧を０．０１Ｖ、上限電圧を１．２Ｖとした以外は正極評価と同様にして、「初期効率」および「レート特性」を求めた。
<Evaluation of lithium ion secondary battery negative electrode>
“Initial efficiency” and “rate characteristics” were determined in the same manner as the positive electrode evaluation except that the lower limit voltage was 0.01 V and the upper limit voltage was 1.2 V.
初期効率は、初回の充電の際に不可逆的な副反応が起きた場合、その反応に電流が消費された分見かけ上充電容量が大きくなることや、活物質の一部が不可逆的に変質して充放電容量そのものが小さくなることによって低下することがある。例えば、活物質として黒鉛を用いた場合には、初回の充電で粒子表面に被膜を形成するため、初期効率はＮＭＣなどに比べて低くなることが知られている。レート特性は、低速放電に比べて高速放電では種々の抵抗の影響が大きくなり容量が低下することから、出力を評価する目安として有用である。 The initial efficiency is that if an irreversible side reaction occurs during the initial charge, the charge capacity is apparently increased due to the consumption of current in the reaction, or a part of the active material is irreversibly altered. In some cases, the charge / discharge capacity itself may be reduced. For example, when graphite is used as the active material, it is known that the initial efficiency is lower than that of NMC or the like because a film is formed on the particle surface by the first charge. The rate characteristic is useful as a measure for evaluating the output because the influence of various resistances is increased and the capacity is reduced in the high-speed discharge compared to the low-speed discharge.
［実施例２２〜実施例２５］［比較例９〜比較例１２］
表９に示す電極を用いて電池を作製し、初期効率およびレート特性を求めた。実施例２２〜実施例２５はいずれも初期効率およびレート特性ともに高いことがわかる。比較例９〜１１の初期効率が低くなった理由として、分散強度が高いペイントコンディショナーや高速運転のハイシェアミキサーを用いたため、カーボンブラックが過分散になり、活性な表面の露出が増えて反応量が増えたことが考えられる。また、レート特性が大幅に低下したことから、出力が著しく悪いことがわかった。比較例１２は初期効率は高いがレート特性が悪化したことから、逆に分散状態が悪かったため、良好な導電パスが形成できず出力が低下したと考えられる。
[Example 22 to Example 25] [Comparative Example 9 to Comparative Example 12]
A battery was fabricated using the electrodes shown in Table 9, and the initial efficiency and rate characteristics were determined. It can be seen that Examples 22 to 25 are both high in initial efficiency and rate characteristics. The reason why the initial efficiencies of Comparative Examples 9 to 11 were low was that because a paint conditioner with high dispersion strength and a high shear mixer with high speed operation were used, carbon black was overdispersed, and the active surface exposure increased and the reaction amount It is thought that increased. Further, since the rate characteristic was greatly lowered, it was found that the output was extremely bad. In Comparative Example 12, although the initial efficiency was high but the rate characteristic was deteriorated, it was considered that the dispersion state was bad, so that a good conductive path could not be formed and the output was lowered.
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