JP6055782B2 - Positive electrode mixture, positive electrode, and nonaqueous electrolyte secondary battery using the same - Google Patents
Positive electrode mixture, positive electrode, and nonaqueous electrolyte secondary battery using the same Download PDFInfo
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- JP6055782B2 JP6055782B2 JP2013551551A JP2013551551A JP6055782B2 JP 6055782 B2 JP6055782 B2 JP 6055782B2 JP 2013551551 A JP2013551551 A JP 2013551551A JP 2013551551 A JP2013551551 A JP 2013551551A JP 6055782 B2 JP6055782 B2 JP 6055782B2
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- positive electrode
- electrode mixture
- active material
- surfactant
- acid
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、正極合剤、正極、およびそれを用いた非水電解質二次電池に関し、詳しくは、正極活物質の分散性、保存安定性および集電体に塗工する際の塗工性に優れ、かつ、集電体に塗工後は、集電体および正極活物質との密着性に優れた正極を得ることができる水系の正極合剤、正極、およびそれを用いた非水電解質二次電池に関する。 The present invention relates to a positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery using the positive electrode mixture, and more specifically, to dispersibility of a positive electrode active material, storage stability, and coating property when applied to a current collector. A water-based positive electrode mixture, a positive electrode, and a non-aqueous electrolyte using the same, which can obtain a positive electrode excellent in adhesion to the current collector and the positive electrode active material after being applied to the current collector. Next battery.
近年、電子部品の小型化、多機能化が進み、携帯型電子機器が多く登場している。これらは小型化、軽量化が望まれており、その電源として用いられる電池においても同様に小型化、軽量化が求められている。また、環境問題や資源問題を背景に、ハイブリッド自動車や電気自動車等が開発され、製造、販売されはじめている。このような、いわゆる電動車両においても、小型かつ軽量で充電および放電ができ、エネルギー密度の高い電源装置の活用が不可欠である。これらの電源装置としてはリチウムイオン電池やニッケル水素電池等の二次電池や電気二重層キャパシタ等が利用される。特にリチウムイオン二次電池をはじめとする非水電解質二次電池は、そのエネルギー密度の高さや、繰り返しの充電、放電に耐えうる耐久性の高さから、電源装置として注目され、開発が鋭意進められている。 In recent years, electronic parts have become smaller and more multifunctional, and many portable electronic devices have appeared. These are desired to be reduced in size and weight, and a battery used as a power source is similarly required to be reduced in size and weight. In addition, against the background of environmental problems and resource problems, hybrid cars and electric cars have been developed, manufactured and sold. In such a so-called electric vehicle, it is indispensable to use a power supply device that can be charged and discharged in a small size and light weight and has a high energy density. As these power supply devices, secondary batteries such as lithium ion batteries and nickel metal hydride batteries, electric double layer capacitors, and the like are used. In particular, non-aqueous electrolyte secondary batteries such as lithium-ion secondary batteries are attracting attention as power supply devices due to their high energy density and high durability that can withstand repeated charging and discharging. It has been.
二次電池の電極は、活物質、導電助剤、さらにはこれらを集電体に結着させるバインダー樹脂により構成される。二次電池は、充放電の際に正極または負極が体積膨張や収縮を繰り返すため、活物質や導電助剤の脱落が起こることで充放電のサイクル寿命を短くする場合がある。そのため、二次電池用バインダー樹脂には電極の膨潤、収縮に耐え得る柔軟性が要求され、従来、正極および負極共にポリフッ化ビニリデン(PVDF)、ポリテトラフルオロエチレン(PTFE)等のフッ素樹脂が多く用いられてきた。 The electrode of the secondary battery is composed of an active material, a conductive additive, and a binder resin that binds these to a current collector. In the secondary battery, since the positive electrode or the negative electrode repeats volume expansion and contraction during charging and discharging, the active material and the conductive auxiliary agent may be dropped, thereby shortening the cycle life of charging and discharging. Therefore, the binder resin for secondary batteries is required to be flexible enough to withstand the swelling and shrinkage of the electrode. Conventionally, both the positive electrode and the negative electrode have many fluorine resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). Has been used.
しかしながら、一般的なフッ素樹脂では集電体に対する密着性が不十分であるため、充放電のサイクル寿命のさらなる向上要求に対して応えることができなかった。特に、ポリフッ化ビニリデンをバインダー樹脂として使用した場合、集電体、または充填剤(正極活物質および導電助剤)との結着力が弱いため、電池製造時および電池使用中に集電体と電極合剤の剥離が生じ、電池の内部抵抗が増大するという問題を有していた。 However, since a general fluororesin has insufficient adhesion to the current collector, it has not been possible to meet the demand for further improvement of the charge / discharge cycle life. In particular, when polyvinylidene fluoride is used as a binder resin, the current collector and electrode are used during battery manufacture and during battery use because the binding force with the current collector or filler (positive electrode active material and conductive additive) is weak. Separation of the mixture occurred and the internal resistance of the battery increased.
このような問題に対して、例えば、特許文献1では、バインダー樹脂であるフッ素樹脂として、フッ化ビニリデンと不飽和二塩基酸のモノエステル等の極性モノマーとの共重合体が提案されている。これによれば、フッ素樹脂と集電体との結着性を改善することが可能である。また、特許文献2および特許文献3には、負極活物質のバインダー樹脂として、スチレン−ブタジエン共重合体(SBR)粒子の水分散エマルションや、SBR粒子とカルボキシメチルセルロース(CMC)のナトリウム塩またはアンモニウム塩からなる組成物が提案されている。特許文献2および3のように、SBR粒子をバインダー樹脂に用いることで、二次電池使用時における、負極活物質の脱落を防止することができる。 For such a problem, for example, Patent Document 1 proposes a copolymer of vinylidene fluoride and a polar monomer such as a monoester of an unsaturated dibasic acid as a fluororesin that is a binder resin. According to this, it is possible to improve the binding property between the fluororesin and the current collector. Patent Documents 2 and 3 disclose, as binder resins for negative electrode active materials, water-dispersed emulsions of styrene-butadiene copolymer (SBR) particles, sodium salts or ammonium salts of SBR particles and carboxymethyl cellulose (CMC). A composition consisting of As in Patent Documents 2 and 3, by using SBR particles as a binder resin, it is possible to prevent the negative electrode active material from falling off when the secondary battery is used.
さらに、特許文献4では、溶剤に溶解させたバインダー樹脂としてのアクリル樹脂に架橋剤を添加して、アクリル樹脂と架橋剤とを電極作製時の加熱、圧着工程で反応させて三次元架橋構造体を得ることにより、二次電池の充放電時における活物質や導電剤の脱落を防止する技術が提案されている。さらにまた、特許文献5では、平均粒径が0.01〜0.5μmの正極活物質表面を界面活性剤で被覆することにより、反応に供される正極活物質の表面積を増大させつつ、正極活物質の凝集を防止し、二次電池を高出力化する技術が提案されている。 Furthermore, in Patent Document 4, a cross-linking agent is added to an acrylic resin as a binder resin dissolved in a solvent, and the acrylic resin and the cross-linking agent are reacted in the heating and pressure-bonding steps during electrode preparation to produce a three-dimensional cross-linked structure. Thus, there has been proposed a technique for preventing the active material and the conductive agent from falling off during charging and discharging of the secondary battery. Furthermore, in Patent Document 5, the surface area of the positive electrode active material subjected to the reaction is increased by coating the surface of the positive electrode active material having an average particle diameter of 0.01 to 0.5 μm with a surfactant. A technique for preventing the aggregation of the active material and increasing the output of the secondary battery has been proposed.
しかしながら、特許文献1で提案されているフッ素系樹脂は、非水系二次電池電極用のバインダー樹脂として用いる場合のように厳しい条件下での使用を考慮すると、未だ十分な耐溶剤性、耐薬品性を有するとはいい難い。また、特許文献2および3に記載のバインダー樹脂の使用においては、SBR粒子は充放電を繰り返しても負極活物質が脱落し難いという利点を有してはいるものの、容量の大きな電池を得ることができないという問題がある。また、SBR粒子は、負極活物質である炭素材料に吸着しやすく、炭素材料表面を被覆する傾向がある。そのため、リチウムイオンを含む電解液が浸透し難く、十分な電気特性を得られない場合がある。さらに、特許文献4で提案されている溶剤溶解型のバインダー樹脂を使用した場合、樹脂溶液を電極基体に塗布した後、有機溶媒を除去すると、樹脂によって電極活物質表面が隙間なく被覆されてしまう。そのため十分な電気特性が得られないという問題を有している。さらにまた、特許文献5で提案されている二次電池は、正極活物質の結着を阻害しやすく、正極活物質合剤層の耐久性が十分ではないという問題を有している。また、特許文献1および4では、バインダー樹脂としてフッ素樹脂を用いているが、フッ素樹脂はN−メチルピロリドン等の特定の溶剤にしか膨潤、溶解しないため、電極作製時の異臭等の人体や環境に対する悪影響が問題である。 However, the fluorine-based resin proposed in Patent Document 1 still has sufficient solvent resistance and chemical resistance in consideration of use under severe conditions such as when used as a binder resin for non-aqueous secondary battery electrodes. It is hard to say that you have sex. Further, in the use of the binder resin described in Patent Documents 2 and 3, although the SBR particles have the advantage that the negative electrode active material is not easily dropped even after repeated charge and discharge, a battery having a large capacity is obtained. There is a problem that can not be. Further, the SBR particles tend to be adsorbed on the carbon material that is the negative electrode active material, and tend to cover the surface of the carbon material. Therefore, the electrolyte containing lithium ions is difficult to permeate and sufficient electrical characteristics may not be obtained. Furthermore, when the solvent-soluble binder resin proposed in Patent Document 4 is used, if the organic solvent is removed after applying the resin solution to the electrode substrate, the surface of the electrode active material is covered with the resin without any gaps. . Therefore, there is a problem that sufficient electrical characteristics cannot be obtained. Furthermore, the secondary battery proposed in Patent Document 5 has a problem that the binding of the positive electrode active material tends to be hindered and the durability of the positive electrode active material mixture layer is not sufficient. In Patent Documents 1 and 4, a fluororesin is used as the binder resin. However, since the fluororesin swells and dissolves only in a specific solvent such as N-methylpyrrolidone, the human body and environment such as a strange odor at the time of electrode preparation Is a problem.
そこで、本発明の目的は、正極活物質の分散性、保存安定性および集電体に塗工する際の塗工性に優れ、かつ、集電体に塗工後は、集電体および正極活物質との密着性に優れた正極を得ることができる水系の正極合剤、正極、およびそれを用いた非水電解質二次電池を提供することにある。 Accordingly, an object of the present invention is to provide excellent dispersion properties, storage stability, and coating properties when applied to a current collector, and after application to the current collector, the current collector and the positive electrode. An object of the present invention is to provide a water-based positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery using the same, which can obtain a positive electrode having excellent adhesion to an active material.
本発明者は上記課題を解消するために鋭意検討した結果、正極合剤に界面活性剤と、特定の高分子材料を水分散性高分子バインダー樹脂として用いることで、正極活物質が溶媒中で容易に均一に分散し、また、得られた正極合剤は集電体に塗布する際の塗工性に優れており、これを乾燥して得られた正極は正極合剤層と集電板との密着性に優れていることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a surfactant as a positive electrode mixture and a specific polymer material as a water-dispersible polymer binder resin so that the positive electrode active material can be used in a solvent. Easily and uniformly dispersed, and the obtained positive electrode mixture has excellent coating properties when applied to a current collector, and the positive electrode obtained by drying the positive electrode mixture has a positive electrode mixture layer and a current collector plate As a result, the present invention has been completed.
また、本発明者は正極合剤に特定の物性を有する界面活性剤を添加することで、正極活物質が溶媒中で容易に均一に分散し、また、得られた正極合剤は集電体に塗布する際の塗工性に優れており、これを乾燥して得られた正極は正極合剤層と集電板との密着性に優れていることを見出した。 In addition, the present inventor adds a surfactant having specific physical properties to the positive electrode mixture, so that the positive electrode active material is easily and uniformly dispersed in the solvent, and the obtained positive electrode mixture is a current collector. It was found that the positive electrode obtained by drying this was excellent in the adhesion between the positive electrode mixture layer and the current collector plate.
すなわち、本発明の正極合剤は、正極活物質と、水分散性高分子バインダー樹脂と、導電助剤と、界面活性剤と、を含有することを特徴とするものである。 That is, the positive electrode mixture of the present invention is characterized by containing a positive electrode active material, a water-dispersible polymer binder resin, a conductive auxiliary agent, and a surfactant.
本発明の正極合剤においては、前記界面活性剤のHLB値は13.0〜20.0であることが好ましい。また、本発明の正極合剤においては、溶媒として水を含むことが好ましい。 In the positive electrode material mixture of the present invention, the surfactant preferably has an HLB value of 13.0 to 20.0. Moreover, in the positive mix of this invention, it is preferable that water is included as a solvent.
また、本発明の正極は、上記本発明の正極合剤が集電体に塗布されてなることを特徴とするものである。 The positive electrode of the present invention is characterized in that the positive electrode mixture of the present invention is applied to a current collector.
さらに、本発明の非水電解質二次電池は、上記本発明の正極を用いたことを特徴とするものである。 Furthermore, the nonaqueous electrolyte secondary battery of the present invention is characterized by using the positive electrode of the present invention.
本発明によれば、正極活物質の分散性、保存安定性および集電体に塗工する際の塗工性に優れ、かつ、集電体に塗工後は、集電体および正極活物質との密着性に優れた正極を得ることができる水系の正極合剤、正極、およびそれを用いた非水電解質二次電池を提供することができる。 According to the present invention, the positive electrode active material is excellent in dispersibility, storage stability, and coating property when applied to the current collector, and after being applied to the current collector, the current collector and the positive electrode active material. An aqueous positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery using the same can be provided.
以下、本発明の実施の形態について、詳細に説明する。
<正極合剤>
本発明の正極合剤は、正極活物質と、水分散性高分子バインダー樹脂と、導電助剤と、界面活性剤と、を含有する。正極合剤に界面活性剤を添加することで、正極活物質および水分散性高分子バインダー樹脂を水系の溶媒に短時間で均一に分散させることができる。また、正極活物質および水分散性高分子バインダー樹脂は凝集、沈降を起こしにくくなるため、集電体に対する塗工性も向上する。さらに、本発明の正極合剤を用いた正極は、集電体および正極活物質との密着性および可撓性に優れている。さらにまた、得られた正極を用いた非水電解質二次電池は、充電および放電の繰り返しや、発熱による高温環境下にあっても充電放電サイクルにおける放電容量の低下を抑制でき、長寿命の二次電池を得ることができる。以下、本発明の正極合剤の各成分、およびその製造方法について詳細に説明する。Hereinafter, embodiments of the present invention will be described in detail.
<Positive electrode mixture>
The positive electrode mixture of the present invention contains a positive electrode active material, a water-dispersible polymer binder resin, a conductive additive, and a surfactant. By adding a surfactant to the positive electrode mixture, the positive electrode active material and the water-dispersible polymer binder resin can be uniformly dispersed in an aqueous solvent in a short time. In addition, since the positive electrode active material and the water-dispersible polymer binder resin are less likely to agglomerate and settle, the applicability to the current collector is also improved. Furthermore, the positive electrode using the positive electrode mixture of the present invention is excellent in adhesion and flexibility with the current collector and the positive electrode active material. Furthermore, the non-aqueous electrolyte secondary battery using the obtained positive electrode can suppress a decrease in discharge capacity in a charge / discharge cycle even under a high temperature environment due to repeated charging and discharging and heat generation, and has a long life. A secondary battery can be obtained. Hereinafter, each component of the positive electrode mixture of the present invention and the production method thereof will be described in detail.
<正極活物質>
本発明の正極合剤においては、正極活物質として、例えば、遷移金属酸化物、遷移金属硫化物、およびリチウム含有複合金属酸化物等を用いることができる。遷移金属としては、例えば、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Mo等を挙げることができ、遷移金属酸化物としては、例えば、MnO、MnO2、V2O5、V6O13、TiO2、Cu2V2O3、非晶質V2O−P2O5、MoO3、V2O5、V6O13等を好適に用いることができる。特に、サイクル安定性と容量の観点からMnO、V2O5、V6O13、TiO2が好適である。遷移金属硫化物としては、TiS2、TiS3、非晶質MoS2、FeS等を好適に用いることができる。また、リチウム含有複合金属酸化物の構造については、特に制限はないが、層状構造、スピネル構造、またはオリビン型構造等のものを好適に用いることができる。<Positive electrode active material>
In the positive electrode mixture of the present invention, for example, transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides, and the like can be used as the positive electrode active material. Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo. Examples of the transition metal oxide include MnO, MnO 2 , V 2 O 5 , V 6 O 13, TiO 2, Cu 2 V 2 O 3, amorphous V 2 O-P 2 O 5 , MoO 3, V 2 O 5, V 6 O 13 and the like can be suitably used. In particular, MnO, V 2 O 5 , V 6 O 13 , and TiO 2 are preferable from the viewpoint of cycle stability and capacity. As the transition metal sulfide, TiS 2 , TiS 3 , amorphous MoS 2 , FeS, or the like can be suitably used. The structure of the lithium-containing composite metal oxide is not particularly limited, but a layered structure, a spinel structure, an olivine structure, or the like can be preferably used.
層状構造を有するリチウム含有複合金属酸化物としては、リチウム含有コバルト酸化物(LiCoO2)、リチウム含有ニッケル酸化物(LiNiO2)、Co−Ni−Mnの複合酸化物を主構造とするリチウム含有複合金属酸化物、Ni−Mn−Alの複合酸化物を主構造とするリチウム含有複合金属酸化物、Ni−Co−Alの複合酸化物を主構造とするリチウム含有複合金属酸化物を挙げることができる。The lithium-containing composite metal oxide having a layered structure includes a lithium-containing composite having a lithium-containing cobalt oxide (LiCoO 2 ), a lithium-containing nickel oxide (LiNiO 2 ), and a Co—Ni—Mn composite oxide as a main structure. Examples thereof include metal oxides, lithium-containing composite metal oxides having Ni-Mn-Al composite oxide as a main structure, and lithium-containing composite metal oxides having Ni-Co-Al composite oxide as a main structure. .
スピネル構造を有するリチウム含有複合金属酸化物としてはマンガン酸リチウム(LiMn2O4)やMnの一部を他の遷移金属で置換したLi[Mn3/2M1/2]O4(ここでMは、Cr、Fe、Co、Ni、Cu等)等を挙げることができる。Examples of the lithium-containing composite metal oxide having a spinel structure include lithium manganate (LiMn 2 O 4 ) and Li [Mn 3/2 M 1/2 ] O 4 in which a part of Mn is substituted with another transition metal (wherein M may include Cr, Fe, Co, Ni, Cu and the like.
オリビン型構造を有するリチウム含有複合金属酸化物としてはLiXMPO4(式中、Mは、Mn、Fe、Co、Ni、Cu、Mg、Zn、V、Ca、Sr、Ba、Ti、Al、Si、BおよびMoから選ばれる少なくとも1種、0≦X≦2)であらわされるオリビン型リン酸リチウム化合物を挙げることができる。リチウム含有複合金属酸化物の中でも、LiFePO4、LiCoPO4は導電性が低いために微粒化させて用いることが多く、これらは多くの細孔を有するため表面積が大きくバインダーとなる樹脂との相溶性が悪い。しかしながら、本発明の正極合剤は界面活性剤を含有しているため、LiFePO4、LiCoPO4であっても好適に用いることができる。Li X MPO 4 (wherein, M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, lithium-containing composite metal oxide having an olivine structure) An olivine type lithium phosphate compound represented by at least one selected from Si, B and Mo, 0 ≦ X ≦ 2) can be given. Among lithium-containing composite metal oxides, LiFePO 4 and LiCoPO 4 are often used by being atomized because of their low conductivity, and since these have many pores, they have a large surface area and are compatible with a resin that serves as a binder. Is bad. However, since the positive electrode mixture of the present invention contains a surfactant, LiFePO 4 and LiCoPO 4 can be preferably used.
本発明の正極合剤においては、正極活物質としては、平均粒子径が0.01μm以上50μm未満のものを好適に用いることができ、より好適には0.1μm〜30μmである。粒子径が上記範囲内であれば、水分散性高分子バインダー樹脂の配合量を少なくすることができ、電池の容量の低下を抑制できると共に、正極活物質の凝集を防ぎ、正極合剤の分散性を良好にして均一な電極を得ることができる。ここで、粒子径とは、粒子の輪郭線上の任意の2点間の距離のうち、最大の距離Lであり、平均粒子径の値とは、走査型電子顕微鏡(SEM)や透過型電子顕微鏡(TEM)等の観察手段を用い、数〜数十視野中に観察される粒子の粒子径の平均値として算出される値である。 In the positive electrode mixture of the present invention, as the positive electrode active material, those having an average particle diameter of 0.01 μm or more and less than 50 μm can be suitably used, and more preferably 0.1 μm to 30 μm. If the particle size is within the above range, the amount of the water-dispersible polymer binder resin can be reduced, the decrease in battery capacity can be suppressed, the aggregation of the positive electrode active material can be prevented, and the positive electrode mixture can be dispersed. A uniform electrode can be obtained with good properties. Here, the particle diameter is the maximum distance L among any two points on the particle outline, and the average particle diameter is a scanning electron microscope (SEM) or a transmission electron microscope. It is a value calculated as an average value of particle diameters of particles observed in several to several tens of fields using an observation means such as (TEM).
なお、正極活物質として、電気伝導性に乏しい鉄系酸化物を用いる場合は、還元焼成時に炭素源物質を存在させることで、炭素材料で覆われた正極活物質として用いることができる。これら炭素源物質は、部分的に元素置換したものであってもよい。また、非水電解質二次電池用正極活物質は、上記の無機化合物と、例えば、ポリアセチレン、ポリ−p−フェニレン等の導電性高分子である有機化合物との混合物であってもよい。 When an iron-based oxide having poor electrical conductivity is used as the positive electrode active material, it can be used as a positive electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These carbon source materials may be partially element-substituted. The positive electrode active material for a non-aqueous electrolyte secondary battery may be a mixture of the above inorganic compound and an organic compound that is a conductive polymer such as polyacetylene or poly-p-phenylene.
<水分散性高分子バインダー樹脂>
本発明の正極合剤においては、水分散性高分子バインダー樹脂とは、後述する水系溶媒に分散することができる高分子バインダー樹脂である。水分散性高分子バインダー樹脂としては、ビニル系重合体、アクリル系重合体、ニトリル系重合体、ポリウレタン系重合体、ジエン系重合体等の非フッ素系重合体や、PVDFやPTFE等のフッ素系重合体を挙げることができる。特に、集電体や正極合剤との接着性の観点から非フッ素系重合体が好ましく、より好ましくは、アクリル樹脂、または、少なくともポリオールとポリイソシアネートとからなる重量平均分子量が8,000〜1,500,000、好適には、重量平均分子量が10,000〜1,000,000のポリウレタン樹脂である。<Water-dispersible polymer binder resin>
In the positive electrode mixture of the present invention, the water-dispersible polymer binder resin is a polymer binder resin that can be dispersed in an aqueous solvent described later. Examples of water-dispersible polymer binder resins include non-fluorine polymers such as vinyl polymers, acrylic polymers, nitrile polymers, polyurethane polymers, and diene polymers, and fluorine-based polymers such as PVDF and PTFE. A polymer can be mentioned. In particular, a non-fluorinated polymer is preferable from the viewpoint of adhesiveness with a current collector or a positive electrode mixture, and more preferably an acrylic resin or a weight average molecular weight of at least a polyol and a polyisocyanate is 8,000 to 1. 500,000, preferably a polyurethane resin having a weight average molecular weight of 10,000 to 1,000,000.
水分散性高分子樹脂バインダーとしてアクリル樹脂を用いる場合、アクリル酸エステルやメタクリル酸エステルと、その他の官能性モノマーの共重合体からなるものを用いてもよい。また、水分散性高分子樹脂バインダーとしてポリウレタン樹脂を用いる場合、重量平均分子量が8,000未満であるとバインダーの耐久性が低下することがあり、一方、重量平均分子量が1,500,000を超えるとバインダーの耐久性は向上するものの、バインダー自体が凝集してしまい、分散性、塗工性が著しく低下してしまう場合がある。また、粒子径としては、0.05〜5μmが好ましく、0.1〜1μmがより好ましい。粒子径が5μmを超えると結着性が低下するおそれがあり、一方、粒子径が0.05μm未満であると正極活物質の表面が覆われてしまい、内部抵抗を増加させてしまうおそれがある。上記ポリウレタン樹脂の合成に用いられるポリオールおよびポリイソシアネートとしては特に制限はなく、既知のものを用いることができる。また、上記アクリル樹脂としても特に制限はなく、既知のものを用いることができる。さらに、上記アクリル樹脂の合成に用いられるアクリル酸エステル、メタクリル酸エステルおよびその他のモノマーについても特に制限はなく、既知のものを用いることができる。なお、本発明の正極合剤においては、ポリウレタン樹脂やアクリル樹脂は、水性エマルションや水性ディスパージョンの形態で用いてもよい。 When an acrylic resin is used as the water-dispersible polymer resin binder, an acrylic resin or a methacrylic acid ester and another functional monomer copolymer may be used. When a polyurethane resin is used as the water-dispersible polymer resin binder, if the weight average molecular weight is less than 8,000, the durability of the binder may be lowered, while the weight average molecular weight is 1,500,000. If it exceeds, the durability of the binder is improved, but the binder itself aggregates, and the dispersibility and coatability may be significantly reduced. Moreover, as a particle diameter, 0.05-5 micrometers is preferable and 0.1-1 micrometer is more preferable. If the particle diameter exceeds 5 μm, the binding property may be lowered. On the other hand, if the particle diameter is less than 0.05 μm, the surface of the positive electrode active material may be covered and the internal resistance may be increased. . There is no restriction | limiting in particular as a polyol and polyisocyanate used for the synthesis | combination of the said polyurethane resin, A well-known thing can be used. Moreover, there is no restriction | limiting in particular as said acrylic resin, A well-known thing can be used. Furthermore, there is no restriction | limiting in particular also about the acrylic ester, methacrylic ester, and other monomer which are used for the synthesis | combination of the said acrylic resin, A well-known thing can be used. In the positive electrode mixture of the present invention, the polyurethane resin or acrylic resin may be used in the form of an aqueous emulsion or an aqueous dispersion.
水性エマルションの調製方法としては、公知の手法を採用することができ、例えば、セッケン等の界面活性剤を用いる界面活性剤法、ポリビニルアルコール等の水溶性ポリマーを保護コロイドとして用いるコロイド法等の乳化重合により製造し、一括重合法、プレエマルジョン滴下法、モノマー滴下法等を用いればよい。また、モノマー濃度、反応温度、攪拌速度等の制御により、水性エマルションにおける各種重合体の平均粒径を変化させることができる。乳化重合により、重合体の粒度分布をシャープにすることができ、このような水性エマルションを用いることにより、電極における各種成分を均質にすることができる。 As a preparation method of the aqueous emulsion, a known method can be adopted, for example, a surfactant method using a surfactant such as soap, an emulsification such as a colloid method using a water-soluble polymer such as polyvinyl alcohol as a protective colloid. It may be produced by polymerization, and a batch polymerization method, a pre-emulsion dropping method, a monomer dropping method, or the like may be used. Moreover, the average particle diameter of the various polymers in the aqueous emulsion can be changed by controlling the monomer concentration, reaction temperature, stirring speed, and the like. By emulsion polymerization, the particle size distribution of the polymer can be sharpened, and by using such an aqueous emulsion, various components in the electrode can be made homogeneous.
水性ディスパージョンとしては、ポリテトラフルオロエチレン系水性ディスパージョンを好適に用いることができる。なお、水性ディスパージョンの調製方法においても、公知の手法を採用することができ、ポリテトラフルオロエチレン系水性ディスパージョンは、ポリテトラフルオロエチレンを水に分散して得ることができる。 As the aqueous dispersion, a polytetrafluoroethylene-based aqueous dispersion can be suitably used. In addition, also in the preparation method of an aqueous dispersion, a well-known method can be employ | adopted and a polytetrafluoroethylene type aqueous dispersion can be obtained by disperse | distributing polytetrafluoroethylene in water.
本発明の正極合剤に係るポリウレタン樹脂の合成に用いられるポリオールとしては、ポリエステルポリオール類を好適に用いることができる。ポリエステルポリオール類としては、例えば、ポリエステルポリオール、ポリエステルポリカーボネートポリオール、ポリカーボネートポリオール等を挙げることができる。これらのポリオールの中で、ポリエステルポリオールが、ポリウレタン樹脂をバインダー樹脂に用いた場合、良好な耐久性、強度を与えるので好ましい。 As the polyol used for the synthesis of the polyurethane resin according to the positive electrode mixture of the present invention, polyester polyols can be suitably used. Examples of the polyester polyols include polyester polyol, polyester polycarbonate polyol, and polycarbonate polyol. Among these polyols, polyester polyols are preferable when a polyurethane resin is used as a binder resin because good durability and strength are provided.
ポリエステルポリオールとしては、低分子多価アルコールと低分子多価アルコールの化学量論的量より少ない量の多価カルボン酸またはそのエステル、無水物、ハライド等のエステル形成性誘導体との直接エステル化反応および/またはエステル交換反応により得ることができるものを挙げることができる。 The polyester polyol is a direct esterification reaction between a low-molecular polyhydric alcohol and a polycarboxylic acid having an amount less than the stoichiometric amount of the low-molecular polyhydric alcohol or an ester-forming derivative such as an ester, an anhydride or a halide thereof. And / or what can be obtained by transesterification can be mentioned.
低分子多価アルコールとしては、例えば、エチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、2−メチル−1,3−プロパンジオール、2−ブチル−2−エチル−1,3−プロパンジオール、1,4−ブタンジオール、ネオペンチルグリコール、3−メチル−2,4−ペンタンジオール、2,4−ペンタンジオール、1,5−ペンタンジオール、3−メチル−1,5−ペンタンジオール、2−メチル−2,4−ペンタンジオール、2,4−ジエチル−1,5−ペンタンジオール、1,6−ヘキサンジオール、1,7−ヘプタンジオール、3,5−ヘプタンジオール、1,8−オクタンジオール、2−メチル−1,8−オクタンジオール、1,9−ノナンジオール、1,10−デカンジオール、ジエチレングリコール、トリエチレングリコール等の脂肪族ジオール類、シクロヘキサンジメタノール、シクロヘキサンジオール等脂環式ジオール類、トリメチロールエタン、トリメチロールプロパン、ヘキシトール類、ペンチトール類、グリセリン、ペンタエリスリトール、テトラメチロールプロパン等の三価以上のアルコール類を挙げることができる。これらは、1種単独で用いてもよく、2種以上を混合して用いてもよい。 Examples of the low molecular weight polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- Propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octane Diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethyleneglycol , Aliphatic diols such as triethylene glycol, alicyclic diols such as cyclohexanedimethanol and cyclohexanediol, trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, pentaerythritol, tetramethylolpropane, etc. Mention may be made of alcohols having a higher value. These may be used singly or in combination of two or more.
多価カルボン酸またはそのエステル形成性誘導体としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、2−メチルコハク酸、2−メチルアジピン酸、3−メチルアジピン酸、3−メチルペンタン二酸、2−メチルオクタン二酸、3,8−ジメチルデカン二酸、3,7−ジメチルデカン二酸、水添ダイマー酸、ダイマー酸等の脂肪族ジカルボン酸類、フタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸類、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸類、トリメリト酸、トリメシン酸、ヒマシ油脂肪酸の三量体等のトリカルボン酸類等の多価カルボン酸、これらの多価カルボン酸の酸無水物、これら多価カルボン酸のクロライド、ブロマイド等のハライド、上記多価カルボン酸のメチルエステル、エチルエステル、プロピルエステル、イソプロピルエステル、ブチルエステル、イソブチルエステル、アミルエステル等の低級エステルや、γ−カプロラクトン、δ−カプロラクトン、ε−カプロラクトン、ジメチル−ε−カプロラクトン、δ−バレロラクトン、γ−バレロラクトン、γ−ブチロラクトン等のラクトン類を挙げることができる。これらは、1種単独で用いてもよく、2種以上を混合して用いてもよい。 Examples of the polyvalent carboxylic acid or its ester-forming derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as dimer acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, trimellitic acid, trimesic acid, and castor oil fatty acid. Polycarboxylic acids such as tricarboxylic acids such as trimers, acid anhydrides of these polycarboxylic acids, Halides such as chlorides and bromides of polyvalent carboxylic acids, lower esters such as methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters and amyl esters of the above polyvalent carboxylic acids, γ-caprolactone, δ- Examples include lactones such as caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone. These may be used singly or in combination of two or more.
また、本発明の正極合剤に係るポリウレタン樹脂の合成に用いられるポリイソシアネートとしても特に制限はなく、既知のポリイソシアネートを用いることができる。ポリイソシアネートとしては、ジイソシアネートおよびトリイソシアネートの混合物が、得られるポリウレタン樹脂の分散性が良好で、安価であるため好適である。 Moreover, there is no restriction | limiting in particular as polyisocyanate used for the synthesis | combination of the polyurethane resin which concerns on the positive mix of this invention, A well-known polyisocyanate can be used. As the polyisocyanate, a mixture of diisocyanate and triisocyanate is preferable because the resulting polyurethane resin has good dispersibility and is inexpensive.
ジイソシアネートとしては、例えば、2,4−および/または2,6−トリレンジイソシアネート、ジフェニルメタン−4,4’−ジイソシアネート、p−フェニレンジイソシアネート、キシリレンジイソシアネート、1,5−ナフチレンジイソシアネート、3,3’−ジメチルジフェニル−4,4’−ジイソシアネート、ジアニシジンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ジイソシアネート類、イソホロンジイソシアネート、ジシクロヘキシルメタン−4,4’−ジイソシアネート、トランス−1,4−シクロヘキシルジイソシアネート、ノルボルネンジイソシアネート等の脂環式ジイソシアネート類、1,6−ヘキサメチレンジイソシアネート、2,2,4(2,4,4)−トリメチルヘキサメチレンジイソシアネート、リシンジイソシアネート等の脂肪族ジイソシアネート類を挙げることができる。特に、脂環式ジイソシアネートが耐加水分解性に優れるので好ましい。これらは、1種単独で用いてもよく、2種以上を混合して用いてもよい。 Examples of the diisocyanate include 2,4- and / or 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3. Aromatic diisocyanates such as' -dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, Cycloaliphatic diisocyanates such as norbornene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 (2,4,4) -trimethylhexamethylene Isocyanates, and aliphatic diisocyanates such as lysine diisocyanate. In particular, alicyclic diisocyanates are preferred because they are excellent in hydrolysis resistance. These may be used singly or in combination of two or more.
トリイソシアネートとしては、トリフェニルメタントリイソシアネート、1−メチルベンゾール−2,4,6−トリイソシアネート、上記ジイソシアネートのイソシアヌレート三量化物、ビューレット三量化物、トリメチロールプロパンアダクト化物等を挙げることができる。特に、イソシアヌレート三量化物がポリウレタン樹脂に対して安定した分散状態を与えるので好ましい。これらは、1種単独で用いてもよく、2種以上を混合して用いてもよい。 Examples of the triisocyanate include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, isocyanurate trimerization, burette trimerization, and trimethylolpropane adduct of the above diisocyanate. it can. In particular, isocyanurate trimers are preferred because they give a stable dispersion to the polyurethane resin. These may be used singly or in combination of two or more.
本発明の正極合剤においては、ポリウレタン樹脂としては、鎖延長剤を用いて重合されたポリウレタン樹脂を用いてもよい。すなわち、ポリウレタン樹脂として高分子量のものが必要な場合は、ポリウレタン樹脂の合成に用いられる既知の鎖延長剤を用いることができる。鎖延長剤としては、多価アミン化合物、多価一級アルコール化合物等が好ましく、多価アミン化合物がより好ましい。 In the positive electrode mixture of the present invention, a polyurethane resin polymerized using a chain extender may be used as the polyurethane resin. That is, when a high molecular weight polyurethane resin is required, a known chain extender used for the synthesis of a polyurethane resin can be used. As the chain extender, a polyvalent amine compound, a polyvalent primary alcohol compound and the like are preferable, and a polyvalent amine compound is more preferable.
多価アミン化合物としては、エチレンジアミン、プロピレンジアミン等の上記例示の低分子ポリオールのアルコール性水酸基がアミノ基に置換された低分子ポリアミン類、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン等のポリエーテルポリアミン類、メンセンジアミン、イソホロンジアミン、ノルボルネンジアミン、ビス(4−アミノ−3−メチルジシクロヘキシル)メタン、ジアミノジシクロヘキシルメタン、ビス(アミノメチル)シクロヘキサン、N−アミノメチルピペラジン、3,9−ビス(3−アミノプロピル)2,4,8,10−テトラオキサスピロ(5,5)ウンデカン等の脂環式ポリアミン類、m−キシレンジアミン、α−(m/pアミノフェニル)エチルアミン、m−フェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジアミノジエチルジメチルジフェニルメタン、ジアミノジエチルジフェニルメタン、ジメチルチオトルエンジアミン、ジエチルトルエンジアミン、α,α’−ビス(4−アミノフェニル)−p−ジイソプロピルベンゼン、ジチオジアニリン等の芳香族ポリアミン類、ヒドラジン、エチレンジアミン、プロピレンジアミン、キシレンジアミン、アジピン酸ジヒドラジド、イソホロンジアミン、ピペラジンおよびその誘導体、フェニレンジアミン、トリレンジアミン、キシレンジアミン、イソフタル酸ジヒドラジド等を挙げることができる。本発明の正極合剤においては、これらは、1種単独で用いてもよく、2種以上を混合して用いてもよい。 Examples of the polyvalent amine compound include low molecular weight polyamines in which the alcoholic hydroxyl group of the above exemplified low molecular polyol such as ethylenediamine and propylenediamine is substituted with an amino group, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine , Polyether polyamines such as polyoxypropylene triamine, mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminomethyl Piperazine, alicyclic polyamines such as 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, m-xylenediamine, α- m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, α'-bis (4-aminophenyl) -Aromatic polyamines such as p-diisopropylbenzene and dithiodianiline, hydrazine, ethylenediamine, propylenediamine, xylenediamine, adipic dihydrazide, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, isophthalic acid And dihydrazide. In the positive electrode material mixture of the present invention, these may be used singly or in combination of two or more.
本発明の正極合剤に係るポリウレタン樹脂の製造方法については特に制限はなく、既知の製造方法を用いることができる。例えば、ポリオール、ジイソシアネートおよびトリイソシアネートを一括で反応させ、予めウレタンプレポリマーを調製し、それを鎖延長剤存在下の水中で鎖延長させることができるプレポリマー法が好ましい。 There is no restriction | limiting in particular about the manufacturing method of the polyurethane resin which concerns on the positive mix of this invention, A known manufacturing method can be used. For example, a prepolymer method is preferred in which a polyol, diisocyanate and triisocyanate are reacted together to prepare a urethane prepolymer in advance and the chain can be extended in water in the presence of a chain extender.
鎖延長剤の使用量については、特に制限されることはなく、任意の量を選択して使用できるが、例えば、ポリウレタン樹脂の合成としてプレポリマー法を選択した場合、プレポリマー中のイソシアネート基の数1に対して鎖延長剤の活性水素の数は0.1〜1.5が、得られる水分散型ポリウレタン組成物の分散性が良好で、変色もないので好ましく、0.5〜1.0がより好ましい。 The amount of the chain extender is not particularly limited, and any amount can be selected and used. For example, when the prepolymer method is selected as the synthesis of the polyurethane resin, the isocyanate group in the prepolymer The number of active hydrogens in the chain extender relative to the number 1 is preferably 0.1 to 1.5 because the resulting water-dispersible polyurethane composition has good dispersibility and no discoloration, and is preferably 0.5 to 1. 0 is more preferable.
本発明の正極合剤に係るアクリル樹脂の合成に用いられるアクリル酸エステルおよびメタクリル酸エステルとしては、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸−n−プロピル、メタクリル酸−n−プロピル、アクリル酸−n−ブチル、メタクリル酸−n−ブチル、アクリル酸−t−ブチル、メタクリル酸−t−ブチル、アクリル酸−n−ヘキシル、メタクリル酸−n−ヘキシル、アクリル酸−2−エチルヘキシル、メタクリル酸−2−エチルヘキシル、アクリル酸シクロヘキシル、メタクリル酸シクロヘキシル、アクリル酸ステアリル、メタクリル酸ステアリル、アクリル酸オクタデシル、メタクリル酸オクタデシル、アクリル酸フェニル、メタクリル酸フェニル、アクリル酸ベンジル、メタクリル酸ベンジル、アクリル酸クロロメチル、メタクリル酸クロロメチル、アクリル酸−2−クロロエチル、メタクリル酸−2−クロロエチル、アクリル酸−2−ヒドロキシエチル、メタクリル酸−2−ヒドロキシエチル、アクリル酸−3−ヒドロキシプロピル、メタクリル酸−3−ヒドロキシプロピル、アクリル酸−2,3,4,5,6−ペンタヒドロキシヘキシル、メタクリル酸−2,3,4,5,6−ペンタヒドロキシヘキシル、アクリル酸−2,3,4,5−テトラヒドロキシペンチル、メタクリル酸−2,3,4,5−テトラヒドロキシペンチル、アクリル酸アミノエチル、アクリル酸プロピルアミノエチル、メタクリル酸ジメチルアミノエチル、メタクリル酸エチルアミノプロピル、メタクリル酸フェニルアミノエチルおよびメタクリル酸シクロヘキシルアミノエチル等が挙げられる。これらは単独ないし2種以上を用いることができる。 Examples of the acrylic ester and methacrylic ester used for the synthesis of the acrylic resin according to the positive electrode mixture of the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid-n-propyl, methacrylic acid. -N-propyl, acrylic acid-n-butyl, methacrylic acid-n-butyl, acrylic acid-t-butyl, methacrylic acid-t-butyl, acrylic acid-n-hexyl, methacrylic acid-n-hexyl, acrylic acid- 2-ethylhexyl, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, stearyl acrylate, stearyl methacrylate, octadecyl acrylate, octadecyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate Benzyl methacrylate, chloromethyl acrylate, chloromethyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy hydroxy Propyl, methacrylic acid-3-hydroxypropyl, acrylic acid-2,3,4,5,6-pentahydroxyhexyl, methacrylic acid-2,3,4,5,6-pentahydroxyhexyl, acrylic acid-2,3 , 4,5-tetrahydroxypentyl, methacrylate-2,3,4,5-tetrahydroxypentyl, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenyl methacrylate Aminoethyl Fine cyclohexyl methacrylate aminoethyl, and the like. These may be used alone or in combination of two or more.
本発明の正極合剤に係るアクリル樹脂においては、上記アクリル酸エステルおよび上記メタクリル酸エステル以外に、官能性モノマーを加えることができる。例えば、単官能性モノマーとしては、スチレン、α−メチルスチレン、1−ビニルナフタレン、3−メチルスチレン、4−プロピルスチレン、4−シクロヘキシルスチレン、4−ドデシルスチレン、2−エチル−4−ベンジルスチレン、4−(フェニルブチル)スチレン、ハロゲン化スチレン等の芳香族ビニル系モノマー;アクリロニトリル、メタクリロニトリル等のシアン化ビニル系モノマー;ブタジエン、イソプレン、2,3−ジメチルブタジエン、2−メチル−3−エチルブタジエン、1,3−ペンタジエン、3−メチル−1,3−ペンタジエン、2−エチル−1,3−ペンタジエン、1,3−ヘキサジエン、2−メチル−1,3−ヘキサジエン、3,4−ジメチル−1,3−ヘキサジエン、1,3−ヘプタジエン、3−メチル−1,3−ヘプタジエン、1,3−オクタジエン、シクロペンタジエン、クロロプレン、ミルセン等の共役ジエン系モノマーが挙げられる。また、多官能性モノマーとしては、例えば、アリルメタクリレート、アリルアクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート、ジアリルフタレート、ジアリルマレート、ジビニルアジペート、ジビニルベンゼンエチレングリコールジメタクリレート、ジビニルベンゼンエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリメタクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラメタクリレート、テトラメチロールメタンテトラアクリレート、ジプロピレングリコールジメタクリレートおよびジプロピレングリコールジアクリレート等が挙げられ、これらは2種以上を併用してもよい。 In the acrylic resin according to the positive electrode mixture of the present invention, a functional monomer can be added in addition to the acrylic ester and the methacrylic ester. For example, monofunctional monomers include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, Aromatic vinyl monomers such as 4- (phenylbutyl) styrene and halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; butadiene, isoprene, 2,3-dimethylbutadiene, 2-methyl-3-ethyl Butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3,4-dimethyl- 1,3-hexadiene, 1,3-heptadiene, 3-methyl-1, - heptadiene, 1,3-octadiene, cyclopentadiene, chloroprene, and a conjugated diene monomer myrcene, and the like. Examples of the multifunctional monomer include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate. , Diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, dipropylene glycol dimethacrylate And dipropi Glycol diacrylate and the like, which may be used in combination of two or more.
本発明に係るアクリル樹脂の製造方法については特に制限はなく、既知の製造方法を用いることができる。 There is no restriction | limiting in particular about the manufacturing method of the acrylic resin which concerns on this invention, A known manufacturing method can be used.
なお、本発明の正極合剤においては、水分散性高分子系バインダー樹脂に、必要に応じて他の重合体粒子を添加してもよい。重合体粒子としては、例えば、ビニル系重合体、アクリル系重合体、ニトリル系重合体、ポリウレタン系重合体、ジエン系重合体等の非フッ素系重合体;PVDFやPTFE等のフッ素系ポリマー;を挙げることができ、特に、接着性の点から非フッ素系重合体が好ましい。なお、本発明の正極合剤においては、これら重合体粒子は、1種単独で用いてもよく、2種以上を混合して用いてもよい。 In the positive electrode mixture of the present invention, other polymer particles may be added to the water-dispersible polymer binder resin as necessary. Examples of polymer particles include non-fluorine polymers such as vinyl polymers, acrylic polymers, nitrile polymers, polyurethane polymers, and diene polymers; fluorine polymers such as PVDF and PTFE; In particular, a non-fluorine polymer is preferable from the viewpoint of adhesiveness. In the positive electrode mixture of the present invention, these polymer particles may be used alone or in combination of two or more.
本発明における正極合剤においては、水分散性高分子バインダー樹脂(重合体粒子)の含有割合は、正極活物質100質量部に対して、固形分で好ましくは0.1〜10質量部であり、より好ましくは0.5〜5質量部である。重合体粒子の含有割合を上記範囲にすることで、本発明の正極合剤を集電体に塗布・乾燥して得られる正極合剤層の集電板に対するは密着性および柔軟性を向上させることができる。 In the positive electrode mixture in the present invention, the content of the water-dispersible polymer binder resin (polymer particles) is preferably 0.1 to 10 parts by mass in solid content with respect to 100 parts by mass of the positive electrode active material. More preferably, it is 0.5-5 mass parts. By making the content ratio of the polymer particles in the above range, the adhesion and flexibility of the positive electrode mixture layer obtained by applying and drying the positive electrode mixture of the present invention to the current collector are improved. be able to.
なお、本発明の正極合剤においては、水分散性高分子系バインダー樹脂の平均粒子径は0.05〜5μmが好ましく、0.1〜1μmがより好ましい。粒子径が大きすぎると結着性が低下するおそれがあり、粒子径が小さすぎると正極活物質の表面が覆われてしまい、内部抵抗を増加させてしまうおそれがある。 In the positive electrode mixture of the present invention, the average particle size of the water-dispersible polymer binder resin is preferably 0.05 to 5 μm, more preferably 0.1 to 1 μm. If the particle size is too large, the binding property may decrease, and if the particle size is too small, the surface of the positive electrode active material may be covered and the internal resistance may be increased.
<導電助剤>
本発明の正極合剤においては、導電助剤としては、アセチレンブラック、ケッチェンブラック、カーボンブラック、グラファイト、気相成長カーボン繊維、およびカーボンナノチューブ、グラフェン、フラーレン等の導電性カーボンを用いることができる。導電助剤を用いることにより、正極活物質同士の電気的接触を向上させることができ、非水電解質二次電池に用いる場合に、放電レート特性を改善することができる。導電助剤の配合量は、正極活物質100質量部に対して、好ましくは0.1〜20質量部、より好ましくは0.1〜10質量部である。<Conductive aid>
In the positive electrode mixture of the present invention, as the conductive assistant, acetylene black, ketjen black, carbon black, graphite, vapor grown carbon fiber, and conductive carbon such as carbon nanotube, graphene, fullerene can be used. . By using a conductive additive, the electrical contact between the positive electrode active materials can be improved, and when used in a non-aqueous electrolyte secondary battery, the discharge rate characteristics can be improved. The blending amount of the conductive assistant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material.
<界面活性剤>
本発明の正極合剤においては、界面活性剤としては、電解質への分散性が高く、リチウムイオン等との反応性が低く、かつ、電解質中のイオン伝導を妨げない限り、特に制限されるものではない。例えば、界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤を挙げることができるが、特に非イオン性界面活性剤を用いることが好ましい。非イオン性界面活性剤は、周囲のイオン(リチウムイオン等)との反応性が低く、電解質中および活物質表面のイオン伝導を妨げないためである。本発明の正極合剤においては、界面活性剤は1種単独で用いてもよく、2種以上を混合して用いてもよい。<Surfactant>
In the positive electrode mixture of the present invention, the surfactant is particularly limited as long as it has high dispersibility in the electrolyte, low reactivity with lithium ions, etc., and does not hinder ion conduction in the electrolyte. is not. For example, examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant, and it is particularly preferable to use a nonionic surfactant. . This is because the nonionic surfactant has low reactivity with surrounding ions (such as lithium ions) and does not hinder ion conduction in the electrolyte and on the active material surface. In the positive electrode mixture of the present invention, the surfactant may be used alone or in combination of two or more.
カチオン性界面活性剤としては、例えば、モノ/ジ長鎖アルキル型の第4級アンモニウム塩、アルキルアミン塩等を挙げることができる。また、アニオン性界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキル硫酸塩、アルキルエーテル硫酸塩、アルケニルエーテル硫酸塩、アルケニル硫酸塩、α−オレフィンスルホン酸塩、α−スルホ脂肪酸またはそのエステル塩、アルカンスルホン酸塩、飽和脂肪酸塩、不飽和脂肪酸塩、アルキルエーテルカルボン酸塩、アルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、N−アシルアミノ酸型界面活性剤、アルキルリン酸エステルまたはその塩、アルケニルリン酸エステルまたはその塩、アルキルスルホコハク酸塩等を挙げることができる。両性界面活性剤としては、カルボキシル型両性界面活性剤、スルホベタイン型両性界面活性剤等を挙げることができる。 Examples of the cationic surfactant include mono / di long chain alkyl type quaternary ammonium salts and alkylamine salts. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, alkenyl ether sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt thereof. , Alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, Examples thereof include alkenyl phosphate esters or salts thereof, and alkylsulfosuccinates. Examples of the amphoteric surfactant include a carboxyl type amphoteric surfactant and a sulfobetaine type amphoteric surfactant.
非イオン性界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレン高級アルキルエーテル等のポリオキシエチレンアルキルエーテル;ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル;ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリオレエート等のポリオキシエチレンソルビタン脂肪酸エステル;ショ糖脂肪酸エステル;テトラオレイン酸ポリオキシエチレンソルビット等のポリオキシエチレンソルビトール脂肪酸エステル;ポリエチレングリコールモノラウレート、ポリエチレングリコールモノステアレート、ポリエチレングリコールジステアレート、ポリエチレングリコールモノオレエート等のポリオキシエチレン脂肪酸エステル;ポリオキシエチレンアルキルアミン;ポリオキシエチレン硬化ヒマシ油;エチレンオキサイドとプロピレンオキサイドとのブロックコポリマー;ソルビタンモノラウレート、ソルビタンモノミリスチレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタントリステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタンセスキオレエート、ソルビタンジステアレート等のソルビタン脂肪酸エステル;グリセロールモノステアレート、グリセロールモノオレエート、ジグリセロールモノオレエート、自己乳化型グリセロールモノステアレート等のグリセリン脂肪酸エステル;アルキルアルカノールアミド等を好適に用いることができる。 Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene higher alkyl ether; Polyoxyethylene alkyl aryl ethers such as oxyethylene nonylphenyl ether; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Polystearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc. Oxyethylene sorbitan fatty acid ester; sucrose fatty acid ester; polyoxyethylene sorbitol fatty acid ester such as polyoxyethylene sorbitol tetraoleate; polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate Polyoxyethylene fatty acid ester such as polyoxyethylene alkylamine; polyoxyethylene hydrogenated castor oil; block copolymer of ethylene oxide and propylene oxide; sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate Rate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate Sorbitan fatty acid esters such as sorbitan sesquioleate and sorbitan distearate; glycerol fatty acid esters such as glycerol monostearate, glycerol monooleate, diglycerol monooleate and self-emulsifying glycerol monostearate; alkyl alkanolamides and the like It can be used suitably.
本発明の正極合剤においては、界面活性剤として非イオン界面活性剤を用いる場合、非イオン界面活性剤は高分子材料であることが好ましく、非イオン界面活性剤の重量平均分子量は、500以上であることが好ましい。非イオン性界面活性剤の重量平均分子量を500以上とすることにより、界面活性剤による正極活物質の分散効果が良好に発揮される。これは、高分子の界面活性剤により、溶媒と界面活性剤の親和性が高くなり、粒子の近傍に溶媒を保持しやすくなるため、粒子間の凝集が抑制されるからであると考えられる。一方、重量平均分子量の上限については特に制限はないが、100,000以下であることが好ましい。本発明の正極合剤における非イオン界面活性剤のより好適な重量平均分子量の範囲は1,000〜50,000である。重量平均分子量をこの範囲にすることで、正極活物質の分散性がより良好となるとともに、イオンの移動がスムーズに行われるようになる。 In the positive electrode mixture of the present invention, when a nonionic surfactant is used as the surfactant, the nonionic surfactant is preferably a polymer material, and the weight average molecular weight of the nonionic surfactant is 500 or more. It is preferable that By setting the weight average molecular weight of the nonionic surfactant to 500 or more, the positive electrode active material is effectively dispersed by the surfactant. This is presumably because the high molecular surfactant increases the affinity between the solvent and the surfactant and makes it easier to hold the solvent in the vicinity of the particles, thereby suppressing aggregation between the particles. On the other hand, although there is no restriction | limiting in particular about the upper limit of a weight average molecular weight, It is preferable that it is 100,000 or less. The more preferable range of the weight average molecular weight of the nonionic surfactant in the positive electrode mixture of the present invention is 1,000 to 50,000. By setting the weight average molecular weight within this range, the dispersibility of the positive electrode active material becomes better, and ions can be moved smoothly.
非イオン性界面活性剤の中でも、イオン伝導性が高く、リチウムイオン電池の電解質にも用いられ得るポリエチレングリコール系界面活性剤が好ましく、ポリエチレングリコール脂肪酸エステル系界面活性剤がより好ましく、さらに好ましくはポリエチレングリコールのステアリン酸エステル類である。ポリエチレングリコールのステアリン酸エステル類は増粘効果も高く、活物質の沈降凝集防止効果も優れている。また、ポリエチレングリコール系界面活性剤を活物質の被覆に用いることで、界面活性剤中のリチウムイオンの移動を促進することができる。なお、本発明においては、ポリエチレングリコール系界面活性剤とは、活性剤化合物中に、エチレングリコール鎖を含むものを指す。 Among nonionic surfactants, polyethylene glycol surfactants that have high ion conductivity and can be used for electrolytes of lithium ion batteries are preferred, polyethylene glycol fatty acid ester surfactants are more preferred, and polyethylene is more preferred. Glycolic stearates. Polyethylene glycol stearates have a high thickening effect and an excellent effect of preventing sedimentation and aggregation of the active material. Moreover, the movement of lithium ions in the surfactant can be promoted by using a polyethylene glycol-based surfactant for coating the active material. In addition, in this invention, a polyethyleneglycol type surfactant refers to what contains an ethylene glycol chain in an activator compound.
本発明の正極合剤に用いる界面活性剤は、グリフィン法によるHLBが13〜20であることが好ましく、より好ましくは15〜20である。特に溶媒に有機溶媒を使用しない場合は、HLBが16〜20であることがより好ましい。HLBがこの範囲の界面活性剤を用いると、界面活性剤の親水基と疎水基がバランスよく配列されているため、水溶媒中で極性を有する正極活物質とバインダー樹脂の均一な分散が促進される。なお、グリフィン法とは、界面活性剤の親水基の式量と分子量を元に下記の式、
HLB値=20×親水部の式量の総和/分子量
にて定義される。The surfactant used in the positive electrode mixture of the present invention preferably has an HLB of 13 to 20, more preferably 15 to 20 by the Griffin method. In particular, when no organic solvent is used as the solvent, the HLB is more preferably 16-20. When HLB uses a surfactant in this range, the hydrophilic group and hydrophobic group of the surfactant are arranged in a well-balanced manner, so that uniform dispersion of the positive electrode active material and the binder resin having polarity in an aqueous solvent is promoted. The The Griffin method is based on the following formula based on the formula weight and molecular weight of the hydrophilic group of the surfactant:
HLB value = 20 × defined by the sum of formula weight of hydrophilic part / molecular weight.
本発明の正極合剤においては、界面活性剤の配合量は、正極活物質100質量部に対して、好ましくは0.1〜10質量部であり、より好ましくは0.5〜5質量部である。界面活性剤の配合量を、上記範囲とすることにより、正極合剤中の正極活物質の分散性および塗工性に優れた正極合剤を得ることができる。 In the positive electrode mixture of the present invention, the blending amount of the surfactant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. is there. By making the compounding quantity of surfactant into the said range, the positive mix which was excellent in the dispersibility and coating property of the positive electrode active material in a positive mix can be obtained.
<溶媒>
本発明の正極合剤に用いる溶媒としては、水分散性高分子バインダー樹脂および正極活物質を均一に分散および沈降凝集を阻害する界面活性剤と親和するものであれば特に制限はなく、水であっても有機溶媒であってもよい。また、本発明の正極合剤においては、溶媒としては、特に水を好適に用いることができるが、上記効果を阻害しない範囲で、有機溶媒を含んでいてもよい。かかる有機溶媒としては、例えば、シクロペンタン、シクロヘキサン等の環状脂肪族炭化水素類;トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類;アセトン、エチルメチルケトン、ジソプロピルケトン、シクロヘキサノン、メチルシクロヘキサン、エチルシクロヘキサン等のケトン類;メチレンクロライド、クロロホルム、四塩化炭素等の塩素系脂肪族炭化水素;酢酸エチル、酢酸ブチル、γ−ブチロラクトン、ε−カプロラクトン等のエステル類;アセトニトリル、プロピオニトリル等のアシロニトリル類;テトラヒドロフラン、エチレングリコールジエチルエーテル等のエーテル類:メタノール、エタノール、イソプロパノール、エチレングリコール、エチレングリコールモノメチルエーテル等のアルコール類;N−メチルピロリドン、N,N−ジメチルホルムアミド等のアミド類を挙げることができる。<Solvent>
The solvent used in the positive electrode mixture of the present invention is not particularly limited as long as it is compatible with a surfactant that uniformly disperses the water-dispersible polymer binder resin and the positive electrode active material and inhibits sedimentation aggregation. Or an organic solvent. Moreover, in the positive electrode material mixture of the present invention, water can be particularly preferably used as the solvent, but an organic solvent may be included as long as the above effects are not impaired. Examples of the organic solvent include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; acetone, ethyl methyl ketone, disopropyl ketone, cyclohexanone, methylcyclohexane and ethyl. Ketones such as cyclohexane; Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, γ-butyrolactone and ε-caprolactone; Acylonitriles such as acetonitrile and propionitrile Ethers such as tetrahydrofuran and ethylene glycol diethyl ether: alcohols such as methanol, ethanol, isopropanol, ethylene glycol and ethylene glycol monomethyl ether; Examples include amides such as loridone and N, N-dimethylformamide.
<その他添加剤>
本発明の正極合剤は、正極活物質と、水分散性高分子バインダー樹脂と、導電助剤と、界面活性剤と、を含有することのみが重要であり、それ以外に特に制限はなく、上記成分以外にも電池反応に影響を及ぼさない範囲で添加剤を含んでいてもよい。例えば、本発明の正極合剤には、上記成分の他に、補強材、増粘剤、消泡・レベリング剤、電解液分解抑制剤等の成分が含まれていてもよい。<Other additives>
The positive electrode mixture of the present invention is only important to contain a positive electrode active material, a water-dispersible polymer binder resin, a conductive auxiliary agent, and a surfactant, and there is no particular limitation other than that, In addition to the above components, additives may be included within a range that does not affect the battery reaction. For example, the positive electrode mixture of the present invention may contain components such as a reinforcing material, a thickener, a defoaming / leveling agent, and an electrolytic solution decomposition inhibitor in addition to the above components.
補強材としては、各種の無機および有機の球状、板状、棒状または繊維状のフィラーを用いてもよい。補強材を用いることにより、さらに強靭で柔軟な電極を得ることができ、優れた長期サイクル特性を付与することができる。これらは1種単独で用いてもよく、2種以上を混合して用いてもよい。補強材の配合量は、正極活物質100質量部に対して、通常0.01〜20質量部、好ましくは1〜10質量部である。補強材の配合量を、上記範囲とすることにより、高い容量と高い負荷特性を付与することができる。 As the reinforcing material, various inorganic and organic spherical, plate-like, rod-like, or fibrous fillers may be used. By using a reinforcing material, a tougher and more flexible electrode can be obtained, and excellent long-term cycle characteristics can be imparted. These may be used alone or in combination of two or more. The compounding quantity of a reinforcing material is 0.01-20 mass parts normally with respect to 100 mass parts of positive electrode active materials, Preferably it is 1-10 mass parts. By setting the blending amount of the reinforcing material within the above range, high capacity and high load characteristics can be imparted.
増粘剤としては、電極製造時に使用する溶媒や電解液、電池使用時に用いる他の材料に対して安定な材料であれば、特に制限はない。例えば、カルボキシルメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、酸化スターチ、リン酸化スターチ、カゼイン等を用いることができる。これらは1種単独で用いてもよく、2種以上を混合して用いてもよい。増粘剤の配合量は、正極活物質100質量部に対して、通常0.01〜20質量部、好ましくは1〜10質量部である。増粘剤の配合量を上記範囲とすることにより、比重の重い正極活物質の沈降凝集を良好に防止することができる。 The thickener is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used during electrode production and other materials used during battery use. For example, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like can be used. These may be used alone or in combination of two or more. The compounding quantity of a thickener is 0.01-20 mass parts normally with respect to 100 mass parts of positive electrode active materials, Preferably it is 1-10 mass parts. By setting the blending amount of the thickener within the above range, it is possible to satisfactorily prevent sedimentation and aggregation of the positive electrode active material having a high specific gravity.
消泡・レベリング剤としては、アルキル系界面活性剤、シリコーン系界面活性剤、フッ素系界面活性剤、金属系界面活性剤等の界面活性剤を用いることができる。界面活性剤を混合することにより、塗工時に発生するはじきを防止することができ、また、電極の平滑性を向上させることができる。消泡・レベリング剤の配合量は、正極活物質100質量部に対して、好ましくは0.01〜5質量部である。消泡・レベリング剤の配合量を上記範囲とすることで、電極塗工時の塗工不具合を防止し、生産性を向上させることができる。 As the defoaming / leveling agent, surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants can be used. By mixing the surfactant, it is possible to prevent the repelling that occurs during coating and to improve the smoothness of the electrode. The blending amount of the defoaming / leveling agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. By making the compounding quantity of a defoaming and leveling agent into the said range, the coating malfunction at the time of electrode coating can be prevented, and productivity can be improved.
電解液分解抑制剤としては、電解液中に使用されるビニレンカーボネート等を用いることができる。電極中の電解液分解抑制剤の配合量は正極活物質100質量部に対して、好ましくは0.01〜5質量部である。電解液分解抑制剤の配合量を上記範囲とすることでサイクル特性および高温特性を、さらに向上させることができる。その他には、フュームドシリカやフュームドアルミナ等のナノ微粒子を挙げることができる。ナノ微粒子を混合することにより電極形成用合剤のチキソ性をコントロールすることができる。本発明の正極合剤におけるナノ微粒子の配合量は、正極活物質100質量部に対して、好ましくは0.01〜5質量部である。ナノ微粒子の配合量を上記範囲とすることで、合剤安定性、生産性をさらに向上させることができ、より高い電池特性を付与することができる。 As the electrolytic solution decomposition inhibitor, vinylene carbonate or the like used in the electrolytic solution can be used. The amount of the electrolytic solution decomposition inhibitor in the electrode is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. By setting the blending amount of the electrolytic solution decomposition inhibitor in the above range, the cycle characteristics and the high temperature characteristics can be further improved. Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the electrode forming mixture can be controlled. The compounding amount of the nanoparticles in the positive electrode mixture of the present invention is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. By making the compounding quantity of a nano fine particle into the said range, mixture stability and productivity can further be improved and a higher battery characteristic can be provided.
<正極合剤の製造方法>
本発明の正極合剤は、上記の正極活物質と、水分散性高分子バインダー樹脂と、導電助剤と、界面活性剤および溶媒、その他必要に応じてその他の添加剤を混合して得ることができる。本発明の正極合剤を製造するにあたって、混合方法については特に制限はなく、例えば、撹拌式、振とう式、および回転式等の混合装置を使用した方法を採用することができる。また、ホモジナイザー、ボールミル、サンドミル、ロールミル、および遊星式混練機等の分散混練装置を使用した方法を採用してもよい。<Method for producing positive electrode mixture>
The positive electrode mixture of the present invention is obtained by mixing the positive electrode active material, a water-dispersible polymer binder resin, a conductive additive, a surfactant and a solvent, and other additives as necessary. Can do. In producing the positive electrode mixture of the present invention, the mixing method is not particularly limited, and for example, a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type can be employed. Further, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader may be employed.
<正極>
次に、本発明の非水電解質二次電池用正極について説明する。
本発明の正極は、上記本発明の正極合剤が集電体に塗布されてなるものである。本発明の正極は、上記本発明の正極合剤を集電体上に塗布する塗布工程と、得られた集電体を乾燥して正極合剤層を形成する乾燥工程と、を経て製造することができる。本発明の正極においては、正極合剤層を集電体の片面に形成してもよいが、両面に形成することが好ましい。以下、本発明の正極の構成および製造方法について詳細に説明する。<Positive electrode>
Next, the positive electrode for nonaqueous electrolyte secondary batteries of this invention is demonstrated.
The positive electrode of the present invention is obtained by applying the positive electrode mixture of the present invention to a current collector. The positive electrode of the present invention is manufactured through an application step of applying the positive electrode mixture of the present invention on a current collector and a drying step of drying the obtained current collector to form a positive electrode mixture layer. be able to. In the positive electrode of the present invention, the positive electrode mixture layer may be formed on one side of the current collector, but is preferably formed on both sides. Hereinafter, the structure and manufacturing method of the positive electrode of the present invention will be described in detail.
<集電体>
本発明の正極に用いる集電体は、電気導電性を有し、かつ電気化学的に耐久性のある材料であれば特に制限されないが、耐熱性を有する金属材料が好ましい。例えば、鉄、銅、アルミニウム、ニッケル、ステンレス鋼、チタン、タンタル、金、白金等を挙げることができる。特に、充電時の酸化劣化が少ないことからアルミニウムまたはアルミニウム合金が好ましい。集電体の形状は特に制限されないが、厚さ5〜100μm程度のシート状のものを好適に用いることができる。<Current collector>
The current collector used for the positive electrode of the present invention is not particularly limited as long as it is an electrically conductive and electrochemically durable material, but a metal material having heat resistance is preferable. For example, iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, etc. can be mentioned. In particular, aluminum or an aluminum alloy is preferable because of less oxidation deterioration during charging. The shape of the current collector is not particularly limited, but a sheet having a thickness of about 5 to 100 μm can be suitably used.
本発明の正極においては、集電体は、正極合剤層との接着強度を高めるため、予め粗面化処理して使用するのが好ましい。粗面化方法としては、機械的研磨法、電解研磨法、化学研磨法等が挙げられる。機械的研磨法においては、研磨剤粒子を固着した研磨布紙、砥石、エメリバフ、鋼線等を備えたワイヤーブラシ等を用いることができる。また、電極層の接着強度や導電性を高めるために、集電体表面に中間層を形成してもよい。 In the positive electrode of the present invention, the current collector is preferably used after roughening in advance in order to increase the adhesive strength with the positive electrode mixture layer. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical polishing method, it is possible to use abrasive cloth paper, abrasive wheels, emery buffs, wire brushes equipped with steel wires and the like to which abrasive particles are fixed. Further, an intermediate layer may be formed on the current collector surface in order to increase the adhesive strength and conductivity of the electrode layer.
<塗布方法>
上記本発明の正極合剤を集電体上に塗布する方法についても特に限定はなく、既知の方法を用いることができる。塗布方法としては、例えば、ダイコーティング法、ドクターコーティング法、ディップコーティング法、ロールコーティング法、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を挙げることができる。<Application method>
There is no limitation in particular also about the method of apply | coating the positive mix of the said invention on a collector, A well-known method can be used. Examples of the coating method include a die coating method, a doctor coating method, a dip coating method, a roll coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method.
<乾燥方法>
上記塗布方法により得られた集電体を乾燥させる方法としては特に制限はないが、例えば、温風、熱風、低湿風による乾燥、真空乾燥、(遠)赤外線や電子線等の照射による乾燥法を挙げることができる。乾燥時間は通常5〜30分間であり、乾燥温度は通常40〜180℃である。<Drying method>
The method of drying the current collector obtained by the above coating method is not particularly limited. For example, drying with warm air, hot air, low-humidity air, vacuum drying, or drying by irradiation with (far) infrared rays or electron beams. Can be mentioned. The drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
<圧延>
本発明の製造方法においては、塗布工程、乾燥工程を経た後、金型プレスやロールプレス等を用いて、加圧処理により正極合剤層の空隙率を下げる圧延工程を経ることが好ましい。空隙率の好適な範囲は5%〜15%であり、より好適には7%〜13%である。空隙率が15%を超えると充電効率や放電効率が悪化するため、好ましくない。一方、空隙率が5%未満の場合は、高い体積容量が得難かったり、正極合剤層が集電体から剥がれやすく不良を発生しやすいといった問題が生じるおそれがある。なお、バインダー樹脂として硬化性樹脂を用いる場合は、この硬化性樹脂を硬化させる工程を有していることが好ましい。<Rolling>
In the production method of the present invention, it is preferable to go through a rolling process in which the porosity of the positive electrode mixture layer is lowered by pressure treatment using a die press, a roll press or the like after passing through a coating process and a drying process. The preferable range of the porosity is 5% to 15%, and more preferably 7% to 13%. If the porosity exceeds 15%, the charging efficiency and the discharging efficiency are deteriorated, which is not preferable. On the other hand, when the porosity is less than 5%, it may be difficult to obtain a high volume capacity, or the positive electrode mixture layer may be easily peeled off from the current collector and may be defective. In addition, when using curable resin as binder resin, it is preferable to have the process of hardening this curable resin.
本発明の正極の厚みは、通常5〜400μmであり、好ましくは30〜300μmである。正極の厚みを上記範囲にすることにより、良好な極板の柔軟性、密着性が得られる。 The thickness of the positive electrode of the present invention is usually 5 to 400 μm, preferably 30 to 300 μm. By setting the thickness of the positive electrode within the above range, good flexibility and adhesion of the electrode plate can be obtained.
<非水電解質二次電池>
次に、本発明の非水電解質二次電池について説明する。
本発明の非水電解質二次電池は、上記本発明の正極を用いたものであり、正極、負極、セパレーターおよび電解液を有している。以下、本発明の非水電解質二次電池の構成およびその製造方法について詳細に説明する。<Nonaqueous electrolyte secondary battery>
Next, the nonaqueous electrolyte secondary battery of the present invention will be described.
The nonaqueous electrolyte secondary battery of the present invention uses the positive electrode of the present invention, and has a positive electrode, a negative electrode, a separator, and an electrolytic solution. Hereinafter, the configuration of the nonaqueous electrolyte secondary battery of the present invention and the manufacturing method thereof will be described in detail.
<非水電解質二次電池用負極>
本発明に係る非水電解質二次電池用負極は、負極活物質、導電助剤、水分散性高分子バインダー樹脂、溶媒およびその他必要に応じて添加剤等を混合して負極合剤スラリーを調整し、集電体に塗布、乾燥、必要に応じて圧延を経ることによって製造することができる。<Negative electrode for non-aqueous electrolyte secondary battery>
The negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is prepared by mixing a negative electrode active material, a conductive additive, a water-dispersible polymer binder resin, a solvent, and other additives as necessary to prepare a negative electrode mixture slurry. And it can manufacture by apply | coating to a collector, drying, and passing through rolling as needed.
負極活物質としては、リチウムイオンを吸蔵、放出が可能な活物質であれば、従来より使用されてきた既知の材質を用いることができ、炭素系活物質と非炭素系活物質のいずれを用いてもよい。炭素系活物質としては、例えば、グラファイト、ソフトカーボン、ハードカーボン等を挙げることができる。非炭素系活物質としては、例えば、リチウム金属、リチウム合金、酸化物、硫化物、リチウム含有金属複合酸化物等公知のものを用いることができる。 As the negative electrode active material, any known material that has been conventionally used can be used as long as it is an active material that can occlude and release lithium ions. Either a carbon-based active material or a non-carbon-based active material can be used. May be. Examples of the carbon-based active material include graphite, soft carbon, and hard carbon. As the non-carbon-based active material, for example, known materials such as lithium metal, lithium alloy, oxide, sulfide, lithium-containing metal composite oxide can be used.
導電助剤および溶媒としては、本発明の正極の作製に用いる上記の導電助剤および上記溶媒を用いることができる。また、バインダー樹脂としては、SBR粒子やPVDF樹脂等の非水電解質二次電池に一般的に用いられるものを用いることができる。 As a conductive support agent and a solvent, said conductive support agent and said solvent used for preparation of the positive electrode of this invention can be used. Moreover, as binder resin, what is generally used for nonaqueous electrolyte secondary batteries, such as SBR particle | grains and PVDF resin, can be used.
本発明に係る非水電解質二次電池用負極に用いる集電体としては、本発明の非水電解質二次電池用正極と同様、電気導電性を有し、かつ電気化学的に耐久性のある材料であれば特に制限はなく、上記本発明の非水電解質二次電池用正極に用いられる集電体と同様のものを用いることができる。 The current collector used in the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is electrically conductive and electrochemically durable, like the positive electrode for a non-aqueous electrolyte secondary battery according to the present invention. If it is material, there will be no restriction | limiting in particular, The thing similar to the electrical power collector used for the positive electrode for nonaqueous electrolyte secondary batteries of the said invention can be used.
<電解液>
本発明に用いられる電解液については特に制限はないが、例えば、非水系の溶媒に支持電解質としてリチウム塩を溶解したものが使用できる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLi等を挙げることができる。特に、溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liを好適に用いることができる。これらは1種単独で用いてもよく、2種以上を混合して用いてもよい。支持電解質の添加量は、電解液に対して、通常1質量%以上、好ましくは5質量%以上、また通常は30質量%以下、好ましくは20質量%以下である。支持電解質の量が少なすぎても多すぎてもイオン導電性は低下してしまい、電池の充電特性、放電特性が低下してしまう。<Electrolyte>
Although there is no restriction | limiting in particular about the electrolyte solution used for this invention, For example, what melt | dissolved lithium salt as a supporting electrolyte in a non-aqueous solvent can be used. Examples of the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like. In particular, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation can be suitably used. These may be used alone or in combination of two or more. The addition amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity decreases, and the charging characteristics and discharging characteristics of the battery decrease.
電解液に使用する溶媒としては、支持電解質を溶解させるものであれば特に制限はないが、ジメチルカーボネート(DMC)、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)、およびメチルエチルカーボネート(MEC)等のアルキルカーボネート類;γ−ブチロラクトン、ギ酸メチル等のエステル類、1,2−ジメトキシエタン、およびテトラヒドロフラン等のエーテル類;スルホラン、およびジメチルスルホキシド等の含硫黄化合物類;を用いることができる。特に、高いイオン伝導性が得やすく、使用温度範囲が広いため、ジメチルカーボネート、エチレンカーボネート、プロピレンカーボネート、ジエチルカーボネート、メチルエチルカーボネートが好ましい。これらは1種単独で用いてもよく、2種以上を混合して用いてもよい。 The solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, but dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate. (BC) and alkyl carbonates such as methyl ethyl carbonate (MEC); esters such as γ-butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; and tetrahydrofuran; including sulfolane and dimethyl sulfoxide. Sulfur compounds can be used. In particular, dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These may be used alone or in combination of two or more.
なお、電解液にはその他添加剤を添加してもよい。添加剤としてはビニレンカーボネート(VC)等のカーボネート系の化合物や、シクロヘキシルベンゼンまたはジフェニルエーテル等を挙げることができる。 Other additives may be added to the electrolytic solution. Examples of the additive include carbonate compounds such as vinylene carbonate (VC), cyclohexylbenzene, diphenyl ether, and the like.
本発明の非水電解質二次電池に上記以外の電解液を用いる場合は、例えば、ポリエチレンオキシド、ポリアクリロニトリル等のポリマー電解質に電解液を含浸したゲル状ポリマー電解質や、硫化リチウム、LiI、Li3N等の無機固体電解質を用いることができる。When an electrolyte other than the above is used for the nonaqueous electrolyte secondary battery of the present invention, for example, a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide or polyacrylonitrile with an electrolyte, lithium sulfide, LiI, Li 3 An inorganic solid electrolyte such as N can be used.
<セパレーター>
セパレーターは気孔部を有する多孔性基材であって、(a)気孔部を有する多孔性セパレーター、(b)片面または両面上に高分子コート層が形成された多孔性セパレーター、または(c)無機セラミック粉末を含む多孔質の樹脂コート層が形成された多孔性セパレーターを用いることができる、例えば、ポリプロピレン系、ポリエチレン系、ポリオレフィン系、アラミド系多孔性セパレーター、ポリビニリデンフルオリド、ポリエチレンオキシド、ポリアクリロニトリル、ポリビニリデンフルオリドヘキサフルオロプロピレン共重合体等の固体高分子電解質用、ゲル状高分子電解質用の高分子フィルム、ゲル化高分子コート層がコーティングされたセパレーター、または無機フィラー、無機フィラー用分散剤からなる多孔膜層がコーティングされたセパレーター等を挙げることができる。<Separator>
The separator is a porous substrate having pores, (a) a porous separator having pores, (b) a porous separator having a polymer coating layer formed on one or both sides, or (c) inorganic A porous separator formed with a porous resin coating layer containing ceramic powder can be used, for example, polypropylene, polyethylene, polyolefin, aramid porous separator, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile , For solid polymer electrolyte such as polyvinylidene fluoride hexafluoropropylene copolymer, polymer film for gel polymer electrolyte, separator coated with gelled polymer coat layer, inorganic filler, dispersion for inorganic filler A porous membrane layer made of an agent It has been a separator, and the like can be given.
<非水電解質二次電池の製造方法>
本発明の非水電解質二次電池の製造方法については、特に制限はない。例えば、負極と正極とをセパレーターを介して重ね合わせ、これを電池形状に応じて巻く、折る等して電池容器に入れ、電池容器に電解液を注入して封口する。本発明の非水電解質二次電池においては、必要に応じてエキスパンドメタルや、ヒューズ、PTC素子等の過電流防止素子、リード板等を入れ、電池内部の圧力上昇、過充放電の防止をすることもできる。電池の形状は、ラミネートセル型、コイン型、ボタン型、シート型、円筒型、角形、扁平型等いずれの形状であってもよい。<Method for producing non-aqueous electrolyte secondary battery>
There is no restriction | limiting in particular about the manufacturing method of the nonaqueous electrolyte secondary battery of this invention. For example, the negative electrode and the positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery and placed in the battery container, and the electrolytic solution is injected into the battery container and sealed. In the non-aqueous electrolyte secondary battery of the present invention, an expanded metal, an overcurrent prevention element such as a fuse and a PTC element, a lead plate, etc. are inserted as necessary to prevent an increase in pressure inside the battery and overcharge / discharge. You can also. The shape of the battery may be any shape such as a laminate cell type, a coin type, a button type, a sheet type, a cylindrical type, a square shape, and a flat type.
以下、実施例を用いて本発明をより詳細に説明する。
<実施例1>
正極活物質として、三元系活物質である日本化学工業社製セルシードNMC−111(LiNi1/3Co1/3Mn1/3O2)を固形分比率95質量%、導電助剤として昭和電工社製VGCF−H(気相成長炭素繊維)を固形分比率2質量%、水分散性高分子バインダー樹脂としてADEKA社製アデカボンタイターHUX−822(ポリウレタンエマルション樹脂:固形分40質量%)を固形分比率1.5質量%、界面活性剤として花王社製エマノーン3299RV(ポリエチレングリコールジステアレート)を固形分比率1.5質量%、および溶媒としての水を合剤固形分が60質量%となるように配合し、1700rpmで10分間プロペラ攪拌を行い、正極合剤を作製した。Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
Cell seed NMC-111 (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) manufactured by Nippon Kagaku Kogyo Co., Ltd., which is a ternary active material, is used as the positive electrode active material. Adekabon titer HUX-822 (polyurethane emulsion resin: solid content 40% by mass) manufactured by ADEKA as a water-dispersible polymer binder resin with a solid content ratio of 2% by mass of VGCF-H (vapor-grown carbon fiber) manufactured by Denko Co., Ltd. Solid content ratio 1.5% by mass, Kao Co., Ltd. Emanon 3299RV (polyethylene glycol distearate) as a solid content ratio 1.5% by mass, and water as a solvent is 60% by mass It mix | blended so that it might become, and propeller stirring was performed for 10 minutes at 1700 rpm, and the positive mix was produced.
作製した正極合剤を24時間静置し、その後、厚さ20μmのアルミニウム箔の片面に50μmのアプリケーターを用いて塗布した。その後、熱風循環式箱型乾燥炉にて150℃で20分間乾燥し、溶媒である水を除去した。室温まで冷却した後、1mmのステンレス製の板に挟み、平板プレス機を用いて1.5ton/cm2の圧力で常温にて1分間の圧延を行い、片面80μmの活物質合剤層を持つ、正極電極板を作製した。正極合剤の作製から正極電極板の作製までの工程につき、分散性、沈降凝集安定性、乾燥後の外観、乾燥後の密着性、電極層の外観、電極層の密着性および電極層の抵抗値について評価を行った。評価方法の詳細は以下のとおりである。得られた結果を表1に併記する。The produced positive electrode mixture was allowed to stand for 24 hours, and then applied to one side of an aluminum foil having a thickness of 20 μm using a 50 μm applicator. Then, it dried for 20 minutes at 150 degreeC with the hot-air circulation type box-type drying furnace, and removed the water which is a solvent. After cooling to room temperature, it is sandwiched between 1 mm stainless steel plates and rolled at room temperature for 1 minute at a pressure of 1.5 ton / cm 2 using a flat plate press to have an active material mixture layer of 80 μm on one side. A positive electrode plate was prepared. Dispersibility, stability of sedimentation, stability after drying, adhesion after drying, adhesion after drying, electrode layer appearance, electrode layer adhesion, and electrode layer resistance, from the preparation of the positive electrode mixture to the preparation of the positive electrode plate The value was evaluated. Details of the evaluation method are as follows. The obtained results are also shown in Table 1.
<実施例2〜10、参考例1〜3、比較例1、2>
水分散性高分子バインダー樹脂、界面活性剤、増粘剤、導電助剤、正極活物質を表1〜4に示すように配合組成を変えた以外は、実施例1と同様にして攪拌・混合を行い、正極合剤を作製し、分散性、沈降凝集の安定性を評価した。作製した正極合剤を用いて、実施例1と同様に塗布・乾燥・圧延を行い、正極板を作製した。評価結果を表1〜4に併記する。
<Examples 2 to 10, Reference Examples 1 to 3, Comparative Examples 1 and 2>
Stirring and mixing in the same manner as in Example 1 except that the composition of the water-dispersible polymer binder resin, surfactant, thickener, conductive additive, and positive electrode active material was changed as shown in Tables 1 to 4. The positive electrode mixture was prepared, and the dispersibility and the stability of sedimentation aggregation were evaluated. Using the produced positive electrode mixture, application, drying and rolling were performed in the same manner as in Example 1 to produce a positive electrode plate. The evaluation results are shown in Tables 1-4.
<分散性>
作製した正極合剤をアルミニウム箔の正極集電体に塗工するに際して、分散不良で解れていない粗い活物質粒子の塊やゲル状の樹脂の塊で塗工面にスジ状の跡が付くものを「不良」、若干跡が付くものを「可」、スジ状の跡が付かないものを「良」として、目視評価を行った。<Dispersibility>
When the prepared positive electrode mixture is applied to the positive electrode current collector of aluminum foil, a coarse active material particle lump or gel-like resin lump that has not been solved due to poor dispersion and has a streak-like mark on the coated surface. Visual evaluation was performed with “bad”, “good” for those with slight traces, and “good” for those with no streak-like traces.
<沈降凝集安定性>
作製した正極合剤を静置し、正極合剤の底面に沈降凝集物が発生した場合や液面に水が分離してしまったものを「不良」、変化していないものを「良」として、評価を行った。<Sedimentation aggregation stability>
If the produced positive electrode mixture is allowed to stand and sedimentation agglomerates occur on the bottom surface of the positive electrode mixture or water has separated on the liquid surface, it is regarded as “bad” and the one that has not changed is regarded as “good”. And evaluated.
<乾燥後の外観>
正極合剤を正極集電体に塗布・乾燥した後、塗膜表面に泡、はじき等の塗膜欠陥が発生したものを「不良」、異常のないものを「良」として、塗膜の目視評価を行った。<Appearance after drying>
After coating and drying the positive electrode mixture on the positive electrode current collector, the coating film surface with bubbles and repellency such as bubbles and repellency was defined as “bad”, and those with no abnormalities as “good”. Evaluation was performed.
<乾燥後の密着性>
正極合剤を正極集電体に塗布・乾燥した後、塗膜表面をJIS K−5600に準じ、カット間隔2mmで格子パターン25マスのクロスカットを行い、交点の粉落ちが激しいものを「不良」、粉落ちが少ないものを「可」、粉落ちが全くないものを「良」として、評価を行った。<Adhesion after drying>
After coating and drying the positive electrode mixture on the positive electrode current collector, the coating film surface was cross-cut with a grid pattern of 25 squares with a cut interval of 2 mm according to JIS K-5600. The evaluation was made with “low” for those with little powder falling and “good” for those with no powder falling.
<電極層の外観>
作製した電極板表面に突起や割れ等が発生しているものを「不良」、異常がなく平滑であるものを「良」として、電極表面の目視評価を行った。<Appearance of electrode layer>
Visual evaluation of the surface of the electrode was performed by assuming that the surface of the produced electrode plate had protrusions or cracks as “defective” and that there was no abnormality and was “good”.
<電極層の密着性>
作製した電極板を用い、JIS K−5600に準じ、カット間隔2mmで格子パターン25マスのクロスカット法試験により、集電体と活物質間の密着性を評価した。評価は0〜5の6段階により行い、数字が少ないものほど密着性が良好であることを示す。<Adhesion of electrode layer>
Using the produced electrode plate, according to JIS K-5600, the adhesion between the current collector and the active material was evaluated by a cross-cut method test with a grid pattern of 25 squares at a cut interval of 2 mm. Evaluation is performed in 6 stages from 0 to 5, and the smaller the number, the better the adhesion.
<電極層の抵抗値>
作製した電極板表面にテスタ(日置社製 ミリオームハイテスタ3540)を用いて表面の抵抗値を測定した。
<Resistance value of electrode layer>
The resistance value of the surface was measured using a tester (Mirium High Tester 3540, manufactured by Hioki Co., Ltd.) on the surface of the produced electrode plate.
1)アデカボンタイターHUX−822(ポリウレタン樹脂 分子量:800,000〜900,000) (株)ADEKA社製
2)HSV−900(ポリフッ化ビニリデン樹脂) アルケマ(株)社製
3)モビニールLDM7523(アクリル/シリコーン樹脂) 日本合成化学(株)社製
4)エマノーン3299RV(ポリエチレングリコールジステアレート系非イオン界面活性剤 HLB:19.2 分子量:約11200) 花王(株)社製
5)エマノーン3199V(ポリエチレングリコールモノステアレート系非イオン界面活性剤 HLB:19.4 分子量:約6800) 花王(株)社製
6)エマノーン1112(ポリエチレングリコールモノラウレート系非イオン界面活性剤 HLB:13.7 分子量:約730) 花王(株)社製
7)アデカミン4MAC−30(カチオン性界面活性剤) (株)ADEKA社製
8)ダイセルCMC#2200 ダイセルファインケム(株)社製
9)VGCF−H(気相成長炭素繊維) 昭和電工(株)社製
10)SP−270(黒鉛粉末) 日本黒鉛工業(株)社製
11)セルシードNMC111(LiNi1/3Co1/3Mn1/3O2) 日本化学工業(株)社製
12)LFP(リン酸鉄リチウム:LiFePO4)
13)NMP(N−メチルピロリドン)1) Adekabon titer HUX-822 (polyurethane resin, molecular weight: 800,000 to 900,000) (manufactured by ADEKA) 2) HSV-900 (polyvinylidene fluoride resin) (manufactured by Arkema) 3) Movinyl LDM7523 (acrylic) / Silicone resin) Nippon Synthetic Chemical Co., Ltd. 4) Emanon 3299RV (polyethylene glycol distearate nonionic surfactant HLB: 19.2 Molecular weight: about 11200) Kao Corporation 5) Emanon 3199V (polyethylene) Glycol monostearate nonionic surfactant HLB: 19.4 molecular weight: about 6800) Kao Corp. 6) Emanon 1112 (polyethylene glycol monolaurate nonionic surfactant HLB: 13.7 molecular weight: about 730) Made by Kao Corporation 7) Adecamine 4MAC-30 (cationic surfactant) manufactured by ADEKA Corporation 8) Daicel CMC # 2200 manufactured by Daicel FineChem Corporation 9) VGCF-H (vapor-grown carbon fiber) Showa Denko K.K. 10) SP-270 (graphite powder) 11) Cellseed NMC111 (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) 12) LFP (manufactured by Nippon Chemical Industry Co., Ltd.) Lithium iron phosphate: LiFePO 4 )
13) NMP (N-methylpyrrolidone)
表1〜4より、本発明の正極合剤は、正極活物質の分散性、保存安定性および集電体に対する塗工性に優れており、これを用いて製造された正極は正極合剤層と集電体と密着性に優れていることがわかる。比較例は、スラリーの状態では良好に分散しているように見えたが、荒い粒子状の塊等が残っており、分散性が悪く、塗膜形成が困難であった。 From Tables 1-4, the positive electrode mixture of this invention is excellent in the dispersibility of a positive electrode active material, storage stability, and the coating property with respect to an electrical power collector, and the positive electrode manufactured using this is a positive electrode mixture layer. It can be seen that it has excellent adhesion to the current collector. The comparative example seemed to be well dispersed in the slurry state, but rough particulate lumps and the like remained, the dispersibility was poor, and coating film formation was difficult.
Claims (5)
前記界面活性剤がポリエチレングリコールのステアリン酸エステル類であることを特徴とする正極合剤。 A positive electrode active material, a water-dispersible polymer binder resin, a conductive additive, a surfactant, and an aqueous solvent ,
A positive electrode mixture, wherein the surfactant is a stearic acid ester of polyethylene glycol .
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JP4406832B2 (en) * | 2004-03-24 | 2010-02-03 | 株式会社デンソー | Lithium secondary battery electrode and lithium secondary battery |
JP4779327B2 (en) * | 2004-09-14 | 2011-09-28 | 株式会社デンソー | ELECTRODE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY USING THE ELECTRODE |
JP4876515B2 (en) * | 2005-09-30 | 2012-02-15 | 株式会社デンソー | ELECTRODE FOR LITHIUM SECONDARY BATTERY, ITS MANUFACTURING METHOD, AND LITHIUM SECONDARY BATTERY |
JP2008021415A (en) * | 2006-07-10 | 2008-01-31 | Nissan Motor Co Ltd | Electrode for non-aqueous electrolyte secondary battery |
JP2012195129A (en) * | 2011-03-16 | 2012-10-11 | Panasonic Corp | Coin-shaped battery and method for manufacturing the same |
-
2012
- 2012-11-30 JP JP2013551551A patent/JP6055782B2/en active Active
- 2012-11-30 WO PCT/JP2012/081151 patent/WO2013099520A1/en active Application Filing
- 2012-11-30 CN CN201280064831.4A patent/CN104025350A/en active Pending
- 2012-11-30 KR KR1020147020659A patent/KR20140116143A/en not_active Application Discontinuation
- 2012-12-20 TW TW101148776A patent/TW201342698A/en unknown
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JPWO2013099520A1 (en) | 2015-04-30 |
KR20140116143A (en) | 2014-10-01 |
WO2013099520A1 (en) | 2013-07-04 |
CN104025350A (en) | 2014-09-03 |
TW201342698A (en) | 2013-10-16 |
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