JP2012094361A - Electrode plate for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery and battery pack - Google Patents
Electrode plate for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery and battery pack Download PDFInfo
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- JP2012094361A JP2012094361A JP2010240236A JP2010240236A JP2012094361A JP 2012094361 A JP2012094361 A JP 2012094361A JP 2010240236 A JP2010240236 A JP 2010240236A JP 2010240236 A JP2010240236 A JP 2010240236A JP 2012094361 A JP2012094361 A JP 2012094361A
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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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
Abstract
Description
本発明は、非水電解液二次電池に用いられる電極板、非水電解液二次電池および電池パックに関するものである。 The present invention relates to an electrode plate, a non-aqueous electrolyte secondary battery, and a battery pack used for a non-aqueous electrolyte secondary battery.
リチウムイオン二次電池に代表される非水電解液二次電池は、高エネルギー密度、高電圧を有し、また充放電時におけるメモリ効果（完全に放電させる前に電池の充電を行なうと次第に電池容量が減少していく現象）が無いことから、携帯機器、及び大型機器など様々な分野で用いられている。 A non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery has a high energy density and a high voltage, and has a memory effect during charging / discharging (when the battery is charged before it is completely discharged, Since there is no phenomenon in which the capacity decreases, it is used in various fields such as portable devices and large devices.
また、現在、世界規模でＣＯ２排出抑制の取り組みが行われており、石油依存度を低減し、低環境負荷で走行可能とすることで、ＣＯ２削減に大いに寄与することができるプラグインハイブリッド自動車、電気自動車に代表される次世代クリーンエネルギー自動車の開発・普及が急務とされている。これらの次世代クリーンエネルギー自動車の開発・普及には、ガソリンに依存しない駆動力が必須である。上記駆動力としてリチウムイオン二次電池に代表される非水電解液二次電池が期待されている。 At present, efforts are being made to reduce CO 2 emissions on a global scale. Plug-in hybrids that can greatly contribute to CO 2 reduction by reducing the dependence on oil and enabling driving with low environmental impact. There is an urgent need to develop and spread next-generation clean energy vehicles such as automobiles and electric cars. Driving power that does not depend on gasoline is essential for the development and popularization of these next-generation clean energy vehicles. Non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries are expected as the driving force.
上記非水電解液二次電池は、正極板、負極板、セパレータ、及び有機電解液から構成される。そして上記正極板及び負極板としては、金属箔などの集電体表面に、電極活物質層形成液を塗布して形成された電極活物質層を備えるものが一般に用いられている。 The non-aqueous electrolyte secondary battery includes a positive electrode plate, a negative electrode plate, a separator, and an organic electrolyte. And as said positive electrode plate and negative electrode plate, what equips the collector surface, such as metal foil, with the electrode active material layer formed by apply | coating an electrode active material layer forming liquid is generally used.
上記電極活物質層形成液は、リチウムイオン挿入脱離反応を示すことにより充放電可能な活物質粒子、樹脂製結着材、及び導電材（但し活物質が導電効果も発揮する場合などには、導電材は省略される場合がある）、あるいはさらに、必要に応じてその他の材料を用い、有機溶媒中で攪拌及び／又は分散させて、スラリー状の電極活物質層形成液に調製される。そして電極活物質層形成液を集電体表面に塗布し、次いで乾燥して集電体上に塗膜を形成し、必要に応じてプレスすることにより電極活物質層を備える電極板を製造する方法が一般的である（例えば特許文献１段落［００１９］乃至［００２６］、特許文献２［請求項１］、段落［００５１］乃至［００５５］）。 The electrode active material layer forming liquid is composed of active material particles that can be charged / discharged by exhibiting lithium ion insertion / release reaction, resin binder, and conductive material (however, when the active material also exhibits a conductive effect) In some cases, the conductive material may be omitted), or, if necessary, other materials may be used and stirred and / or dispersed in an organic solvent to prepare a slurry-like electrode active material layer forming liquid. . Then, the electrode active material layer forming liquid is applied to the current collector surface, then dried to form a coating film on the current collector, and if necessary, an electrode plate having the electrode active material layer is manufactured by pressing. The method is general (for example, paragraphs [0019] to [0026] in Patent Document 1, paragraph 1 [Claim 1], paragraphs [0051] to [0055]).
このとき、電極活物質層形成液に含有される活物質粒子は、該形成液中に分散される粒子状の化合物であって、集電体表面に塗布されただけでは該集電体表面に固着され難い材料である。したがって樹脂製結着材を含まない電極活物質層形成液を集電体に塗布して乾燥して塗膜を形成しても、該塗膜は集電体から容易に剥離してしまう。そのため、従来の電極板における電極活物質層は、樹脂製結着材を介して、活物質粒子を集電体上に固着させて、形成されることが一般的であり、該樹脂製結着材は実質的には、必須の構成物質であった。例えば、特許文献３に記載の発明においても、大粒径活物質と小粒径活物質とを用いて電極活物質層を構成する発明が開示されているが、その実施例をみるといずれも樹脂製結着材（ポリフッ化ビニリデン）が使用されており、活物質粒子の大小あるいはその組み合わせにかかわらず、樹脂製結着材を使用することが必要であることが理解される。 At this time, the active material particles contained in the electrode active material layer forming liquid are particulate compounds dispersed in the forming liquid, and are simply applied to the current collector surface. It is a material that is not easily fixed. Accordingly, even when an electrode active material layer forming liquid not containing a resin binder is applied to a current collector and dried to form a coating film, the coating film is easily peeled off from the current collector. Therefore, an electrode active material layer in a conventional electrode plate is generally formed by fixing active material particles on a current collector through a resin binder, and the resin binder The material was essentially an essential constituent. For example, the invention described in Patent Document 3 also discloses an invention in which an electrode active material layer is configured by using a large particle size active material and a small particle size active material. It is understood that a resin binder (polyvinylidene fluoride) is used, and it is necessary to use a resin binder regardless of the size of the active material particles or a combination thereof.
上述するとおり、非水電解液二次電池は、次世代クリーンエネルギーの駆動力としての利用が期待されている。しかしながら、自動車やパワーツールなどに対してはもちろんのこと、携帯電話等の比較的小型の装置に用いられる場合であっても、装置が多機能化される傾向にあるために、出入力特性、初期充放電効率において、まだまだ改良が求められている。 As described above, the nonaqueous electrolyte secondary battery is expected to be used as a driving force for next-generation clean energy. However, not only for automobiles and power tools, but also when used in relatively small devices such as mobile phones, the devices tend to be multifunctional, There is still a need for improvement in the initial charge / discharge efficiency.
尚、本発明者らは、非水電解液二次電池用電極板の出入力特性を向上させるために鋭意検討し、電極活物質層中における樹脂製結着材の存在に着目した。上述のとおり、これまで樹脂製結着材は、実質的に電極活物質層を形成するための必須の構成成分として用いられていた。しかし、活物質粒子間、および集電体と活物質粒子間に樹脂性結着材が存在することにより、電極板の電気抵抗が高くなり、リチウムイオン及び電子の移動の妨げとなっていることが推察された。 The inventors of the present invention have made extensive studies in order to improve the input / output characteristics of the electrode plate for a non-aqueous electrolyte secondary battery, and have focused on the presence of a resin binder in the electrode active material layer. As described above, the resin binder has been used as an essential component for substantially forming the electrode active material layer. However, the presence of the resinous binder between the active material particles and between the current collector and the active material particles increases the electrical resistance of the electrode plate and hinders the movement of lithium ions and electrons. Was inferred.
本発明は上記の実状に鑑みて成し遂げられた。即ち、本発明は、出入力特性の優れた非水電解液二次電池用電極板を提供し、また、上記電極板を用いた非水電解液二次電池および電池パックの提供を実現することを目的とする。 The present invention has been accomplished in view of the above circumstances. That is, the present invention provides an electrode plate for a non-aqueous electrolyte secondary battery having excellent input / output characteristics, and also provides a non-aqueous electrolyte secondary battery and a battery pack using the electrode plate. With the goal.
本発明者らは、活物質粒子を、結着物質粒子である金属酸化物粒子の存在によって集電体表面に固着させて電極活物質層を構成可能であり、出入力特性を向上できることを見出した。また、該金属酸化物粒子の平均粒径が、上記活物質粒子の平均粒径より小さいものとすることにより、初期充放電効率を向上させることができることを見出し、本発明を完成させた。 The present inventors have found that the active material particles can be fixed to the surface of the current collector by the presence of the metal oxide particles as the binding material particles to form the electrode active material layer, and the input / output characteristics can be improved. It was. Further, the inventors have found that the initial charge / discharge efficiency can be improved by setting the average particle size of the metal oxide particles to be smaller than the average particle size of the active material particles, thereby completing the present invention.
すなわち、本発明は、
（１）集電体と、上記集電体の表面の少なくとも一部に形成される電極活物質層とを備える非水電解液二次電池用電極板であって、上記電極活物質層が、活物質粒子および結着物質粒子を含有しており、上記結着物質粒子が、リチウムイオン挿入脱離反応を示さない金属酸化物粒子であり、上記結着物質粒子の平均粒径が、上記活物質粒子の平均粒径より小さいことを特徴とする非水電解液二次電池用電極板、
（２）上記金属酸化物が、結晶性であることを特徴とする上記（１）に記載の非水電解液二次電池用電極板、
（３）上記電極活物質層は、隣り合う結着物質粒子同士が、少なくとも一部において連続することにより繋がっている箇所を含むことを特徴とする上記（２）に記載の非水電解液二次電池用電極板、
（４）上記結着物質は、更に炭素成分を含有していることを特徴とする上記（１）から（３）のいずれか１つに記載の非水電解液二次電池用電極板、
（５）上記活物質粒子の平均粒径が、上記結着物質粒子の平均粒径の３倍以上であることを特徴とする上記（１）から（４）のいずれか１つに記載の非水電解液二次電池用電極板、
（６）上記電極活物質層は、結着物質粒子により、活物質粒子同士が互いに固着されるとともに、結着物質粒子により、活物質粒子が上記集電体に固着されて構成されていることを特徴とする上記（１）から（５）のいずれか１つに記載の非水電解液二次電池用電極板、
（７）複数の結着物質粒子が、活物質粒子の表面の少なくとも一部を覆っていることを特徴とする上記（１）から（６）のいずれか１つに記載の非水電解液二次電池用電極板、
（８）正極板と、負極板と、上記正極板と上記負極板との間に設けられるセパレータと、非水溶媒を含む電解液とを少なくとも備えた非水電解液二次電池であって、
上記正極板または負極板のいずれか一方、あるいは両方が、上記（１）から（７）のいずれか１つに記載の非水電解液二次電池用電極板であることを特徴とする非水電解液二次電池、
（９）収納ケースと、正極端子および負極端子を備える非水電解液二次電池と、過充電および過放電保護機能を有する保護回路とを少なくとも備え、上記収納ケースに上記非水電解液二次電池および上記保護回路が収納されて構成される電池パックにおいて、
上記非水電解液二次電池が、正極板と、負極板と、上記正極板と上記負極板との間に設けられるセパレータと、非水溶媒を含む電解液とを少なくとも備えた非水電解液二次電池であり、
上記正極板または負極板のいずれか一方、あるいは両方が、上記（１）から（７）のいずれか１つに記載の非水電解液二次電池用電極板であることを特徴とする電池パック、
を要旨とするものである。
That is, the present invention
(1) A non-aqueous electrolyte secondary battery electrode plate comprising a current collector and an electrode active material layer formed on at least a part of the surface of the current collector, wherein the electrode active material layer comprises: Active material particles and binder material particles, wherein the binder material particles are metal oxide particles that do not exhibit lithium ion insertion / release reaction, and the average particle size of the binder material particles is An electrode plate for a non-aqueous electrolyte secondary battery, wherein the electrode plate is smaller than the average particle size of the substance particles,
(2) The electrode plate for a non-aqueous electrolyte secondary battery according to (1), wherein the metal oxide is crystalline,
(3) The non-aqueous electrolyte 2 according to (2), wherein the electrode active material layer includes a portion where adjacent binder material particles are connected by being continuous at least in part. Secondary battery electrode plate,
(4) The electrode plate for a non-aqueous electrolyte secondary battery according to any one of (1) to (3), wherein the binder material further contains a carbon component,
(5) The non-active material according to any one of (1) to (4), wherein the average particle diameter of the active material particles is three times or more than the average particle diameter of the binder material particles. Electrode plate for water electrolyte secondary battery,
(6) The electrode active material layer is configured such that the active material particles are fixed to each other by the binding material particles, and the active material particles are fixed to the current collector by the binding material particles. The electrode plate for a non-aqueous electrolyte secondary battery according to any one of (1) to (5) above,
(7) The non-aqueous electrolyte 2 according to any one of (1) to (6), wherein the plurality of binder particles cover at least a part of the surface of the active material particles. Secondary battery electrode plate,
(8) A non-aqueous electrolyte secondary battery comprising at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte containing a non-aqueous solvent,
Either the positive electrode plate or the negative electrode plate, or both are the electrode plates for a nonaqueous electrolyte secondary battery according to any one of (1) to (7) above. Electrolyte secondary battery,
(9) A storage case, a non-aqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal, and a protection circuit having an overcharge and over-discharge protection function are provided, and the non-aqueous electrolyte secondary battery is provided in the storage case. In the battery pack configured to house the battery and the protection circuit,
The non-aqueous electrolyte secondary battery includes at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a non-aqueous solvent. A secondary battery,
Either one of the positive electrode plate or the negative electrode plate, or both are the electrode plates for a nonaqueous electrolyte secondary battery according to any one of (1) to (7). ,
Is a summary.
本発明は、活物質粒子を金属酸化物の結着物質粒子により集電体表面に固着することで、出入力特性の向上が可能であり、結着物質粒子である金属酸化物粒子の平均粒径が活物質粒子の平均粒径よりも小さいものであるため、電極活物質層中における活物質粒子の充填効率が上がり、初期充放電効率に優れた非水電解液二次電池用電極板の提供を可能とした。 The present invention can improve the input / output characteristics by fixing the active material particles to the current collector surface with the metal oxide binder material particles, and the average particle size of the metal oxide particles as the binder material particles. Since the diameter is smaller than the average particle diameter of the active material particles, the filling efficiency of the active material particles in the electrode active material layer is increased, and the electrode plate for a non-aqueous electrolyte secondary battery having excellent initial charge / discharge efficiency is obtained. It was possible to provide.
また、本発明の電極板を、正極板および／または負極板として使用する、本発明の非水電解液二次電池および本発明の電池パックは、本発明の電極板の出入力特性の向上にともない、非水電解液二次電池自体の出入力性能、および電池パック自体の出入力性能を向上させることが可能である。 In addition, the nonaqueous electrolyte secondary battery of the present invention and the battery pack of the present invention using the electrode plate of the present invention as a positive electrode plate and / or a negative electrode plate can improve the input / output characteristics of the electrode plate of the present invention. Accordingly, it is possible to improve the input / output performance of the nonaqueous electrolyte secondary battery itself and the input / output performance of the battery pack itself.
以下に、本発明の非水電解液二次電池用電極板（以下、単に「電極板」という場合がある）、非水電解液二次電池用電極板の製造方法、および非水電解液二次電池を実施するための形態について、順に説明する。 Hereinafter, an electrode plate for a non-aqueous electrolyte secondary battery of the present invention (hereinafter sometimes simply referred to as “electrode plate”), a method for producing an electrode plate for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte solution 2 The form for implementing a secondary battery is demonstrated in order.
[非水電解液二次電池用電極板]
本発明の非水電解液二次電池用電極板は、図１に本発明の一実施態様である非水電解液二次電池用電極板１０として示すとおり、集電体１と、上記集電体１の表面の少なくとも一部に形成される電極活物質層２とを備える。電極活物質層２は、活物質粒子２１および結着物質粒子２２が含まれている。活物質粒子２１同士は、結着物質粒子２２により固着されており、また活物質粒子２１は、結着物質粒子２２により集電体１表面に固着されている。特に本発明は、結着物質粒子２２の平均粒径が、活物質粒子２１の平均粒径より小さいことを特徴とする。そして本発明における電極活物質層は、従来の電極板のように樹脂製結着材のみを使用して活物質粒子を集電体上に固着させるのではなく、リチウムイオン挿入脱離反応を示さない金属酸化物粒子によって活物質粒子が集電体上に固着されてなるものである。また、本発明の電極板の多くの実施形態では、電極活物質層は、結着物質粒子の存在により直接に集電体上に積層されているため、電極活物質層と集電体との間における電子の移動が非常にスムーズである。
[Electrode plate for non-aqueous electrolyte secondary battery]
The electrode plate for a non-aqueous electrolyte secondary battery of the present invention includes a current collector 1 and the current collector as shown in FIG. 1 as an electrode plate 10 for a non-aqueous electrolyte secondary battery which is an embodiment of the present invention. And an electrode active material layer 2 formed on at least a part of the surface of the body 1. The electrode active material layer 2 includes active material particles 21 and binder material particles 22. The active material particles 21 are fixed to each other by the binding material particles 22, and the active material particles 21 are fixed to the surface of the current collector 1 by the binding material particles 22. In particular, the present invention is characterized in that the average particle size of the binder material particles 22 is smaller than the average particle size of the active material particles 21. The electrode active material layer in the present invention exhibits a lithium ion insertion / desorption reaction rather than fixing the active material particles on the current collector using only the resin binder as in the conventional electrode plate. The active material particles are fixed on the current collector with no metal oxide particles. Further, in many embodiments of the electrode plate of the present invention, the electrode active material layer is laminated directly on the current collector due to the presence of the binder material particles, so that the electrode active material layer and the current collector The movement of electrons between them is very smooth.
本発明の電極板は、出入力特性に優れる。かかる高出入力化を可能とした要因の少なくとも１つは、当該電極板における電極活物質層が、結着物質粒子である金属酸化物粒子により活物質粒子が集電体上に固着されて構成されることにあると考えられる。 The electrode plate of the present invention is excellent in input / output characteristics. At least one of the factors enabling such high input / output is that the electrode active material layer in the electrode plate is composed of the active material particles fixed on the current collector by the metal oxide particles as the binder material particles. It is thought that there is to be done.
また、本発明において、上記結着物質粒子である金属酸化物粒子の平均粒径は、上記活物質粒子の平均粒径よりも小さいものであるため、電極活物質層中における活物質粒子の充填効率が上がり、初期充放電効率を向上させることができる。 In the present invention, since the average particle diameter of the metal oxide particles as the binder material particles is smaller than the average particle diameter of the active material particles, the filling of the active material particles in the electrode active material layer Efficiency increases and initial charge / discharge efficiency can be improved.
尚、本発明を説明する場合、あるいは本発明の一態様において、結着物質により固着される、という場合には、以下の２つの態様を含む。即ち、上記固着の態様は、被固着物間（例えば、活物質粒子間、活物質粒子と集電体表面との間、あるいは導電材を使用する場合には、導電材と活物質粒子間、導電材粒子間など）に、結着物質粒子である金属酸化物粒子が介在して両者を固着させる場合（以下、「固着態様１」）と、被固着物同士が直接接触し、接触部分を囲んで結着物質粒子が存在することによって被固着物同士を固着させる場合（以下、「固着態様２」）とを含む。本発明の多くの実施形態では、上述する固着態様１および２のいずれか、あるいは両方が、電極活物質層中に存在する。特に、本発明における結着物質粒子である金属酸化物粒子は、活物質粒子よりも平均粒径が小さいため、電極活物質層中における活物質粒子の充填率を高め、且つ、活物質粒子間に多数の金属酸化物粒子が充填した状態とすることができ、このとき、金属酸化物粒子同士は互いに接着しながら活物質粒子を覆い、集電体上に活物質粒子を固着させることができる。 In the case of explaining the present invention, or in the case of being fixed by a binding substance in one aspect of the present invention, the following two aspects are included. That is, the above-described fixing mode is between the objects to be fixed (for example, between the active material particles, between the active material particles and the current collector surface, or when using a conductive material, between the conductive material and the active material particles, When the metal oxide particles as the binder material particles are interposed between the conductive material particles and the like (hereinafter referred to as “fixing mode 1”), the adherends are in direct contact with each other, And the case where the adherends are fixed together by the presence of the binding substance particles (hereinafter referred to as “fixing mode 2”). In many embodiments of the present invention, either one or both of the fixing modes 1 and 2 described above are present in the electrode active material layer. In particular, since the metal oxide particles that are the binder material particles in the present invention have an average particle size smaller than that of the active material particles, the filling ratio of the active material particles in the electrode active material layer is increased, and In this case, the metal oxide particles can cover the active material particles while adhering to each other, and the active material particles can be fixed on the current collector. .
本発明は、電極活物質層において、上記固着態様１および２のいずれか、あるいは両方を含んで構成される場合には、導電性の向上の点で優れた効果を発揮する。上記効果を理解するために、導電材粒子を含む電極活物質層において、特に導電材粒子間の固着に着目する。導電材粒子同士が、上記固着態様１によって固着されている場合、本発明の結着物質粒子が金属酸化物粒子であるため、従来の樹脂製結着材のみを使用した電極板に比べて、導電材粒子間での電子のやりとりの障害となり難い。またさらに、導電材粒子同士が、上記固着態様２によって導電材粒子同士が固着されている場合には、粒子同士は直接に接しているため、当然に電子の流れがスムーズであり、優れた導電性が確保される。上記効果は、導電材粒子と活物質粒子間との固着に関しても、同様のことが言える。加えて、集電体と電極活物質層との境界においても、集電体面と活物質粒子や導電材粒子とが、結着物質粒子を介して固着されるか、あるいはこれらが直接に接触して接触部分の周囲に結着物質粒子が存在することによって固着される。そのため、上述と同様の理由で、集電体と電極活物質層間の電子の流れがスムーズである。即ち、本発明の電極板は、金属酸化物粒子が結着物質粒子として電極活物質層中に存在し、且つ、固着態様１および／または２によって種々の構成材料を固着させていることにより電気抵抗を低く保つことが可能であり、特に固着態様１および２が混在することが好ましい。 In the case where the electrode active material layer is configured to include either or both of the fixing modes 1 and 2, the present invention exhibits an excellent effect in terms of improving the conductivity. In order to understand the above effect, attention is paid particularly to the adhesion between the conductive material particles in the electrode active material layer containing the conductive material particles. When the conductive material particles are fixed to each other by the fixing mode 1, since the binding material particles of the present invention are metal oxide particles, compared to a conventional electrode plate using only a resin binding material, It is unlikely to be an obstacle to the exchange of electrons between conductive material particles. Furthermore, when the conductive material particles are fixed to each other by the fixing mode 2, the particles are in direct contact with each other, so that the flow of electrons is naturally smooth, and excellent conductive properties are obtained. Sex is secured. The same can be said for the above-mentioned effect regarding the adhesion between the conductive material particles and the active material particles. In addition, at the boundary between the current collector and the electrode active material layer, the current collector surface and the active material particles or the conductive material particles are fixed through the binder material particles, or they are in direct contact with each other. Then, it is fixed by the presence of the binder particles around the contact portion. Therefore, the flow of electrons between the current collector and the electrode active material layer is smooth for the same reason as described above. That is, the electrode plate according to the present invention has the metal oxide particles as binder material particles in the electrode active material layer and has various constituent materials fixed by the fixing modes 1 and / or 2. The resistance can be kept low, and it is particularly preferable that the fixing modes 1 and 2 are mixed.
また、本発明の電極板は、電極活物質層に含有される結着物質粒子である金属酸化物粒子は、非晶質、結晶性、あるいはこれらの両方を含んでいても良いが、結晶性の場合、結着物質粒子の粒子径を小さくすることが容易であり、活物質粒子の平均粒径よりも平均粒径の小さな結着物質粒子を形成しやすく、電極活物質層中の活物質粒子の充填効率を向上できるため好ましい。本発明の電極板は、隣り合う結着物質粒子同士が少なくとも一部において連続することにより繋がっている箇所を含んでいてもよい。上述のとおり、本発明における結着物質粒子は、活物質粒子を集電体上に固着させるものである。このとき、本発明は、結着物質粒子同士の少なくとも一部において互いに結着物質粒子が連続していることにより、電極活物質層の膜密着性が向上することが推察された。この膜密着性の向上が、電極板の出入力特性の向上に有効に寄与すると思われる。電極活物質層の膜密着性を向上させるという観点からは、隣り合う結着物質粒子同士が連続する部分は、電極活物質層に有意に存在することがより望ましい。尚、本発明において結着物質粒子同士が連続するか否は、透過型電子顕微鏡で電極活物質層における隣り合う結着物質の断面を観察することによって確認することができる。 Further, in the electrode plate of the present invention, the metal oxide particles, which are binder material particles contained in the electrode active material layer, may contain amorphous, crystalline, or both. In this case, it is easy to reduce the particle size of the binder material particles, and it is easy to form binder material particles having an average particle size smaller than the average particle size of the active material particles, and the active material in the electrode active material layer It is preferable because the particle packing efficiency can be improved. The electrode plate of the present invention may include a portion where adjacent binding material particles are connected by being continuous at least in part. As described above, the binder material particles in the present invention are for fixing the active material particles on the current collector. At this time, in the present invention, it was speculated that the adhesion of the electrode active material layer was improved by the fact that the binder material particles were continuous with each other in at least a part of the binder material particles. This improvement in film adhesion is considered to contribute effectively to the improvement in the input / output characteristics of the electrode plate. From the viewpoint of improving the film adhesion of the electrode active material layer, it is more desirable that the portion where adjacent binder material particles are continuous is significantly present in the electrode active material layer. In the present invention, whether or not the binder particles are continuous can be confirmed by observing a cross section of adjacent binder materials in the electrode active material layer with a transmission electron microscope.
本発明の電極活物質層において、隣り合う結着物質粒子同士が連続する箇所を含むよう構成するためには、後述する製造方法に従い本発明の電極板を製造することが望ましい。即ち、本発明の電極板を製造する方法において、電極活物質層形成液を集電体上に塗布して塗膜を形成し、加熱などの手段を実施することによって該塗膜から電極活物質層を形成する。その際、該集電体上において、活物質粒子の周囲に存在する金属元素含有化合物が熱分解、酸化などの反応を起こして、活物質粒子の周囲に結着物質粒子である金属酸化物粒子が生成される。このとき、隣接する結着物質粒子同士（あるいはその前駆体）の一部が接合していると、該接合部分において、結着物質粒子の成長が同時に進行し易い。上記接合部分において結着物質粒子の成長が同時に進行する結果、本発明の電極活物質層において、隣り合う結着物質粒子同士が連続する箇所を含むように構成される。 In order to configure the electrode active material layer of the present invention so as to include a portion where adjacent binder material particles are continuous, it is desirable to manufacture the electrode plate of the present invention according to the manufacturing method described later. That is, in the method for producing an electrode plate of the present invention, an electrode active material layer-forming liquid is applied onto a current collector to form a coating film, and the electrode active material is formed from the coating film by performing means such as heating. Form a layer. At that time, on the current collector, the metal element-containing compound existing around the active material particles undergoes a reaction such as thermal decomposition and oxidation, and the metal oxide particles that are the binder material particles around the active material particles Is generated. At this time, if a part of the adjacent binding substance particles (or their precursors) are joined, the growth of the binding substance particles easily proceeds simultaneously in the joined part. As a result of the simultaneous growth of the binder material particles in the joint portion, the electrode active material layer of the present invention is configured to include a portion where adjacent binder material particles are continuous with each other.
本発明の電極板は、非水電解液二次電池の正極板、負極板のいずれか一方として用いることができ、あるいは正極板及び負極板の両方に本発明の電極板を用いてもよい。 The electrode plate of the present invention can be used as either a positive electrode plate or a negative electrode plate of a non-aqueous electrolyte secondary battery, or the electrode plate of the present invention may be used for both the positive electrode plate and the negative electrode plate.
本発明の電極板は、正極板として使用する場合には、結着物質粒子が金属酸化物粒子よりなるため、樹脂製結着材のみを用いた場合と比較して出入力性能が高い。その上、本発明の電極板は、多くの金属酸化物粒子が適用できるという点で用途範囲が広く、加えて、従来の負極板と合わせて使用できるので好ましい。 When the electrode plate of the present invention is used as a positive electrode plate, since the binder material particles are made of metal oxide particles, the input / output performance is higher than when only the resin binder is used. In addition, the electrode plate of the present invention has a wide range of uses in that many metal oxide particles can be applied, and in addition, it can be used in combination with a conventional negative electrode plate, which is preferable.
また、本発明の電極板を負極板として使用する場合には、上記正極板と同様に出入力性能が高く、且つ、初期充放電効率を向上させることが可能な点で優れている。加えて、本発明の電極板は、銅やアルミなどの集電体と結着物質粒子である金属酸化物粒子との密着性が優れ、さらには負極活物質粒子の周囲に存在する金属酸化物粒子膜がＳＥＩ（ｓｏｌｉｄｅｌｅｃｔｒｏｌｙｔｅ ｉｎｔｅｒｆａｃｅ）として機能し、その結果、サイクル特性が良好になるという観点から好ましい。 Moreover, when using the electrode plate of this invention as a negative electrode plate, it is excellent at the point which can improve input / output performance similarly to the said positive electrode plate, and can improve initial stage charge / discharge efficiency. In addition, the electrode plate of the present invention has excellent adhesion between a current collector such as copper and aluminum and metal oxide particles as binder material particles, and further, metal oxide present around the negative electrode active material particles It is preferable from the viewpoint that the particle film functions as a SEI (Solidelectrolyte interface), and as a result, the cycle characteristics are improved.
また特に、本発明の電極板は、正負両極に用いられた場合には、高速充放電が可能な上、サイクル特性が良好になるなどの望ましい効果が発揮される。本発明の形態の説明において、必要に応じて本発明を正極板と負極板とに分けて説明するが、特に断りがない場合には、本発明の電極板とは、正極板および負極板のいずれも含み、また活物質粒子とは、正極活物質粒子および負極活物質粒子のいずれも含む意味で用いられる。 In particular, when the electrode plate of the present invention is used for both positive and negative electrodes, desirable effects such as high-speed charge / discharge and good cycle characteristics are exhibited. In the description of the embodiment of the present invention, the present invention is divided into a positive electrode plate and a negative electrode plate as necessary, but unless otherwise specified, the electrode plate of the present invention refers to the positive electrode plate and the negative electrode plate. The term “active material particles” includes both positive electrode active material particles and negative electrode active material particles.
次に、電極活物質層が、該電極活物質層中に分散する複数の核体と、上記核体を包囲する包囲体とを有する、本発明の電極板、および本発明における電極活物質層の構造について、図１を用いて説明する。尚、核体と包囲体とから構成される本発明において、上記核体は、活物質粒子であり、上記包囲体は、リチウムイオン挿入脱離反応を示さない金属酸化物粒子である結着物質粒子から構成される。したがって、核体である活物質粒子が、包囲体を構成する結着物質粒子に包囲されることによって、集電体上に存在することから、出入力特性の向上という効果については、上述する本発明の電極板と同様である。また核体と包囲体とを有する本発明の電極板は、包囲体のうち、集電体近傍の包囲体を構成する結着物質粒子が集電体の表面に繋がっていることから、電極活物質層と集電体との間における電子の移動がスムーズである点についても同様である。 Next, the electrode active material layer includes a plurality of nuclei dispersed in the electrode active material layer, and an enclosure surrounding the nuclei, and the electrode active material layer according to the invention The structure will be described with reference to FIG. In the present invention composed of a nucleus and an envelope, the nucleus is an active material particle, and the envelope is a metal oxide particle that does not exhibit a lithium ion insertion / release reaction. Composed of particles. Therefore, since the active material particles that are the nuclei are surrounded on the current collector by being surrounded by the binding material particles constituting the enclosure, the effect of improving the input / output characteristics is described above. This is the same as the electrode plate of the invention. In addition, the electrode plate of the present invention having a nucleus and an enclosure includes an electrode active material because the binder particles constituting the enclosure in the vicinity of the current collector are connected to the surface of the current collector. The same applies to the smooth movement of electrons between the material layer and the current collector.
本発明における電極活物質層の構造は、図１に示すとおり、電極活物質層２内に分散する複数の核体６である活物質粒子２１と、この複数の核体６の周囲に存在し、核体６を包囲する包囲体７を構成する結着物質粒子２２により構成される二重構造をなす。また集電体１近傍に存在する、包囲体７を構成する結着物質粒子２２は、集電体１表面と繋がっており、これによって集電体１上に、直接に、電極活物質層２を備える本発明の電極板１０が完成される。尚、電極活物質層２には、図示省略する空隙が随所に存在しており、これによって電極板１０を用いて電池を構成した際に、非水電解液が電極活物質層２に浸透可能である。 As shown in FIG. 1, the structure of the electrode active material layer in the present invention exists around the active material particles 21, which are a plurality of nuclei 6 dispersed in the electrode active material layer 2, and the plurality of nuclei 6. A double structure is formed by the binding material particles 22 constituting the envelope 7 that surrounds the core 6. Further, the binder material particles 22 constituting the enclosure 7 existing in the vicinity of the current collector 1 are connected to the surface of the current collector 1, whereby the electrode active material layer 2 is directly formed on the current collector 1. Thus, the electrode plate 10 of the present invention including the above is completed. The electrode active material layer 2 has voids (not shown) everywhere, so that a non-aqueous electrolyte can penetrate into the electrode active material layer 2 when a battery is constructed using the electrode plate 10. It is.
上述するとおり、上記核体を包囲する包囲体は、複数の結着物質粒子から構成されており、該包囲体に複数の核体が包囲されている。これら包囲体を構成する結着物質粒子のうち、隣接する結着物質粒子同士の一部が互いに繋がっていてよい。このように、核体が包囲体に包囲されることによって構成される本発明の電極板は、該包囲体がリチウムイオン挿入脱離反応を示さない金属酸化物粒子である結着物質粒子から構成され、核体が、活物質粒子であることにより、出入力特性に優れる。隣接する結着物質粒子が少なくとも一部において互いに繋がっていることは、透過型電子顕微鏡（ＴＥＭ）により確認できる。即ち結着物質が結晶性の場合、結着物質粒子同士が連接した部分において、相互の結晶格子像が繋がって見えることから確認することができ、また非晶質の場合には結着物質粒子相互が連続する部分の断面において、結着物質相互の境界が認められないことから確認することができる。 As described above, the envelope that surrounds the nucleus is composed of a plurality of binder particles, and the nucleus is surrounded by the envelope. Among the binding substance particles constituting these enclosures, a part of the adjacent binding substance particles may be connected to each other. As described above, the electrode plate of the present invention constituted by the nuclear body being surrounded by the enclosure is composed of binder material particles, which are metal oxide particles in which the enclosure does not exhibit lithium ion insertion / release reaction. In addition, since the core is an active material particle, the input / output characteristics are excellent. It can be confirmed by a transmission electron microscope (TEM) that adjacent binder particles are connected to each other at least in part. That is, when the binding substance is crystalline, it can be confirmed from the fact that the crystal lattice images are connected to each other at the portion where the binding substance particles are connected to each other. This can be confirmed from the fact that the boundary between the binding materials is not recognized in the cross section of the continuous portion.
本発明において、電極活物質層における活物質粒子は、複数の結着物質粒子によって少なくとも一部が覆われているものであって、更に活物質粒子表面の一部が非水電解液と接触可能に露出していても良い。面を有している状態が存在していても良い。活物質粒子表面の少なくとも一部を多数の結着物質粒子が覆っていることにより、理由は定かではないが初期充放電効率を向上することができる。 In the present invention, the active material particles in the electrode active material layer are at least partially covered with a plurality of binding material particles, and a part of the surface of the active material particles can be in contact with the non-aqueous electrolyte. May be exposed. There may be a state having a surface. By covering at least a part of the surface of the active material particles with a large number of binder material particles, the initial charge / discharge efficiency can be improved, although the reason is not clear.
尚、包囲体に包囲される活物質粒子は、１次粒子であってもよいし、２次粒子であってもよいし、これらが混在していてもよい。上記包囲体を構成する結着物質粒子の平均粒径は、核体である活物質粒子の平均粒径よりも小さいものであることが特定される。 The active material particles surrounded by the enclosure may be primary particles, secondary particles, or a mixture of these. It is specified that the average particle size of the binder material particles constituting the enclosure is smaller than the average particle size of the active material particles as the core.
本発明の一態様において、包囲体を構成する隣り合う結着物質粒子同士が、少なくとも一部において連続することにより繋っている箇所を含む場合には、電極活物質層の膜密着性が向上し、これによって出入力特性の向上に寄与するため望ましい。包囲体を構成する結着物質粒子同士が、少なくとも一部において連続して繋がっているか否かは、上述する隣接する結着物質粒子同士が、連続して繋がっているか否かの確認方法と同様であるため、ここでは割愛する。 In one embodiment of the present invention, when the binder particles adjacent to each other constituting the enclosure include a portion connected by being continuous at least in part, film adhesion of the electrode active material layer is improved. This is desirable because it contributes to improving the input / output characteristics. Whether or not the binding substance particles constituting the enclosure are continuously connected at least in part is the same as the method for confirming whether or not the adjacent binding substance particles described above are continuously connected. Therefore, I will omit it here.
結着物質に含有される炭素成分：
本発明における結着物質中には、炭素成分が含有されていても良い。結着物質中に含有される炭素成分とは、結着物質中に存在する炭素成分であって、任意で添加される導電材などの炭素を含有する添加成分や、炭素材料を用いた負極活物質粒子を除くものである。上述する結着物質中に含有される炭素成分は、樹脂成分、あるいは樹脂成分の分解物、炭素元素含有の化合物の残渣あるいは炭素単体として活物質中に含有される。高分子物質の分解物としては、エーテル基含有化合物、エステル基含有化合物、カルボキシル基含有化合物、アセチレン系化合物、セルロース系化合物、あるいはこれらの混合物が挙げられるがこれに限定されない。
Carbon components contained in the binder:
The binder material in the present invention may contain a carbon component. The carbon component contained in the binder material is a carbon component present in the binder material, and an optional component containing carbon such as a conductive material that is optionally added, and a negative electrode active using a carbon material. Excluding material particles. The carbon component contained in the binder material described above is contained in the active material as a resin component, a decomposition product of the resin component, a residue of a carbon element-containing compound, or a carbon simple substance. Examples of the decomposition product of the polymer substance include, but are not limited to, an ether group-containing compound, an ester group-containing compound, a carboxyl group-containing compound, an acetylene compound, a cellulose compound, or a mixture thereof.
結着物質に含まれる炭素成分の存在は、一般的には、得られた電極板における電極活物質層の組成分析により検出された炭素元素量が、電極活物質や導電材由来の炭素元素量の和よりも多いかどうかで、確認することができる。ただし、含有される炭素成分の量が微量な場合には、組成分析に炭素成分量が反映されないこともある。このように微量な炭素成分であっても、後述する元素マッピングなどによって、結着物質中に炭素成分が含有されていることを確認することができる。 The presence of the carbon component contained in the binder material is generally determined by the amount of carbon element detected by the compositional analysis of the electrode active material layer in the obtained electrode plate being the amount of carbon element derived from the electrode active material or conductive material. It can be confirmed whether it is more than the sum of. However, when the amount of the carbon component contained is very small, the amount of the carbon component may not be reflected in the composition analysis. Even in such a small amount of carbon component, it can be confirmed that the carbon component is contained in the binding material by element mapping described later.
上記炭素成分は、後述する樹脂成分や、金属酸化物を形成するための前駆体である金属元素含有化合物として用いる有機金属化合物の有機鎖など、電極活物質層形成液中に添加される物質中の炭素に由来する。これらは、本発明の電極板の製造において、電極活物質層中に形成される結着物質中に炭素成分として残存可能となるよう、加熱工程の加熱温度などを調整し、結着物質である金属酸化物に含有させることができる。ただし、結着物質中に炭素成分を含有させる方法は、これに限定されるものではない。 The carbon component is a substance added to the electrode active material layer forming liquid, such as an organic chain of an organic metal compound used as a metal component-containing compound which is a resin component to be described later or a precursor for forming a metal oxide. Derived from carbon. These are binder materials by adjusting the heating temperature in the heating step so that they can remain as carbon components in the binder material formed in the electrode active material layer in the production of the electrode plate of the present invention. It can be contained in a metal oxide. However, the method for containing the carbon component in the binder is not limited to this.
本発明の電極板の電極活物質層に、金属酸化物と炭素成分を含む結着物質を設けるためには、たとえば、炭素成分を提供可能な有機物や有機金属化合物を含み、且つ、導電材や、グラファイトから構成される負極活物質粒子などの炭素材料を添加する前の電極活物質層形成液を基板上に塗布して塗膜を形成し、適切な加熱温度あるいは適切な加熱雰囲気で加熱することにより、形成される結着物質中に炭素成分が存在することを予備的に確かめる予備実験を行う。次いで、必要な材料が含有された電極活物質層形成液を集電体上に塗布して予備実験と同様の条件で加熱工程を実施することにより、導電材や、グラファイトから構成される負極活物質粒子などの炭素材料以外の炭素成分が含有される結着物質を備える電極板を製造することができる。以上により得られた電極板では、電極活物質層の組成分析の結果によらず、結着物質中には、導電材を構成する炭素以外の炭素成分が残存すると理解される。 In order to provide the electrode active material layer of the electrode plate of the present invention with a binder containing a metal oxide and a carbon component, for example, the electrode plate contains an organic substance or an organometallic compound capable of providing a carbon component, and a conductive material or The electrode active material layer forming liquid before adding a carbon material such as negative electrode active material particles composed of graphite is applied on the substrate to form a coating film, and heated at an appropriate heating temperature or an appropriate heating atmosphere. Thus, a preliminary experiment is performed to preliminarily confirm that the carbon component is present in the formed binding material. Next, an electrode active material layer forming liquid containing the necessary material is applied onto the current collector and a heating step is performed under the same conditions as in the preliminary experiment, thereby making it possible to produce a negative electrode active material composed of a conductive material or graphite. An electrode plate including a binding substance containing a carbon component other than a carbon material such as substance particles can be manufactured. In the electrode plate obtained as described above, it is understood that carbon components other than carbon constituting the conductive material remain in the binder material regardless of the result of the composition analysis of the electrode active material layer.
結着物質中に、炭素成分が含有されているか否かを、より具体的に確認するためには、透過型電子顕微鏡を用い、走査透過型電子顕微鏡法（ＳＴＥＭ法）によって、ＥＤＸ検出器でナノオーダーの元素分析により示される元素マッピングによって炭素元素を確認することができる。あるいは、ＥＥＬＳ分光器によるナノオーダーの状態評価、ＨＡＡＤＦ検出器で組成コントラスト像を得ることによっても結着物質中に含有される炭素成分を確認することができる。より具体的には、電子顕微鏡写真観察において、本発明における電極活物質層には、活物質粒子などを固着させるための結着物質が、活物質粒子間や活物質粒子の周囲等に存在することを観察することができる。そして、上記元素マッピングや、組成コントラスト像を利用する方法によれば、該結着物質内に点在する炭素元素を確認することにより炭素成分の含有を確認することができる。また上記炭素成分は、グラファイト粒子や導電材が、同様の方法により集中的な炭素原子の存在として確認されるのとは異なり、著しくスケールの小さい炭素元素として観察されるため、グラファイト粒子や導電材とは明らかに区別される。 In order to confirm more specifically whether or not a carbon component is contained in the binding substance, a transmission electron microscope is used, and an EDX detector is used by scanning transmission electron microscopy (STEM method). Carbon elements can be confirmed by element mapping shown by nano-order elemental analysis. Alternatively, the carbon component contained in the binder can be confirmed by nano-order state evaluation using an EELS spectrometer and obtaining a composition contrast image using a HAADF detector. More specifically, in observation of an electron micrograph, in the electrode active material layer in the present invention, a binding material for fixing active material particles or the like is present between active material particles or around active material particles. Can be observed. And according to the method using the element mapping or the composition contrast image, it is possible to confirm the carbon component content by confirming the carbon elements scattered in the binder. Further, the carbon component is observed as a carbon element having a remarkably small scale, unlike graphite particles and conductive materials, which are confirmed as the presence of concentrated carbon atoms by the same method. Is clearly distinguished.
本発明の電極板において結着物質中に更に炭素成分が含有されていると、電極板のサイクル特性の向上という有利な効果が発揮されることを本発明者らは確認している。活物質粒子は、リチウムイオンが挿入脱離することにより膨潤および収縮が繰り返されて劣化し、これが電極板のサイクル特性を低下させる原因の１つとなることが知られているが、本発明の電極板では、活物質粒子の周囲に存在する結着物質に炭素成分が含有されていると、サイクル特性を向上することができる。 The present inventors have confirmed that when the carbon material is further contained in the binder material in the electrode plate of the present invention, the advantageous effect of improving the cycle characteristics of the electrode plate is exhibited. The active material particles are known to deteriorate due to repeated swelling and shrinkage caused by insertion and desorption of lithium ions, and this is one of the causes of reducing the cycle characteristics of the electrode plate. In the plate, when the carbon component is contained in the binding material existing around the active material particles, the cycle characteristics can be improved.
また、結着物質に炭素成分が含有されることのさらなる効果として、電極板の体積抵抗値の低減効果が発揮されることを本発明者らは見出した。この体積抵抗値の低減効果は、結着物質に炭素成分が含有されることによって、結着物質内における導電性が向上し、この結果、電極活物質層内における電子の流れがスムーズになり、体積抵抗値が下がるという好ましい効果は発揮されるのではないかと推察している。 Further, the present inventors have found that the effect of reducing the volume resistance value of the electrode plate is exhibited as a further effect of the carbon component contained in the binder material. The effect of reducing the volume resistance value is that the carbon component is contained in the binder material, so that the conductivity in the binder material is improved. As a result, the flow of electrons in the electrode active material layer becomes smooth, It is presumed that the preferable effect of lowering the volume resistance value is exhibited.
尚、本発明において、結着物質中に炭素成分を含む場合、炭素成分の量は特に限定されず、一般的な組成分析において、反映されない程度の微量な含有量であっても、電極板の出入力特性の向上に寄与し得るが、炭素成分が充分にサイクル特性の向上、および体積抵抗値の低減に寄与するためには、結着物質を構成する金属酸化物の金属元素１００モル％に対して上記炭素成分が５モル％以上含有されていることが好ましく、またその上限は特に限定されないが、５０モル％以下の含有量が好ましい。 In the present invention, when the binder material contains a carbon component, the amount of the carbon component is not particularly limited, and even if the content of the electrode plate is not reflected in a general composition analysis, Although it can contribute to the improvement of the input / output characteristics, in order for the carbon component to sufficiently contribute to the improvement of the cycle characteristics and the reduction of the volume resistance value, the metal element of the metal oxide constituting the binder material is added to 100 mol%. On the other hand, the carbon component is preferably contained in an amount of 5 mol% or more, and the upper limit is not particularly limited, but a content of 50 mol% or less is preferred.
尚、本発明において、グラファイト粒子や導電材とは明らかに区別されるスケールの小さい炭素成分が、電極活物質層中の結着物質外に、さらに存在していてもよい。また、上記構造の電極活物質層中には、さらに導電材、樹脂材料などの任意の物質が含まれていても良い。 In the present invention, a carbon component having a small scale that is clearly distinguished from the graphite particles and the conductive material may be further present outside the binding material in the electrode active material layer. In addition, the electrode active material layer having the above structure may further contain an arbitrary substance such as a conductive material or a resin material.
以上に説明する電極活物質層の構造は、核体と、包囲体とからなる、謂わば、二重構造により構成される。上記二重構造の一例は、後述する実施例１の走査型電子顕微鏡写真図５（Ａ）から理解される。また上記二重構造は、本発明の電極板を製造する方法の一態様からも理解することができる。即ち、本発明の電極板を製造する方法の一態様では、電極活物質層形成液を集電体上に塗布して塗膜を形成し、該塗膜を加熱などの手段によって電極活物質層を形成する。その際、該集電体上において、既存の活物質粒子を核体とし、これを包囲するよう存在する金属酸化物前駆体である金属元素含有化合物が熱分解などの反応を起こして金属元素が酸化し、核体の周囲に包囲体を構成する金属酸化物粒子が生成される。この結果、上記二重構造が完成する。またこのとき、包囲体を構成する結着物質粒子同士の結晶格子が連続する箇所を含んだ電極活物質層が形成されうる。 The structure of the electrode active material layer described above is constituted by a so-called double structure composed of a nucleus and an enclosure. An example of the double structure can be understood from a scanning electron micrograph of FIG. Moreover, the said double structure can be understood also from one aspect | mode of the method of manufacturing the electrode plate of this invention. That is, in one aspect of the method for producing an electrode plate of the present invention, an electrode active material layer forming liquid is applied onto a current collector to form a coating film, and the coating film is heated by means such as heating. Form. At that time, on the current collector, existing active material particles are used as nuclei, and the metal element-containing compound, which is a metal oxide precursor existing so as to surround the core, causes a reaction such as thermal decomposition, so that the metal element is Oxidizes to produce metal oxide particles that form an enclosure around the core. As a result, the double structure is completed. At this time, an electrode active material layer including a portion where the crystal lattices of the binder material particles constituting the enclosure are continuous can be formed.
核体と包囲体とからなる上記二重構造について、特に核体と包囲体との界面について着眼すると、１つの特徴が存在する。核体をなす物質である活物質粒子は、結晶性の金属化合物である。ここで、包囲体を構成する金属酸化物粒子が結晶性の場合、本発明の電極板は、結晶性の核体を、金属酸化物粒子から構成される包囲体が包囲したとき形成される両者の界面において、両者の結晶格子が連続する領域と、不連続な領域とが存在する態様とすることができる。上記態様には、特に、核体の結晶格子と、包囲体を構成する結着物質粒子の結晶格子が異なる場合には、両者の界面全域において、両者の結晶格子は不連続となる態様が含まれる。尚、上記結晶格子の連続性については、透過型電子顕微鏡により、その結晶格子を観察することにより、確認することができる。これらの態様を示す本発明は、以下に述べる優れた性質を備える。 Regarding the above-mentioned double structure composed of a nucleus and an enclosure, there is one feature when focusing on the interface between the nucleus and the enclosure. Active material particles, which are substances that form nuclei, are crystalline metal compounds. Here, when the metal oxide particles constituting the enclosure are crystalline, the electrode plate of the present invention is formed when the crystalline nucleus is surrounded by the enclosure composed of the metal oxide particles. In this interface, a mode in which both crystal lattices are continuous and a discontinuous region is present. The above aspect includes an aspect in which, when the crystal lattice of the nucleus is different from the crystal lattice of the binder particles constituting the enclosure, both crystal lattices are discontinuous in the entire interface between the two. It is. The continuity of the crystal lattice can be confirmed by observing the crystal lattice with a transmission electron microscope. The present invention showing these aspects has the excellent properties described below.
即ち、本発明者らは、上述する結晶格子が不連続な領域の存在が、サイクル特性の向上に寄与するということを推察した。即ち、非水電解液二次電池は、リチウムイオンなどのアルカリイオンが活物質の結晶構造に繰り返し挿入脱離するうちに、該結晶構造が劣化し、あるいはさらに破壊され、サイクル特性が低下する。上述する結晶構造の劣化・破壊は、結晶構造の連続する結晶格子に沿って発生すると考えられる。ところが本発明の電極板は、上述するとおり、核体である活物質粒子と、リチウムイオン挿入脱離反応を示す金属酸化物である結着物質粒子から構成される包囲体とからなる二重構造の界面において、両者の結晶格子が不連続な領域が存在する。このため、核体、包囲体それぞれで生じた結晶構造の劣化が、上記不連続な領域では互いに影響を及ぼさないと考えられた。したがって、サイクル特性が低下し難く、換言すると、上記二重構造が、良好なサイクル特性の発揮に寄与すると推察された。実際にも、上記二重構造の示されない従来の電極板と比較して、本発明のサイクル特性の向上が確認されており、後述する実施例１においても、サイクル特性が良好であるという結果が示された。 That is, the present inventors have inferred that the presence of the above-described region where the crystal lattice is discontinuous contributes to improvement of cycle characteristics. That is, in the non-aqueous electrolyte secondary battery, while alkali ions such as lithium ions are repeatedly inserted into and desorbed from the crystal structure of the active material, the crystal structure deteriorates or is further destroyed, and the cycle characteristics deteriorate. It is considered that the above-described deterioration / destruction of the crystal structure occurs along a continuous crystal lattice of the crystal structure. However, as described above, the electrode plate of the present invention has a double structure comprising an active material particle that is a nucleus and an enclosure composed of binder material particles that are metal oxides that exhibit a lithium ion insertion / release reaction. At the interface, there is a region where the crystal lattices of both are discontinuous. For this reason, it was considered that the deterioration of the crystal structure generated in each of the nucleus and the enclosure did not affect each other in the discontinuous region. Therefore, it is presumed that the cycle characteristics are unlikely to deteriorate, in other words, the double structure contributes to the display of good cycle characteristics. Actually, the improvement of the cycle characteristics of the present invention has been confirmed as compared with the conventional electrode plate not showing the double structure, and the result that the cycle characteristics are good also in Example 1 described later. Indicated.
（集電体）
本発明に用いられる集電体は、一般的に非水電解液二次電池用正極板における正極集電体あるいは非水電解液二次電池用負極板における負極集電体として用いられるものであれば、特に限定されない。例えば、アルミニウム箔、ニッケル箔、銅箔などの単体又は合金から形成されているもの、もしくはカーボンシート、カーボン板、及びカーボンテキスタイル等の高い導電性を有する箔ものが好ましく用いられる。尚、本発明に用いられる集電体は、必要に応じて、電極活物質層の形成が予定される面において、表面加工処理がなされている集電体であってもよい。表面加工処理がなされている集電体としては、導電性物質が積層されているもの、化学研磨処理、コロナ処理、酸素プラズマ処理などの表面処理がなされていてもの等が挙げられる。あるいは、上記集電体は、物理的に任意の凹凸などが表面に設けられていてもよい。
(Current collector)
The current collector used in the present invention is generally used as a positive electrode current collector in a positive electrode plate for a non-aqueous electrolyte secondary battery or a negative electrode current collector in a negative electrode plate for a non-aqueous electrolyte secondary battery. There is no particular limitation. For example, a foil made of a simple substance such as an aluminum foil, a nickel foil, or a copper foil or an alloy, or a highly conductive foil such as a carbon sheet, a carbon plate, and a carbon textile is preferably used. The current collector used in the present invention may be a current collector that has been subjected to surface processing on the surface on which the electrode active material layer is to be formed, if necessary. Examples of the current collector that has been subjected to surface processing treatment include those in which a conductive material is laminated, surface treatments such as chemical polishing treatment, corona treatment, and oxygen plasma treatment. Alternatively, the current collector may be physically provided with any unevenness on the surface.
上記集電体としては、例えば、図４（Ａ）に示すとおり、非水電解液二次電池用電極板２０に用いられる集電体１として、それ自体が集電機能を有する金属箔などの集電基材３のみを用いることができる。集電基材３としては、上述するアルミニウム箔、ニッケル箔、カーボンシートなどが例示される。かかる場合には、集電基材３の表面１０１の少なくとも一部に電極活物質層２が設けられる。 As the current collector, for example, as shown in FIG. 4A, the current collector 1 used for the electrode plate 20 for a non-aqueous electrolyte secondary battery is a metal foil having a current collecting function itself. Only the current collecting substrate 3 can be used. Examples of the current collecting base 3 include the above-described aluminum foil, nickel foil, carbon sheet, and the like. In such a case, the electrode active material layer 2 is provided on at least a part of the surface 101 of the current collecting base material 3.
また、異なる集電体の例としては、図４（Ｂ）に示すとおり、非水電解液二次電池用電極板２０’に用いられる集電体１’として、それ自体が集電機能を有する集電基材３の上面に、導電性を有する任意の導電性層４が設けられてなる集電体１’を用いることができる。導電性層４は、電極活物質層２と集電基材３と間の電子の移動を妨げない程度の導電性を示すものであればよい。例えば、導電性層４は、銅または銅合金からなる積層層、あるいは任意の導電性微粒子がメッキあるいはスパッタリングなどにより堆積されてなる層、あるいは一枚以上の導電性薄膜が設けられてなる層などであってよく、またこれらの例に限定されない。集電体１’において、導電性層４の表面が、集電体１’の表面１０２となり、電極活物質層２は、表面１０２の少なくとも一部に設けられる。尚、図４（Ｂ）では、任意の導電性層４が１層である態様を示した。しかし、集電体１’の構成はこれに限定されず、導電性層４は、２以上の任意の導電性層が積層された積層構成であってもよい。 In addition, as an example of a different current collector, as shown in FIG. 4B, the current collector 1 ′ used for the electrode plate 20 ′ for the nonaqueous electrolyte secondary battery itself has a current collecting function. A current collector 1 ′ in which an arbitrary conductive layer 4 having conductivity is provided on the upper surface of the current collecting substrate 3 can be used. The electroconductive layer 4 should just show electroconductivity of the grade which does not prevent the movement of the electron between the electrode active material layer 2 and the current collection base material 3. FIG. For example, the conductive layer 4 is a laminated layer made of copper or a copper alloy, a layer in which arbitrary conductive fine particles are deposited by plating or sputtering, or a layer in which one or more conductive thin films are provided. However, the present invention is not limited to these examples. In the current collector 1 ′, the surface of the conductive layer 4 becomes the surface 102 of the current collector 1 ′, and the electrode active material layer 2 is provided on at least a part of the surface 102. FIG. 4B shows a mode in which the arbitrary conductive layer 4 is a single layer. However, the configuration of the current collector 1 ′ is not limited to this, and the conductive layer 4 may have a stacked configuration in which two or more arbitrary conductive layers are stacked.
また、異なる集電体の例としては、図４（Ｃ）に示すとおり、非水電解液二次電池用電極板２０’’に用いられる集電体１’’として、それ自体が集電機能を有する集電基材３の上面に、断続的に形成された任意の断続層５が設けられてなる集電体を用いることができる。断続層５は、上述する導電性層４と同じく導電性の層であってもよいし、あるいは導電性を示さない層であってもよい。即ち、非水電解液二次電池用電極板２０’’では、集電体１’’の表面は、断続層５の表面である表面１０３と、断続層５が設けられておらず集電基材３自体の表面である表面１０３’とからなる。このとき、電極活物質層２は、表面１０３および表面１０３’のいずれとも接するよう形成することができる。非水電解液二次電池用電極板２０’’では、断続層５は、導電性を有していても、有していなくてもよい。断続層５が導電性を有していない層であっても、集電体１’’の表面１０３’において電極活物質層２と集電基材３とが直接接するため、電極活物質層２と集電体１’’との間において電子の移動が確保される。ただし、非水電解液二次電池用電極板２０’’自体の電気抵抗をより小さいものにするという観点からは、断続層５も、導電性を示すことが好ましい。 Further, as an example of a different current collector, as shown in FIG. 4C, the current collector 1 ″ used for the electrode plate 20 ″ for the nonaqueous electrolyte secondary battery itself has a current collecting function. It is possible to use a current collector in which an arbitrary intermittent layer 5 formed intermittently is provided on the upper surface of the current collecting base material 3 having. The intermittent layer 5 may be a conductive layer similar to the conductive layer 4 described above, or may be a layer that does not exhibit conductivity. That is, in the electrode plate 20 ″ for the non-aqueous electrolyte secondary battery, the surface of the current collector 1 ″ is the surface 103 which is the surface of the intermittent layer 5, and the current collector base is not provided with the intermittent layer 5. It consists of surface 103 'which is the surface of material 3 itself. At this time, the electrode active material layer 2 can be formed so as to be in contact with both the surface 103 and the surface 103 ′. In the electrode plate 20 ″ for a nonaqueous electrolyte secondary battery, the intermittent layer 5 may or may not have conductivity. Even if the intermittent layer 5 is a non-conductive layer, the electrode active material layer 2 is in direct contact with the current collector base 3 on the surface 103 ′ of the current collector 1 ″. And the current collector 1 ″ ensure the movement of electrons. However, from the viewpoint of reducing the electrical resistance of the electrode plate 20 ″ for the nonaqueous electrolyte secondary battery itself, it is preferable that the intermittent layer 5 also exhibits conductivity.
また、断続層５が導電性を示す場合、図４（Ｄ）に示すように、集電体１’’の表面であって断続層５上にのみ、選択的に電極活物質層２’を設けて、非水電解液二次電池用電極板２０’’’を構成してもよい。即ち、集電体１’’の表面のうち、表面１０３の少なくとも一部に、選択的に電極活物質層２’を設けても良い。あるいは、図示しないが、断続層５が導電性を示さない場合、集電体１’’の表面１０３’の少なくとも一部に選択的に電極活物質層２’を設けてもよい。 Further, when the intermittent layer 5 exhibits conductivity, as shown in FIG. 4D, the electrode active material layer 2 ′ is selectively formed only on the intermittent layer 5 on the surface of the current collector 1 ″. The electrode plate 20 ′ ″ for a non-aqueous electrolyte secondary battery may be provided. That is, the electrode active material layer 2 ′ may be selectively provided on at least a part of the surface 103 of the surface of the current collector 1 ″. Alternatively, although not shown, when the intermittent layer 5 does not exhibit conductivity, the electrode active material layer 2 ′ may be selectively provided on at least a part of the surface 103 ′ of the current collector 1 ″.
尚、上述する集電体の説明は、本発明に用いられる集電体を何ら限定するものではない。本発明に用いられる集電体は、以上に例示するとおり、集電機能を有する集電基材のみであってもよく、かかる態様では、電極活物質層が設けられる集電体の表面とは、該集電基材の表面を指す。あるいは、本発明において、集電体とは、集電機能を有する集電基材と、該集電基材上に設けられる任意の積層層を有していてもよい。かかる態様では、電極活物質層が設けられる集電体の表面とは、集電基材と電極活物質層との間の少なくとも一領域で電子の移動が確保される範囲において、上記積層層の表面、あるいは、積層層が設けられていない集電基材表面、あるいは、上記積層層の表面および積層層が設けられていない集電基材表面の両方を指す。 The description of the current collector described above does not limit the current collector used in the present invention. As exemplified above, the current collector used in the present invention may be only a current collecting base material having a current collecting function, and in such an embodiment, the surface of the current collector on which the electrode active material layer is provided is defined. , Refers to the surface of the current collecting substrate. Alternatively, in the present invention, the current collector may have a current collecting base material having a current collecting function and an arbitrary laminated layer provided on the current collecting base material. In such an embodiment, the surface of the current collector on which the electrode active material layer is provided is within the range in which the movement of electrons is ensured in at least one region between the current collector base material and the electrode active material layer. It refers to the surface, or the surface of the current collecting base material on which the laminated layer is not provided, or the surface of the current collecting base material on which the surface of the laminated layer is not provided.
本発明に用いられる集電体は、耐熱温度が８００℃以下、さらには６００℃以下、特には４００℃以下のものを選択することが可能である。かかる集電体の選択は、後述する本発明の電極板を製造する方法における電極活物質層形成工程における温度条件などとの関係によって決定される。本発明の電極板を製造する方法では、電極活物質層形成工程が加熱工程である場合に、例えば４００℃以下の加熱温度で集電体上に直接に電極活物質層を形成することができる。したがって、上記集電体は、耐熱温度が８００℃以下、さらには６００℃以下、特には４００℃以下のものを選択することができ、該集電体上に直接に電極活物質層が形成されてなる本発明の電極板を提供することができる。 As the current collector used in the present invention, one having a heat resistant temperature of 800 ° C. or lower, further 600 ° C. or lower, and particularly 400 ° C. or lower can be selected. The selection of the current collector is determined by the relationship with the temperature condition in the electrode active material layer forming step in the method for producing the electrode plate of the present invention described later. In the method for producing the electrode plate of the present invention, when the electrode active material layer forming step is a heating step, the electrode active material layer can be formed directly on the current collector at a heating temperature of 400 ° C. or less, for example. . Accordingly, the current collector can be selected to have a heat resistant temperature of 800 ° C. or lower, more preferably 600 ° C. or lower, and particularly 400 ° C. or lower, and an electrode active material layer is directly formed on the current collector. An electrode plate of the present invention can be provided.
上記集電体の厚みは、一般に非水電解液二次電池用正極板または負極板の集電体として使用可能な厚みであれば特に限定されないが、１０〜２００μｍであることが好ましく、１５〜５０μｍであることがより好ましい。 The thickness of the current collector is not particularly limited as long as it can be used as a current collector for a positive electrode plate or a negative electrode plate for a non-aqueous electrolyte secondary battery, but is preferably 10 to 200 μm. More preferably, it is 50 μm.
（電極活物質層）
本発明における電極活物質層は、少なくとも、活物質粒子と、結着物質粒子として、リチウムイオン挿入脱離反応を示さず、上記活物質粒子の平均粒径よりも小さい平均粒径である金属酸化物粒子とを含んで構成される。
(Electrode active material layer)
The electrode active material layer in the present invention is a metal oxide that does not exhibit lithium ion insertion / release reaction as active material particles and binder material particles, and has an average particle size smaller than the average particle size of the active material particles. It is comprised including an object particle.
本発明の電極板において、電極活物質層の厚みは、当該電極板に求められる初期充放電効率や出入力特性を勘案して、適宜設計することができる。一般的には、電極活物質層の厚みは、２００μｍ以下、より一般的には１００μｍ以上かつ１５０μｍ以下の厚みで設計される。ただし、本発明においては、電極活物質層を非常に薄く形成することが可能である。そのため、用いられる活物質粒子の粒子径にもよるが、電極活物質層の厚みが、３００ｎｍ以上２００μｍ以下の電極活物質層を形成することができる。出入力特性を向上させつつも初期充放電効率を向上させ得るという観点からは、特に電極活物質層の膜厚を３００ｎｍ以上１５０μｍ以下にすることが好ましく、５００ｎｍ以上１００μｍ以下とすることがより好ましい。即ち、電極活物質層の厚みが、上述の範囲のように薄い場合には、用いられる活物質粒子は粒子径が小さいものであり、少なくとも電極活物質層の膜厚以下の粒子径であることを意味する。また、電極活物質層の厚みが、上述の範囲のように薄い場合には、電極活物質層内における活物質粒子と集電体との距離が、短くなるので、電極板の抵抗を下げることができる。尚、本発明において電極活物質層の膜厚の下限は、主として用いられる活物質粒子の粒子径に依存し、使用可能な活物質粒子の粒子径の縮小化に伴い、さらに膜厚を薄くすることが可能である。 In the electrode plate of the present invention, the thickness of the electrode active material layer can be appropriately designed in consideration of the initial charge / discharge efficiency and input / output characteristics required for the electrode plate. In general, the thickness of the electrode active material layer is designed to be 200 μm or less, more generally 100 μm or more and 150 μm or less. However, in the present invention, the electrode active material layer can be formed very thin. Therefore, although depending on the particle diameter of the active material particles used, an electrode active material layer having an electrode active material layer thickness of 300 nm or more and 200 μm or less can be formed. From the viewpoint of improving the initial charge / discharge efficiency while improving the input / output characteristics, the thickness of the electrode active material layer is particularly preferably 300 nm to 150 μm, and more preferably 500 nm to 100 μm. . That is, when the thickness of the electrode active material layer is thin as in the above range, the active material particles used have a small particle diameter, and are at least a particle diameter equal to or smaller than the film thickness of the electrode active material layer. Means. In addition, when the thickness of the electrode active material layer is as thin as the above range, the distance between the active material particles and the current collector in the electrode active material layer is shortened, so that the resistance of the electrode plate is reduced. Can do. In the present invention, the lower limit of the film thickness of the electrode active material layer mainly depends on the particle diameter of the active material particles used, and the film thickness is further reduced as the particle diameter of usable active material particles is reduced. It is possible.
活物質粒子：
本発明の正極板における電極活物質層に含有される正極活物質粒子としては、一般的に非水電解液二次電池用正極板において用いられるリチウムイオン挿入脱離反応を示す活物質粒子であれば、特に限定されない。上記正極活物質の具体的な例としては、例えばＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉＯ２、ＬｉＦｅＯ２、ＬｉＴｉＯ２、ＬｉＦｅＰＯ４などのリチウム複合酸化物などを挙げることができる。また、本発明の負極板における電極活物質層に含有される負極活物質粒子としては、一般的に非水電解液二次電池用負極板において用いられるリチウムイオン挿入脱離反応を示す活物質粒子であれば、特に限定されない。上記負極活物質の具体的な例としては、例えばグラファイトやＬｉ４Ｔｉ５Ｏ１２などを挙げることができる。
Active material particles:
The positive electrode active material particles contained in the electrode active material layer in the positive electrode plate of the present invention may be active material particles that exhibit a lithium ion insertion / release reaction generally used in positive electrode plates for non-aqueous electrolyte secondary batteries. There is no particular limitation. The above Examples of the positive electrode active material, for example LiCoO 2, LiMn 2 O 4, LiNiO 2, LiFeO 2, LiTiO 2, LiFePO 4 and the like lithium composite oxides such as. In addition, as the negative electrode active material particles contained in the electrode active material layer in the negative electrode plate of the present invention, active material particles generally exhibiting lithium ion insertion and desorption reactions used in negative electrode plates for non-aqueous electrolyte secondary batteries If it is, it will not be specifically limited. Specific examples of the negative electrode active material include graphite and Li 4 Ti 5 O 12 .
本発明に用いられる活物質粒子の粒子径は、特に限定されず、任意の大きさのものを適宜選択して使用することができる。特に、本発明において粒子径の小さい活物質粒子を用いる場合には、電極活物質層中における活物質粒子の表面面積の総量を増大させることができるとともに、１つの活物質粒子内におけるリチウムの移動距離を短縮することが可能であるため、飛躍的に出入力特性を向上させることができる。したがって、より高い出入力特性を求める場合には、粒子径の寸法の小さいものを選択することが望ましい。具体的には、用いる活物質粒子の粒子径は、好ましくは１０μｍ未満、より好ましくは５μｍ以下、特に好ましくは１μｍ以下である。従来の、樹脂製結着材を用いたスラリー状の電極活物質層形成液では、用いる活物質粒子径が１０μｍ未満となると塗工適性が不良になる傾向にあり、５μｍ以下であると該形成液の流動性が著しく悪くなり、印刷機などの量産設備に適用が困難となり、さらに１μｍ以下であると、活物質粒子を形成液中に分散すること自体が困難になる傾向にあった。 The particle diameter of the active material particles used in the present invention is not particularly limited, and those having an arbitrary size can be appropriately selected and used. In particular, when active material particles having a small particle diameter are used in the present invention, the total amount of the surface area of the active material particles in the electrode active material layer can be increased and lithium can move within one active material particle. Since the distance can be shortened, the input / output characteristics can be dramatically improved. Therefore, when a higher input / output characteristic is required, it is desirable to select one having a small particle size. Specifically, the particle diameter of the active material particles to be used is preferably less than 10 μm, more preferably 5 μm or less, and particularly preferably 1 μm or less. In a conventional slurry-like electrode active material layer forming liquid using a resin binder, when the active material particle diameter used is less than 10 μm, the coating suitability tends to be poor, and when it is 5 μm or less, the formation is performed. The fluidity of the liquid is remarkably deteriorated, making it difficult to apply to mass production equipment such as a printing press. Further, if it is 1 μm or less, it tends to be difficult to disperse the active material particles in the forming liquid.
また本発明において、電極活物質層中に含有される活物質粒子の平均粒径は、結着物質粒子である金属酸化物粒子との関係では、該金属酸化物粒子の平均粒径よりも大きい必要がある。望ましくは、電極活物質層中に含まれる活物質粒子の平均粒径は、結着物質粒子である金属酸化物粒子の平均粒径の３倍以上、好ましくは、５倍以上、より好ましくは、３０倍以上である。以上のとおり、活物質粒子の平均粒径が、結着物質粒子の平均粒径よりも著しく大きい場合には、電極活物質層中において、活物質粒子の充填率を充分に大きくすることができ、且つ、活物質粒子間に存在する空間に多数の結着物質粒子が充填された状態が可能となり、初期充放電効率向上効果に優れる。 In the present invention, the average particle diameter of the active material particles contained in the electrode active material layer is larger than the average particle diameter of the metal oxide particles in relation to the metal oxide particles that are binder particles. There is a need. Desirably, the average particle size of the active material particles contained in the electrode active material layer is 3 times or more, preferably 5 times or more, more preferably, the average particle size of the metal oxide particles as the binder material particles. 30 times or more. As described above, when the average particle size of the active material particles is significantly larger than the average particle size of the binder material particles, the filling rate of the active material particles can be sufficiently increased in the electrode active material layer. In addition, the space between the active material particles can be filled with a large number of binder material particles, and the effect of improving the initial charge / discharge efficiency is excellent.
上記、電極活物質層中に含有される活物質粒子の平均粒径、あるいは、後述する結着物質である金属酸化物粒子の平均粒径は、電子顕微鏡観察結果を画像解析式粒度分布測定ソフトウェア（例えば株式会社マウンテック製、ＭＡＣ ＶＩＥＷなど）を用いて任意に選択された複数（例えば３０ケ程度）の活物質粒子の最長径を測定し、その平均値を算出することにより求めることができる。 The average particle diameter of the active material particles contained in the electrode active material layer or the average particle diameter of the metal oxide particles as a binder described later can be obtained by using an image analysis type particle size distribution measurement software. It can be obtained by measuring the longest diameter of a plurality (for example, about 30) of active material particles arbitrarily selected using, for example, MAC VIEW manufactured by Mountec Co., Ltd. and calculating an average value thereof.
金属酸化物粒子：
上記電極活物質層中に含有される金属酸化物粒子は、平均粒径が、活物質粒子の平均粒径よりも小さいものであって、金属元素に結合する酸素元素を有する化合物であればよく、このような条件を満たす限り、一般的に金属と理解される元素の酸化物であれば、特に限定されない。より具体的には、上記金属酸化物粒子は、Ｌｉ、Ｂｅ、Ｎａ、Ｍｇ、Ａｌ、Ｓｉ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｒｂ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｉｎ、Ｓｎ、Ｃｓ、Ｂａ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、Ｈｇ、Ｔｌ、Ｐｂ、Ｂｉ、Ｆｒ、Ｒａ、およびＣｅなどの金属元素の１種の金属酸化物粒子、または２種以上の金属元素を含む複合金属酸化物粒子であって、リチウムイオン挿入脱離反応を示さない化合物とすることができる。また理由は明らかではないが、上記金属元素の中でも、特に第３周期乃至第５周期に属する金属元素を含有する金属酸化物を結着物質として電極活物質層中に含む場合、より高い出入力特性向上効果が示されるため好ましい。更に、上記第３周期乃至第５周期に属する金属の中でも、鉄、チタン及びコバルト、マンガンは安価で取扱性も容易である上、非常に優れた出入力特性向上効果を示すことから、これらの金属酸化物粒子を結着物質粒子とすることが特に好ましい。
Metal oxide particles:
The metal oxide particles contained in the electrode active material layer may be any compound having an average particle size smaller than the average particle size of the active material particles and having an oxygen element bonded to the metal element. As long as these conditions are satisfied, the oxide is not particularly limited as long as it is an oxide of an element generally understood as a metal. More specifically, the metal oxide particles include Li, Be, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Ga. , Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg , Tl, Pb, Bi, Fr, Ra and Ce, one kind of metal oxide particles, or composite metal oxide particles containing two or more kinds of metal elements, and lithium ion insertion / desorption reaction It can be set as the compound which does not show. The reason is not clear, but among the above metal elements, particularly when a metal oxide containing a metal element belonging to the third to fifth periods is included as a binder in the electrode active material layer, higher input / output is achieved. This is preferable because an effect of improving characteristics is shown. Further, among the metals belonging to the third to fifth periods, iron, titanium, cobalt, and manganese are inexpensive and easy to handle, and exhibit an extremely excellent output / input characteristic improving effect. It is particularly preferred that the metal oxide particles are binder material particles.
本発明電極板において、結着物質である金属酸化物粒子は、リチウムイオン挿入脱離反応を示さないものであれば、上述する金属元素のうちのいずれか１種の金属元素に酸素が結合した金属酸化物粒子、あるいは上述する金属元素から選択される２種以上の金属元素を含み、少なくとも１種の金属元素に酸素が結合した複合金属酸化物粒子のいずれであってもよい。例えば、１種の金属元素を含む金属酸化物の例としては、酸化ナトリウム、酸化マグネシウム、酸化アルミニウム、酸化珪素、酸化カリウム、酸化カルシウム、酸化スカンジウム、酸化チタン、酸化バナジウム、酸化クロム、酸化マンガン、酸化鉄、酸化コバルト、酸化ニッケル、酸化亜鉛、酸化ガリウム、酸化ストロンチウム、酸化イットリウム、酸化ジルコニウム、酸化モリブデン、酸化ルテニウム、酸化タンタル、酸化タングステン、酸化セリウムなどを挙げることができる。特に、酸化チタン及び／又は酸化鉄を結着物質として電極活物質層中に含んでいると、本発明の電極板は出入力特性の向上が顕著なものとなるため好ましい。また、２種以上の金属元素を含み、リチウムイオン挿入脱離反応を示さない複合金属酸化物としては、例えば、ガドリニウムが置換された酸化セリウム、イットリウムが置換された酸化ジルコニウム、鉄とチタンの混合酸化物、インジウムとスズが混合された酸化物等を挙げることができる。 In the electrode plate of the present invention, as long as the metal oxide particles as the binding material do not exhibit a lithium ion insertion / release reaction, oxygen is bonded to any one of the above metal elements. Either metal oxide particles or composite metal oxide particles containing two or more metal elements selected from the metal elements described above and having oxygen bonded to at least one metal element may be used. For example, examples of metal oxides containing one kind of metal element include sodium oxide, magnesium oxide, aluminum oxide, silicon oxide, potassium oxide, calcium oxide, scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, Examples thereof include iron oxide, cobalt oxide, nickel oxide, zinc oxide, gallium oxide, strontium oxide, yttrium oxide, zirconium oxide, molybdenum oxide, ruthenium oxide, tantalum oxide, tungsten oxide, and cerium oxide. In particular, when the electrode active material layer contains titanium oxide and / or iron oxide as a binder, the electrode plate of the present invention is preferable because the improvement of the input / output characteristics becomes remarkable. Examples of composite metal oxides that contain two or more metal elements and do not exhibit lithium ion insertion / release reactions include, for example, cerium oxide substituted with gadolinium, zirconium oxide substituted with yttrium, and a mixture of iron and titanium. An oxide, an oxide in which indium and tin are mixed, and the like can be given.
電極活物質層中において、結着物質粒子の平均粒径と、活物質粒子の平均粒径との関係は、前記したとおりであるが、特に、結着物質粒子の平均粒径が１０ｎｍ以上１μｍ未満、より好ましくは１００ｎｍを上回り、１μｍ未満であることにより、活物質粒子の平均粒径に対し、結着物質粒子の平均粒径を有意に小さくなるよう設計しやすく、望ましい。結着物質粒子の平均粒径が１μｍ以上であることを禁止する趣旨ではないが、１μｍ以上とすることは製造上の困難点があり、また、１μｍ未満とすることによって、活物質粒子間の隙間に結着物質粒子を充填させた状態にすることが容易であって、初期充放電効率の向上効果がより発揮されやすい。また、結着物質粒子の平均粒径が１０ｎｍ未満である場合には、理由は明らかではないが、該結着物質粒子が電極板において活物質の作用を発揮しうる金属酸化物であったとしても、初期充放電効率向上効果が得られ難い傾向にある。特に、結着物質粒子の平均粒径が１００ｎｍを上回る場合に、本発明の効果である、出入力特性の向上が顕著に発揮され好ましい。 In the electrode active material layer, the relationship between the average particle size of the binder material particles and the average particle size of the active material particles is as described above. In particular, the average particle size of the binder material particles is 10 nm or more and 1 μm. If it is less than, more preferably more than 100 nm and less than 1 μm, the average particle size of the binder particles can be easily designed to be significantly smaller than the average particle size of the active material particles, which is desirable. Although it is not intended to prohibit the average particle size of the binder material particles from being 1 μm or more, it is difficult to produce the binder particles having a particle size of 1 μm or more. It is easy to make the gap filled with the binder particles, and the effect of improving the initial charge / discharge efficiency is more easily exhibited. Further, when the average particle diameter of the binder material particles is less than 10 nm, the reason is not clear, but the binder material particles are metal oxides that can exhibit the action of the active material in the electrode plate. However, the effect of improving the initial charge / discharge efficiency tends to be difficult to obtain. In particular, when the average particle size of the binder particles exceeds 100 nm, the improvement of the input / output characteristics, which is the effect of the present invention, is remarkably exhibited, which is preferable.
上記活物質粒子と、これを集電体上に固着させるための結着物質粒子である金属酸化物粒子との組み合わせの観点では、正極活物質粒子と、正極活物質となり得る金属酸化物粒子であるがリチウムイオン挿入脱離反応を示さない金属酸化物粒子との組み合わせ、あるいは、負極活物質粒子と、負極活物質となり得る金属酸化物粒子であるがリチウムイオン挿入脱離反応を示さない金属酸化物粒子との組み合わせが好ましい。 From the viewpoint of the combination of the active material particles and metal oxide particles that are binding material particles for fixing the active material particles on the current collector, positive electrode active material particles and metal oxide particles that can be a positive electrode active material. Combination of metal oxide particles that do not show lithium ion insertion / release reaction, or negative electrode active material particles and metal oxide particles that can be a negative electrode active material but do not show lithium ion insertion / release reaction A combination with physical particles is preferred.
本発明における金属酸化物が、非晶質であるか結晶性であるかは、当該金属酸化物、あるいは当該金属酸化物を含む試料を、Ｘ線解析装置で解析し、当該金属酸化物のピークの有無により確認することができ、金属酸化物のピークが検出された場合は結晶性、ピークが検出されなかった場合は非晶質であることを意味する。例えば、金属元素として鉄を例に結晶性の酸化鉄と、非晶質の酸化鉄についてそれぞれのＸ線解析装置における具体的な分析結果を用いて説明する。 Whether the metal oxide in the present invention is amorphous or crystalline is analyzed by analyzing the metal oxide or a sample containing the metal oxide with an X-ray analyzer, and obtaining a peak of the metal oxide. In the case where a metal oxide peak is detected, it indicates crystallinity, and in the case where no peak is detected, it indicates amorphous. For example, taking iron as an example of the metal element, crystalline iron oxide and amorphous iron oxide will be described using specific analysis results in the respective X-ray analyzers.
まず、Ｆｅ（ＮＯ３）・９Ｈ２Ｏ[分子量：４０４]４．０ｇをメタノール１５ｇに加えて溶解させ、さらにエチレングリコール１０ｇを混合し、試料溶液を作成した。次いで、上記試料溶液をガラス基板上に塗布したサンプル１及び２を作成し、サンプル１は、３００℃で１時間加熱し、一方、サンプル２は５００℃で１時間加熱した。次いで、加熱後のサンプル１及び２の塗膜面を削り、それぞれ、分析試料１及び２とし、これらについて組成分析を行った。ここで、分析試料１の組成分析の結果、Ｆｅ元素が３４Ａｔｏｍｉｃ％、Ｏ元素が６６Ａｔｏｍｉｃ％であり、また分析試料２の組成分析の結果、Ｆｅ元素が３８Ａｔｏｍｉｃ％、Ｏ元素が６２Ａｔｏｍｉｃ％であった。したがって分析試料１及び２に含有される鉄は、いずれも酸化していることが確認された。 First, 4.0 g of Fe (NO 3 ) · 9H 2 O [molecular weight: 404] was added to 15 g of methanol and dissolved, and 10 g of ethylene glycol was further mixed to prepare a sample solution. Samples 1 and 2 were then prepared by applying the sample solution on a glass substrate, sample 1 was heated at 300 ° C. for 1 hour, while sample 2 was heated at 500 ° C. for 1 hour. Next, the coated surfaces of samples 1 and 2 after heating were scraped to obtain analytical samples 1 and 2, respectively, which were subjected to composition analysis. Here, as a result of the composition analysis of the analysis sample 1, the Fe element was 34 atomic% and the O element was 66 atomic%, and as a result of the composition analysis of the analysis sample 2, the Fe element was 38 atomic% and the O element was 62 atomic%. . Therefore, it was confirmed that both the irons contained in the analytical samples 1 and 2 were oxidized.
次に、分析試料１及び２の結晶性について、Ｘ線解析装置で評価した。それぞれの分析結果について、分析試料１については図８に、分析試料２については図９示した。図８及び図９から明らかなように、図８はブロードなチャートが示されるだけで何らピークが観察させず、非晶質な状態であると理解される。一方、図９では、横軸の３２と５８付近にピークが確認でき、これによって結晶性の酸化鉄がガラス基板上に生成されていることが理解される。
このように、本発明では、金属元素が酸化物となっているか否かを組成分析により確認するとともに、Ｘ線解析装置によって得られたチャートから、その金属酸化物が非晶質であるのか、結晶性であるのかを確認することができる。
Next, the crystallinity of the analysis samples 1 and 2 was evaluated with an X-ray analyzer. The analysis results are shown in FIG. 8 for analysis sample 1 and FIG. 9 for analysis sample 2. As is apparent from FIGS. 8 and 9, FIG. 8 is understood to be in an amorphous state because only a broad chart is shown and no peak is observed. On the other hand, in FIG. 9, a peak can be confirmed in the vicinity of 32 and 58 on the horizontal axis, which indicates that crystalline iron oxide is generated on the glass substrate.
Thus, in the present invention, whether or not the metal element is an oxide is confirmed by composition analysis, and whether the metal oxide is amorphous from the chart obtained by the X-ray analyzer, It can be confirmed whether it is crystalline.
本発明において、結着物質粒子である金属酸化物粒子が、リチウムイオン挿入脱離反応を示さないものであることは、電気化学測定（サイクリックボルタンメトリー）法により確認することができる。 In the present invention, it can be confirmed by an electrochemical measurement (cyclic voltammetry) method that the metal oxide particles as the binder particles do not show a lithium ion insertion / release reaction.
具体的には、活物質粒子の適切な電圧範囲において、電極電位が設定され、測定が実施される。例えば、活物質粒子としてＬｉＭｎ２Ｏ４を使用する場合には、金属酸化物粒子がリチウム挿入脱離するか否かを３．０Ｖから４．３Ｖまで掃引したのち、再び３．０Ｖまで戻す作業を３回程度繰り返して確認する。走査速度は１ｍＶ/秒が好ましい。例えば金属酸化物粒子が、ＬｉＭｎ２Ｏ４であれば、サイクリックボルタモグラムにおいて、約３．９Ｖ付近にＬｉＭｎ２Ｏ４のＬｉ脱離反応に相当する酸化ピークが出現し、約４．１Ｖ付近にＬｉ挿入反応に相当する還元ピークが出現する。上記ピークの出現によって、ＬｉＭｎ２Ｏ４のリチウムイオンの挿入脱離反応が確認される。ＬｉＭｎ２Ｏ４を用いた際のサイクリックボルタモグラムにおいて２回目のサイクル結果を図１０に示す。尚、適切な電圧範囲とは、サイクリックボルタンメトリー試験において、試験に用いられる活物質粒子の電圧範囲であって、金属酸化物粒子におけるリチウムイオンの挿入脱離を示すピークの有無が確認できる程度の電圧範囲を意味する。 Specifically, the electrode potential is set and measurement is performed in an appropriate voltage range of the active material particles. For example, when LiMn 2 O 4 is used as the active material particles, it is swept from 3.0 V to 4.3 V whether or not the metal oxide particles are inserted and released from lithium, and then returned to 3.0 V again. Repeat three times to confirm. The scanning speed is preferably 1 mV / sec. For example, if the metal oxide particles are LiMn 2 O 4 , in the cyclic voltammogram, an oxidation peak corresponding to the Li elimination reaction of LiMn 2 O 4 appears in the vicinity of about 3.9 V, and in the vicinity of about 4.1 V. A reduction peak corresponding to the Li insertion reaction appears. The appearance of the peak confirms the insertion / extraction reaction of LiMn 2 O 4 lithium ions. FIG. 10 shows the results of the second cycle in the cyclic voltammogram when LiMn 2 O 4 is used. Note that the appropriate voltage range is the voltage range of the active material particles used in the cyclic voltammetry test, and is such that the presence or absence of a peak indicating insertion / extraction of lithium ions in the metal oxide particles can be confirmed. Refers to the voltage range.
一方、リチウムイオンの挿入脱離反応を示さない金属酸化物粒子の例として、酸化鉄を用いて同様にサイクリックボルタンメトリー試験を実施した場合には、サイクリックボルタモグラムには、ピークが検出されない。酸化鉄を用いた際のサイクリックボルタモグラムにおいて２回目のサイクル結果を図１１に示す。 On the other hand, when a cyclic voltammetry test is similarly performed using iron oxide as an example of metal oxide particles that do not exhibit lithium ion insertion / release reaction, no peak is detected in the cyclic voltammogram. FIG. 11 shows the results of the second cycle in the cyclic voltammogram when using iron oxide.
尚、本発明の電極板を製造するにあたり、電極活物質層中に含有が予定される金属酸化物粒子のリチウムイオン挿入脱離反応の有無は、上述のとおり確認することができる。したがって、予め確認した上で、リチウムイオン挿入脱離反応を示さない金属酸化物粒子が、電極活物質層中における結着物質粒子として決定される。一方、すでに完成された電極板における電極活物質層中にリチウムイオン挿入脱離反応を示さない金属酸化物粒子が含有されているか否かは、例えば、以下のとおり確認することができる。即ち、電極活物質層を削ってサンプルを作成し、該サンプルの組成分析を実施することにより、サンプル中に、いかなる金属酸化物粒子が含有されているかを推定することができる。そして、推定された金属酸化物粒子よりなる塗膜を、アルミニウムなどの基板上に形成し、これをサイクリックボルタンメトリー試験に供することにより、当該金属酸化物粒子がリチウムイオン挿入脱離反応を示すか示さないかを確認することができる。 In producing the electrode plate of the present invention, the presence or absence of the lithium ion insertion / release reaction of the metal oxide particles to be contained in the electrode active material layer can be confirmed as described above. Therefore, after confirming in advance, the metal oxide particles that do not exhibit the lithium ion insertion / release reaction are determined as the binder particles in the electrode active material layer. On the other hand, whether or not metal oxide particles that do not exhibit lithium ion insertion / release reaction are contained in the electrode active material layer of the electrode plate that has already been completed can be confirmed, for example, as follows. That is, it is possible to estimate what kind of metal oxide particles are contained in the sample by cutting the electrode active material layer to prepare a sample and conducting composition analysis of the sample. Then, by forming a coating film composed of the estimated metal oxide particles on a substrate such as aluminum and subjecting it to a cyclic voltammetry test, whether the metal oxide particles exhibit a lithium ion insertion / release reaction It can be confirmed whether it is not shown.
本発明において、電極活物質層中における活物質粒子と金属酸化物粒子の配合比率は特に特定されず、使用される活物質粒子の種類や大きさ、金属酸化物粒子の種類、電極に求められる機能などを勘案して適宜決定することができる。電極活物質層中において、結着物質粒子である金属酸化物粒子の占める割合は、３重量％以上、３０重量％以下であることが好ましい。 In the present invention, the mixing ratio of the active material particles and the metal oxide particles in the electrode active material layer is not particularly specified, and the type and size of the active material particles used, the type of metal oxide particles, and the electrode are required. It can be determined appropriately in consideration of functions and the like. In the electrode active material layer, the proportion of the metal oxide particles as the binder material particles is preferably 3% by weight or more and 30% by weight or less.
樹脂成分、有機金属化合物：
電極活物質中に残存する炭素成分の供給源となる樹脂成分としては、具体的には、ポリエーテル系樹脂、ポリエステル系樹脂、ポリエチレン系樹脂等のオレフィン系樹脂、ポリ塩化ビニル樹脂等のビニル系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、セルロース系樹脂、ポリスチレン系樹脂、メタクリル樹脂、フッ素系樹脂、ポリアミド樹脂、シリコーン樹脂、ウレタン系樹脂、フェノール系樹脂、ポリイミド樹脂、尿素樹脂、エポキシ樹脂、珪素樹脂、ポリシロキサン樹脂等の単体又はこれらの２種以上の混合物、あるいはこれらの変性した樹脂なども使用することができる。より具体的には例えば、ポリエチレングリコール、カルボキシメチルセルロース、エチルセルロース、ニトロセルロース、酢酸セルロース、デンプン、ポリビニルアルコール、エチレングリコール等を例示することができる。これらの有機物は、電極活物質形成溶液を調製する際に、その粘度を調整する作用を発揮する。一方、有機金属化合物としては、チタンジイソプロポキシビス（エチルアセトアセテート）、チタンジイソプロポキシビス（トリエタノールアミネート）等が挙げられる。これら粘度調整材として作用可能な、有機物や有機金属化合物を電極活物質形成溶液に配合させ、集電体上に当該溶液を塗布した後、適切な温度で加熱することにより、形成される電極活物質層中に炭素成分を残存させることができる。
Resin component, organometallic compound:
Specific examples of the resin component that is a supply source of the carbon component remaining in the electrode active material include olefin resins such as polyether resins, polyester resins, and polyethylene resins, and vinyl resins such as polyvinyl chloride resins. Resin, polycarbonate resin, acrylic resin, cellulose resin, polystyrene resin, methacrylic resin, fluorine resin, polyamide resin, silicone resin, urethane resin, phenol resin, polyimide resin, urea resin, epoxy resin, silicon resin A simple substance such as a polysiloxane resin, a mixture of two or more of these, or a modified resin thereof can also be used. More specifically, for example, polyethylene glycol, carboxymethyl cellulose, ethyl cellulose, nitrocellulose, cellulose acetate, starch, polyvinyl alcohol, ethylene glycol and the like can be exemplified. These organic substances exhibit an effect of adjusting the viscosity when preparing an electrode active material forming solution. On the other hand, examples of the organometallic compound include titanium diisopropoxybis (ethyl acetoacetate) and titanium diisopropoxybis (triethanolaminate). The electrode active material formed by blending an organic substance or an organometallic compound that can act as a viscosity modifier in the electrode active material forming solution, applying the solution onto the current collector, and heating at an appropriate temperature. The carbon component can remain in the material layer.
その他の材料：
上記電極活物質層は、上述する活物質粒子および結着物質粒子である金属酸化物粒子のみから構成することが可能であるが、本発明の趣旨を逸脱しない範囲において、さらなる添加剤が含有されていてもよい。たとえば、本発明の電極板は、導電材を使用することなく良好な導電性を発揮させることが可能であるが、より優れた導電性が望まれる場合や、活物質粒子の含有量を増大させたい場合などには、導電材を使用することが望ましい。
Other materials:
The electrode active material layer can be composed only of the above-mentioned active material particles and metal oxide particles that are binder material particles, but further additives are contained within the scope of the present invention. It may be. For example, the electrode plate of the present invention can exhibit good conductivity without using a conductive material, but when better conductivity is desired or the content of active material particles is increased. For example, it is desirable to use a conductive material.
上記導電材としては、通常、非水電解液二次電池用電極板に用いられるものを使用することができ、アセチレンブラック、ケッチェンブラック等のカーボンブラック等の炭素材料が例示されるが、これに限定されるものではない。導電材の平均粒径は２０ｎｍ〜５０ｎｍ程度であることが好ましい。また異なる導電材としては炭素繊維（ＶＧＣＦ）が公知である。上記平均粒径は、活物質粒子の平均粒径を測定する方法と同様に、電子顕微鏡による実測から求められる算術平均により求められる。 As the conductive material, those usually used for electrode plates for non-aqueous electrolyte secondary batteries can be used, and examples thereof include carbon materials such as acetylene black and carbon black such as ketjen black. It is not limited to. The average particle size of the conductive material is preferably about 20 nm to 50 nm. Carbon fiber (VGCF) is known as a different conductive material. The average particle diameter is obtained by an arithmetic average obtained from actual measurement using an electron microscope, as in the method of measuring the average particle diameter of the active material particles.
導電材を電極活物質層に含有させる場合には、その含有量は特に限定されないが、一般的には、活物質粒子１００重量部、あるいは活物質粒子および結着物質粒子の総量１００重量部に対して、導電材の割合が５重量部以上２０重量部以下となるようにすることが望ましい。 When the conductive material is contained in the electrode active material layer, the content is not particularly limited, but in general, it is 100 parts by weight of the active material particles or 100 parts by weight of the total amount of the active material particles and the binder material particles. On the other hand, it is desirable that the ratio of the conductive material is 5 parts by weight or more and 20 parts by weight or less.
また本発明は、樹脂製結着材を使用せずとも活物質粒子を集電体上に固着させることができるものであるが、これは電極活物質層に樹脂成分が含有されることを禁止する趣旨ではない。たとえば、電極板を用いて電池を組み立てる場合には、電解液を電極の細孔内部へしみこませる必要があり、この際、電解液の浸透性を向上させるために電極活物質層中に、樹脂成分を１〜１０％ほど含有させる場合がある。このように、必要に応じて、本発明においても電極活物質層中に少量の樹脂材料を含有させてもよい。あるいは、結着物質として、金属酸化物に加え、樹脂製結着材も電極活物質層中に含有されていてもよい。 In the present invention, the active material particles can be fixed on the current collector without using a resin binder, but this prohibits the resin component from being contained in the electrode active material layer. It is not the purpose. For example, when assembling a battery using an electrode plate, it is necessary to immerse the electrolyte into the pores of the electrode. At this time, in order to improve the permeability of the electrolyte, a resin is contained in the electrode active material layer. The component may be contained in an amount of 1 to 10%. Thus, if necessary, a small amount of resin material may be contained in the electrode active material layer in the present invention. Alternatively, as the binder, in addition to the metal oxide, a resin binder may be contained in the electrode active material layer.
（直流抵抗測定）
本発明において、電極板の出入力特性は、製造された電極板の直流抵抗値（Ω）を測定することにより、評価することができる。即ち、電極板の直流抵抗値が、低くなるということは出力が高くなることを意味し、その結果、出入力特性が向上したと理解することができる。上記直流抵抗値は、以下に示す方法で測定することができる。
(DC resistance measurement)
In the present invention, the input / output characteristics of the electrode plate can be evaluated by measuring the DC resistance value (Ω) of the manufactured electrode plate. That is, a decrease in the DC resistance value of the electrode plate means an increase in output, and as a result, it can be understood that the input / output characteristics are improved. The DC resistance value can be measured by the following method.
直流抵抗値の測定は、試験セルを用いて、次のように算出する。２種類の放電レート（たとえば放電レート１Ｃと５Ｃ）で放電試験を実施した場合において、放電開始後１０秒後の電圧値（ｍＶ）を測定する。たとえば、放電レート１Ｃの条件での放電試験を実施した場合については電圧値（Ｖ１）（ｍＶ）、放電レート５Ｃの条件での放電試験を実施した場合についても、放電開始後１０秒後の電圧値（Ｖ５）（ｍＶ）を測定する。そして、これらの測定値（Ｖ１，Ｖ５）と、放電レート１Ｃ、５Ｃそれぞれに対応する定電流値（Ｉ１，Ｉ５）（ｍＡ）に基づき、下記（１）式により、直流抵抗値（Ω）が算出される。尚、この試験で抵抗値が小さいときは、電子とリチウムイオンの流れがスムーズであり、作用板の出入力特性が向上していると評価される。 The DC resistance value is measured using a test cell as follows. When a discharge test is performed at two types of discharge rates (for example, discharge rates 1C and 5C), a voltage value (mV) 10 seconds after the start of discharge is measured. For example, the voltage value (V1) (mV) when the discharge test is performed under the condition of the discharge rate 1C, and the voltage 10 seconds after the start of the discharge when the discharge test is performed under the condition of the discharge rate 5C. The value (V5) (mV) is measured. Based on these measured values (V1, V5) and the constant current values (I1, I5) (mA) corresponding to the discharge rates 1C, 5C, the direct current resistance value (Ω) is calculated by the following equation (1). Calculated. When the resistance value is small in this test, it is evaluated that the flow of electrons and lithium ions is smooth and the input / output characteristics of the action plate are improved.
[非水電解液二次電池用電極板を製造する方法]
次に、本発明の非水電解液二次電池用電極板を製造する方法、（以下、「本発明電極板の製造方法」ともいう）の例について説明する。本発明電極板を製造するにあたり、まず結着物質粒子である金属酸化物粒子の前駆体となる金属元素含有化合物および活物質粒子、あるいはさらに任意の添加剤を含む、電極活物質層形成液を調製する。そして本発明の電極板を製造する方法は、この電極活物質層形成液を集電体表面の所望の領域に塗布して塗膜を形成する塗布工程と、電極活物質層形成液を塗布して形成した塗膜より電極活物質層を形成する電極活物質層形成工程と、を順に備える。
[Method for producing electrode plate for non-aqueous electrolyte secondary battery]
Next, an example of a method for producing the electrode plate for a non-aqueous electrolyte secondary battery of the present invention (hereinafter also referred to as “method for producing the electrode plate of the present invention”) will be described. In producing the electrode plate of the present invention, first, an electrode active material layer forming liquid containing a metal element-containing compound and active material particles, which are precursors of metal oxide particles as binding material particles, or further optional additives. Prepare. And the method of manufacturing the electrode plate of the present invention comprises applying an electrode active material layer forming solution by applying the electrode active material layer forming solution to a desired region on the surface of the current collector to form a coating film. An electrode active material layer forming step of forming an electrode active material layer from the coating film formed in this order.
上記電極活物質層形成工程は、上記塗膜に含まれる溶媒を除去するとともに、上記塗膜中に含有される金属元素含有化合物を反応させて金属酸化物粒子を生成し、該金属酸化物粒子によって上記活物質粒子を上記集電体上に固着させることによって、上記集電体上に該金属酸化物粒子と上記活物質粒子とを含有する電極活物質層を形成する工程であってよい。 In the electrode active material layer forming step, the solvent contained in the coating film is removed and the metal element-containing compound contained in the coating film is reacted to generate metal oxide particles. In this step, the active material particles may be fixed on the current collector to form an electrode active material layer containing the metal oxide particles and the active material particles on the current collector.
あるいは、本発明電極板の製造方法では、電極活物質層形成液の塗布工程と、上記電極活物質層形成工程との間に、任意の工程を設け、塗膜中の溶媒を除去した後に、電極活物質層形成工程を実施してもよい。即ち、電極活物質層形成工程は、予め溶媒の除去された塗膜中に含有される金属元素含有化合物を反応させて金属酸化物粒子を生成し、該金属酸化物によって上記活物質粒子を集電体上に固着させることによって、上記集電体上に該金属酸化物粒子と上記活物質粒子とを含有する電極活物質層を形成する工程であってもよい。 Alternatively, in the method for producing an electrode plate of the present invention, an optional step is provided between the coating step of the electrode active material layer forming liquid and the electrode active material layer forming step, and after removing the solvent in the coating film, An electrode active material layer forming step may be performed. That is, in the electrode active material layer forming step, a metal element-containing compound contained in the coating film from which the solvent has been removed is reacted to generate metal oxide particles, and the active material particles are collected by the metal oxide. It may be a step of forming an electrode active material layer containing the metal oxide particles and the active material particles on the current collector by being fixed on the current collector.
尚、上記方法は、正極板を製造する場合には、正極活物質層を集電体上に積層形成するために、電極活物質層形成液には、正極活物質粒子およびこれに適した金属元素含有化合物を添加し、また負極板を製造する場合には、負極活物質層を集電体上に積層形成するために、電極活物質層形成液には、負極活物質粒子およびこれに適した金属元素含有化合物を添加する。ただし、本発明の製造方法において、「正極」および「負極」を、まとめて「電極」として示す場合がある。 In the above method, when producing a positive electrode plate, the positive electrode active material layer and the metal suitable therefor are used as the electrode active material layer forming liquid in order to form a positive electrode active material layer on the current collector. When an element-containing compound is added and a negative electrode plate is produced, the negative electrode active material layer and the electrode active material layer forming liquid are suitable for the negative electrode active material layer formation liquid in order to form a negative electrode active material layer on the current collector. Add the metal element-containing compound. However, in the manufacturing method of the present invention, “positive electrode” and “negative electrode” may be collectively referred to as “electrode”.
上記電極活物質層形成工程は、例えば、加熱工程、減圧乾燥工程、減圧加熱工程、あるいはこれらの組み合わせなどが例示されるが、これらに限定されず、集電体上に塗布された電極活物質層形成液により形成された塗膜を電極活物質層として形成可能な手段を実施する工程であればよい。例えば、上記電極活物質層形成工程は、上記塗膜中に含有される溶媒を除去する手段を実施し、次いで金属元素含有化合物を反応させる手段を実施するなど、２以上の手段を含んでもよい。金属元素含有化合物から金属酸化物を生成させるには、通常、金属元素含有化合物を熱分解して酸化する等の方法が採用されるが、金属元素化合物から金属酸化物を生成することができれば、これに限らない。 Examples of the electrode active material layer forming step include, but are not limited to, a heating step, a reduced pressure drying step, a reduced pressure heating step, or a combination thereof, and an electrode active material applied on a current collector. What is necessary is just the process of implementing the means which can form the coating film formed with the layer formation liquid as an electrode active material layer. For example, the electrode active material layer forming step may include two or more means such as a means for removing the solvent contained in the coating film and then a means for reacting the metal element-containing compound. . In order to produce a metal oxide from a metal element-containing compound, a method such as thermal decomposition and oxidation of the metal element-containing compound is usually employed, but if a metal oxide can be produced from a metal element compound, Not limited to this.
上記電極活物質層形成工程が、加熱手段を実施する加熱工程である場合には、本発明の電極板は、上記電極活物質層形成液を集電体上に塗布し、電極活物質形成液に含有される金属元素含有化合物の熱分解開始温度以上の温度で加熱して熱分解させ、金属元素を酸化せしめてリチウム挿入脱離反応を示さない金属酸化物粒子を生成し、該金属酸化物粒子によって活物質粒子を集電体上に固着させ、電極活物質層を形成することによって製造することができる。このとき、活物質粒子の平均粒径よりも生成される金属酸化物粒子の平均粒径の方が小さくなるように、加熱温度・加熱時間などの製造条件を適宜決定する。上記電極活物質層形成液中に含まれる活物質粒子や導電材粒子は、結着物質粒子である金属酸化物粒子が介在して両者を固着させる前記固着態様１に加え、固着態様２として前記したような粒子同士の直接の接触を良好に保って固着される態様が含まれる。このように、固着態様１および２に示されるような固着の状態を可能とするのは、本発明の電極板を製造する方法において、金属元素含有化合物が溶媒に溶解され、且つ、活物質粒子等を混合した電極活物質層形成液を集電体上に塗布して電極活物質層を形成する際に、加熱などの手段により溶媒が除去され、生成される金属酸化物粒子（結着物質粒子）が、粒子間、あるいは粒子同士が直接に接触する接触部分の周囲に生成されるからである。この結果、上記方法は、導電性が良好で電気抵抗を低く保つことが可能な電極板を製造することができる。尚、本発明電極板の製造方法において、電極活物質層形成液中に含まれる金属元素含有化合物は、溶媒に溶解した状態のものも含めて金属元素含有化合物と呼ぶ。 In the case where the electrode active material layer forming step is a heating step for carrying out a heating means, the electrode plate of the present invention is obtained by applying the electrode active material layer forming liquid onto a current collector, The metal oxide containing compound is heated at a temperature equal to or higher than the thermal decomposition start temperature of the metal element-containing compound and thermally decomposed to oxidize the metal element to produce metal oxide particles that do not exhibit lithium insertion / extraction reaction. The active material particles can be fixed on the current collector by the particles to form an electrode active material layer. At this time, the production conditions such as the heating temperature and the heating time are appropriately determined so that the average particle size of the metal oxide particles produced is smaller than the average particle size of the active material particles. In addition to the fixing mode 1 in which the active material particles and the conductive material particles contained in the electrode active material layer forming liquid are bonded to each other through metal oxide particles as binding material particles, Such a mode is included in which the particles are firmly fixed and kept in direct contact with each other. As described above, the fixing state as shown in the fixing modes 1 and 2 is possible because the metal element-containing compound is dissolved in the solvent and the active material particles in the method for producing the electrode plate of the present invention. When forming an electrode active material layer by applying an electrode active material layer forming liquid mixed with the above to a current collector, the solvent is removed by means such as heating, and the resulting metal oxide particles (binding material) This is because the particles are generated between the particles or around the contact portion where the particles directly contact each other. As a result, the above method can produce an electrode plate that has good electrical conductivity and can keep electric resistance low. In the method for producing an electrode plate of the present invention, the metal element-containing compound contained in the electrode active material layer forming liquid is referred to as a metal element-containing compound, including those dissolved in a solvent.
活物質粒子：
上記電極活物質層形成液に含有される活物質粒子は、上述において既に説明した正極活物質粒子、あるいは負極活物質粒子と同様であるため、ここではその説明を割愛する。
Active material particles:
Since the active material particles contained in the electrode active material layer forming liquid are the same as the positive electrode active material particles or the negative electrode active material particles already described above, the description thereof is omitted here.
金属酸化物の前駆体である金属元素含有化合物：
上記電極活物質層形成液中に溶解される金属元素含有化合物は、電極活物質層中に含有され、リチウムイオン挿入脱離反応を示さない金属酸化物の前駆体であって、活物質粒子同士を固着させ、また、活物質粒子を集電体上に固着させる結着物質粒子となる金属酸化物粒子の前駆体である。したがって、上記金属元素含有化合物は、溶液中に溶解された状態で基板上に塗布され、熱分解開始温度以上で加熱されたときに、上述する金属酸化物粒子を生成することができるものであればよい。尚、使用する金属元素含有化合物から生成される金属酸化物粒子が、リチウムイオン挿入脱離反応を示さないものであることは、予備実験において、同様の金属元素含有化合物が含有される溶液を基板上に塗布してこれを加熱することによって金属酸化物粒子を形成し、上述するサイクリックボルタンメトリー法により確認することができる。
Metal element-containing compounds that are precursors of metal oxides:
The metal element-containing compound dissolved in the electrode active material layer forming liquid is a metal oxide precursor that is contained in the electrode active material layer and does not exhibit a lithium ion insertion / release reaction, and the active material particles And a precursor of metal oxide particles to be binding material particles for fixing the active material particles on the current collector. Therefore, the metal element-containing compound is capable of generating the above-described metal oxide particles when applied on a substrate in a state dissolved in a solution and heated at a temperature equal to or higher than the thermal decomposition start temperature. That's fine. Note that the metal oxide particles produced from the metal element-containing compound used do not exhibit lithium ion insertion / release reaction. In preliminary experiments, a solution containing the same metal element-containing compound was used as a substrate. The metal oxide particles can be formed by coating on and heating this, and can be confirmed by the cyclic voltammetry method described above.
上記金属元素含有化合物は、結着物質粒子となる前記金属酸化物中の金属元素を含有する化合物であり、具体的には、Ｌｉ、Ｂｅ、Ｎａ、Ｍｇ、Ａｌ、Ｓｉ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｒｂ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｉｎ、Ｓｎ、Ｃｓ、Ｂａ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、Ｈｇ、Ｔｌ、Ｐｂ、Ｂｉ、Ｆｒ、Ｒａ、およびＣｅなどの金属元素の１種の金属酸化物粒子、または２種以上の金属元素を含む化合物が挙げられるが、第３周期乃至第５周期に属する金属元素含有化合物を用いると、生成される電極板の出入力特性がより高くなる傾向にあるため好ましい。 The metal element-containing compound is a compound containing a metal element in the metal oxide to be a binder particle, specifically, Li, Be, Na, Mg, Al, Si, K, Ca, Sc Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs , Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Fr, Ra, and Ce, one kind of metal oxide particles, or two or more kinds However, it is preferable to use a metal element-containing compound belonging to the third period to the fifth period because the input / output characteristics of the produced electrode plate tend to be higher.
また金属元素含有化合物としては、例えば金属塩が好ましく使用されるが、有機金属化合物も使用することができる。金属塩としては、塩化物、硝酸塩、硫酸塩、過塩素酸塩、酢酸塩、リン酸塩、臭素酸塩、炭酸塩等を挙げることができる。中でも、本発明においては、塩化物、硝酸塩、酢酸塩は汎用品として入手が容易なので、使用することが好ましい。とりわけ、硝酸塩は安価で広範囲の種類の集電体に対して製膜性がよいので、好ましく使用される。 Further, as the metal element-containing compound, for example, a metal salt is preferably used, but an organometallic compound can also be used. Examples of the metal salt include chloride, nitrate, sulfate, perchlorate, acetate, phosphate, bromate, carbonate, and the like. Among them, in the present invention, chloride, nitrate, and acetate are preferably used because they are easily available as general-purpose products. In particular, nitrates are preferably used because they are inexpensive and have good film-forming properties for a wide variety of current collectors.
金属元素含有化合物として用いられる金属塩の具体的な例示としては、塩化マグネシウム、硝酸アルミニウム、塩化アルミニウム、塩化カルシウム、酢酸スカンジウム、四塩化チタン、オキソ硫酸バナジウム、クロム酸アンモニウム、塩化クロム、二クロム酸アンモニウム、酢酸クロム、硝酸クロム、硫酸クロム、硝酸マンガン、硫酸マンガン、塩化鉄（Ｉ）、塩化鉄（ＩＩＩ）、硝酸鉄（Ｉ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸アンモニウム鉄（ＩＩＩ）、塩化コバルト、硝酸コバルト、酢酸コバルト、塩化ニッケル、硝酸ニッケル、酢酸ニッケル、塩化銅、硝酸銅、塩化亜鉛、酢酸亜鉛、硝酸イットリウム、塩化イットリウム、塩化酸化ジルコニウム、硝酸酸化ジルコニウム、四塩化ジルコニウム、塩化銀、酢酸銀、硝酸インジウム、酢酸インジウム、硫酸スズ、塩化セリウム、酢酸セリウム、硝酸セリウム、シュウ酸セリウム、硝酸二アンモニウムセリウム、硫酸セリウム、塩化サマリウム、硝酸サマリウム、塩化鉛、酢酸鉛、硝酸鉛、ヨウ化鉛、リン酸鉛、硫酸鉛、塩化ランタン、酢酸ランタン、硝酸ランタン、硝酸ガドリニウム、塩化ストロンチウム、酢酸ストロンチウム、硝酸ストロンチウム、五塩化ニオブ、リン酸モリブデン酸アンモニウム、硫化モリブデン、塩化パラジウム、酢酸パラジウム、硝酸パラジウム、五塩化アンチモン、三塩化アンチモン、三フッ化アンチモン、テルル酸、亜硫酸バリウム、塩化バリウム、塩素酸バリウム、過塩素酸バリウム、酢酸バリウム、硝酸バリウム、タングステン酸、タングステン酸アンモニウム、六塩化タングステン、五塩化タンタル、塩化ハフニウム、硫酸ハフニウム等を挙げることができる。 Specific examples of metal salts used as metal element-containing compounds include magnesium chloride, aluminum nitrate, aluminum chloride, calcium chloride, scandium acetate, titanium tetrachloride, vanadium oxosulfate, ammonium chromate, chromium chloride, dichromic acid. Ammonium, chromium acetate, chromium nitrate, chromium sulfate, manganese nitrate, manganese sulfate, iron (I) chloride, iron (III) chloride, iron (I) nitrate, iron (III) nitrate, iron (II) sulfate, ammonium iron sulfate ( III), cobalt chloride, cobalt nitrate, cobalt acetate, nickel chloride, nickel nitrate, nickel acetate, copper chloride, copper nitrate, zinc chloride, zinc acetate, yttrium nitrate, yttrium chloride, zirconium chloride, zirconium nitrate, zirconium tetrachloride , Silver chloride, silver acetate, indium nitrate , Indium acetate, tin sulfate, cerium chloride, cerium acetate, cerium nitrate, cerium oxalate, cerium nitrate, cerium sulfate, samarium chloride, samarium nitrate, lead chloride, lead acetate, lead nitrate, lead iodide, phosphoric acid Lead, lead sulfate, lanthanum chloride, lanthanum acetate, lanthanum nitrate, gadolinium nitrate, strontium chloride, strontium acetate, strontium nitrate, niobium pentachloride, ammonium molybdate phosphate, molybdenum sulfide, palladium chloride, palladium acetate, palladium nitrate, pentachloride Antimony, antimony trichloride, antimony trifluoride, telluric acid, barium sulfite, barium chloride, barium chlorate, barium perchlorate, barium acetate, barium nitrate, tungstic acid, ammonium tungstate, tungsten hexachloride , Mention may be made of tantalum pentachloride, hafnium chloride, sulfuric acid hafnium and the like.
金属元素含有化合物は、結着物質粒子となる金属酸化物に相当する金属元素を含む化合物を、１種又は２種以上組み合わせて用いる。例えば、結着物質粒子として酸化チタン粒子や、酸化鉄粒子を生成する場合には、四塩化チタン等のチタン化合物や、塩化鉄（Ｉ）、塩化鉄（ＩＩＩ）、硝酸鉄（Ｉ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸アンモニウム鉄（ＩＩＩ）等の鉄化合物を用いる。また２種以上の金属を含む金属複合酸化物であるガドリニウムが置換された酸化セリウムを生成するためには、塩化セリウム、酢酸セリウム、硝酸セリウム、シュウ酸セリウム、硝酸二アンモニウムセリウム、硫酸セリウム等のセリウム化合物と、硝酸ガドリニウム等のガドリニウム化合物とを併用し、イットリウムが置換された酸化ジルコニウムを生成するためには、塩化酸化ジルコニウム、硝酸酸化ジルコニウム、四塩化ジルコニウム等のジルコニウム化合物と、硝酸イットリウム、塩化イットリウム等のイットリウム化合物とを併用する。また鉄とチタンの混合酸化物を生成するためには、四塩化チタン等のチタン化合物と、塩化鉄（Ｉ）、塩化鉄（ＩＩＩ）、硝酸鉄（Ｉ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸アンモニウム鉄（ＩＩＩ）等の鉄化合物とを併用し、インジウムとスズが混合された酸化物を生成するためには、硝酸インジウム、酢酸インジウム等のインジウム化合物と、硫酸スズ等のスズ化合物とを併用する。 As the metal element-containing compound, a compound containing a metal element corresponding to a metal oxide to be a binder particle is used alone or in combination of two or more. For example, when titanium oxide particles or iron oxide particles are produced as binder particles, titanium compounds such as titanium tetrachloride, iron chloride (I), iron chloride (III), iron nitrate (I), nitric acid Iron compounds such as iron (III), iron (II) sulfate, and ammonium iron (III) sulfate are used. In order to produce cerium oxide substituted with gadolinium, which is a metal complex oxide containing two or more metals, cerium chloride, cerium acetate, cerium nitrate, cerium oxalate, diammonium cerium nitrate, cerium sulfate, etc. In order to produce zirconia substituted with yttrium by using a cerium compound and a gadolinium compound such as gadolinium nitrate, a zirconium compound such as chlorinated zirconium oxide, zirconium nitrate oxide, zirconium tetrachloride, yttrium nitrate, chloride Use with yttrium compounds such as yttrium. In order to produce a mixed oxide of iron and titanium, a titanium compound such as titanium tetrachloride, iron (I) chloride, iron (III) chloride, iron (I) nitrate, iron (III) nitrate, iron sulfate (II) In combination with an iron compound such as ammonium iron sulfate (III) to produce an oxide in which indium and tin are mixed, an indium compound such as indium nitrate and indium acetate and tin such as tin sulfate Used in combination with a compound.
尚、電極活物質層中における活物質粒子の平均粒径よりも、生成される金属酸化物粒子の平均粒径が小さくなるよう製造するための１つの態様として、先駆体として用いる金属元素含有化合物を、チタン化合物、鉄化合物の中から選択することが望ましい。ただし、選択される金属元素含有化合物はこれに限定されない。 In addition, as one aspect for producing so that the average particle diameter of the generated metal oxide particles is smaller than the average particle diameter of the active material particles in the electrode active material layer, a metal element-containing compound used as a precursor Is preferably selected from titanium compounds and iron compounds. However, the metal element-containing compound selected is not limited to this.
上述する電極活物質層形成液において、溶媒中における、添加される１種または２種以上の金属元素含有化合物の添加量の合計の比率は、０．０１〜５ｍｏｌ／Ｌ、特に０．１〜２ｍｏｌ／Ｌが好ましい。上記濃度が０．０１ｍｏｌ／Ｌ以上であることにより、集電体と該集電体表面で生成される電極活物質層とが良好に密着し、活物質粒子の固着が図られる。また、上記濃度が、５ｍｏｌ／Ｌ以下であることにより、上記電極活物質層形成液は集電体表面へ良好に塗布できる程度の良好な粘度を維持することができ、均一な塗膜が形成される。 In the electrode active material layer forming liquid described above, the ratio of the total amount of one or more metal element-containing compounds added in the solvent is 0.01 to 5 mol / L, particularly 0.1 to 5 mol / L. 2 mol / L is preferred. When the concentration is 0.01 mol / L or more, the current collector and the electrode active material layer generated on the surface of the current collector are satisfactorily adhered, and the active material particles are fixed. Further, when the concentration is 5 mol / L or less, the electrode active material layer forming liquid can maintain a good viscosity enough to be applied to the current collector surface, and a uniform coating film is formed. Is done.
（その他の添加剤）
また上記電極活物質層形成液には、上述する活物質粒子および金属元素含有化合物以外にも、導電材あるいは、本発明の趣旨を逸脱しない範囲において、その他の添加剤を添加してもよい。上記導電材及びその他の添加剤は、本発明の電極活物質層の説明において記載した内容と同様のものを用いることができる。
(Other additives)
In addition to the active material particles and the metal element-containing compound described above, other additives may be added to the electrode active material layer forming liquid without departing from the spirit of the present invention. As the conductive material and other additives, the same materials as described in the description of the electrode active material layer of the present invention can be used.
導電材を電極活物質層形成液に添加する場合には、集電体表面上において生成される活物質粒子、あるいは活物質粒子および形成が予定される金属酸化物の総量１００重量部に対して、導電材の添加量が５重量部〜２０重量部であることが望ましい。尚、上述は、２０重量を超えて導電材を添加することを除外する趣旨ではない。 When the conductive material is added to the electrode active material layer forming liquid, the active material particles generated on the current collector surface, or the active material particles and the total amount of metal oxides scheduled to be formed are 100 parts by weight. In addition, the addition amount of the conductive material is desirably 5 to 20 parts by weight. In addition, the above is not the meaning which excludes adding a conductive material exceeding 20 weight.
（溶媒）
上記電極活物質層形成液を調製するために用いられる溶媒としては、特に限定されないが、例えば、水、あるいは、メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、ノルマルブチルアルコール、イソブチルアルコール、セカンダリーブチルアルコール、ターシャリーブチルアルコール等の総炭素数が５以下の低級アルコール、アセチルアセトン、ジアセチル、ベンゾイルアセトン等のジケトン類、アセト酢酸エチル、ピルビン酸エチル、ベンゾイル酢酸エチル、ベンゾイル蟻酸エチル等のケトエステル類、トルエン、あるいはこれらの２種以上の組み合わせからなる混合溶媒等を挙げることができる。
(solvent)
The solvent used for preparing the electrode active material layer forming liquid is not particularly limited. For example, water or methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, secondary Lower alcohols having a total carbon number of 5 or less such as butyl alcohol and tertiary butyl alcohol, diketones such as acetylacetone, diacetyl and benzoylacetone, ketoesters such as ethyl acetoacetate, ethyl pyruvate, ethyl benzoylacetate and ethyl benzoylformate, Examples thereof include toluene or a mixed solvent composed of a combination of two or more of these.
尚、上記電極活物質層形成液は、集電体上に形成が予定される電極活物質層における活物質粒子、金属酸化物粒子、あるいはさらに必要に応じて導電材などのその他の添加剤を必要量含まれるように勘案して、これらの配合量が決定される。その際、溶媒に添加される溶質（即ち、活物質粒子、金属元素含有化合物および任意の添加剤）の比率は、塗布工程において集電体上への塗布性及び、電極活物質層形成工程における溶媒の除去を勘案し、適宜調整する。一般的には、電極活物質層形成液を１００重量％としたときに、含有される溶質の総量は、３０〜７０重量％となるよう調整される。 The electrode active material layer forming liquid contains active material particles, metal oxide particles in the electrode active material layer scheduled to be formed on the current collector, or other additives such as a conductive material if necessary. These blending amounts are determined in consideration of the necessary amount. At that time, the ratio of the solute added to the solvent (that is, the active material particles, the metal element-containing compound, and the optional additive) depends on the coating property on the current collector and the electrode active material layer forming step in the coating step. Adjust as appropriate in consideration of removal of the solvent. Generally, when the electrode active material layer forming liquid is 100% by weight, the total amount of solutes contained is adjusted to be 30 to 70% by weight.
次に、以上のとおり調製された電極活物質層形成液を、集電体上に塗布して塗膜を形成する。尚、本発明の電極板を製造する方法において用いられる集電体は、上記非水電解液二次電池用電極板に用いられる集電体と同様であるため、ここではその説明を割愛する。 Next, the electrode active material layer forming liquid prepared as described above is applied onto a current collector to form a coating film. The current collector used in the method for producing the electrode plate of the present invention is the same as the current collector used for the electrode plate for a non-aqueous electrolyte secondary battery, and the description thereof is omitted here.
本発明の電極板を製造する方法における塗布工程では、形成液の塗布方法として公知の塗布方法を、適宜選択して実施することができる。たとえば、印刷法、スピンコート、ディップコート、バーコート、スプレーコート等によって、集電体表面の任意の領域に上記電極活物質層形成液を塗布して塗膜を形成することができる。また、集電体表面が多孔質であったり、凹凸が多数設けられていたり、三次元立体構造を有したりする場合には、塗布方法は、上記方法以外であって手動で塗布することも可能である。尚、本発明において使用する集電体は、必要に応じて、予めコロナ処理や酸素プラズマ処理等を行うことで、電極活物質層の製膜性をさらに改善することができるため好ましい。 In the coating step in the method for producing the electrode plate of the present invention, a known coating method can be appropriately selected and carried out as a forming liquid coating method. For example, the electrode active material layer forming liquid can be applied to any region of the current collector surface to form a coating film by printing, spin coating, dip coating, bar coating, spray coating, or the like. In addition, when the current collector surface is porous, has a large number of irregularities, or has a three-dimensional structure, the coating method is other than the above method and may be applied manually. Is possible. Note that the current collector used in the present invention is preferable because corona treatment, oxygen plasma treatment, and the like can be performed in advance as necessary to further improve the film forming property of the electrode active material layer.
上記電極活物層形成液の集電体への塗布量は、製造される電極板の用途等に応じて任意に決めることができるが、本発明における電極活物質層は、上述のとおり非常に薄く形成することが可能であるため、薄膜化を図りたい場合には、最終的な電極活物質層の厚みが３００ｎｍ〜１５０μｍ、特には５００ｎｍ〜１００μｍ程度となるように薄く塗布してよい。以上の通り、基板に電極活物質層形成液を塗布することにより、結着物質粒子である金属酸化物粒子の前駆体である金属元素含有化合物が含有される電極活物質層形成用の塗膜が形成される。 The amount of the electrode active material layer-forming liquid applied to the current collector can be arbitrarily determined according to the application of the electrode plate to be produced, etc., but the electrode active material layer in the present invention is very In order to reduce the thickness, the final electrode active material layer may be thinly applied so that the final electrode active material layer has a thickness of about 300 nm to 150 μm, particularly about 500 nm to 100 μm. As described above, a coating film for forming an electrode active material layer containing a metal element-containing compound that is a precursor of metal oxide particles that are binding material particles by applying an electrode active material layer forming liquid to a substrate Is formed.
上記塗布工程と、電極活物質層形成工程との間、あるいは、電極活物質層形成工程の後には、さらにプレス工程を実施してもよい。上記プレス工程は、集電体上に形成された上記電極活物質層形成用塗膜を、必要に応じて乾燥させて溶媒を除去し、その後、プレスすることによって実施することができる。したがって、プレス工程後に電極活物質層形成工程を実施する場合には、該電極活物質層形成工程前に予め、塗膜中の溶媒の一部または全部が除去されていてよい。プレス方法は、従来の樹脂製結着材が含まれるスラリー状の電極活物質層形成液を集電体上に塗布して乾燥させ、次いで実施されるプレスと同様の方法で実施することができるが、これに限定されない。このように本発明の電極板を製造する方法は、プレス工程を実施することによって、最終的に製造される電極板における電極活物質層の空隙率を調整し、また体積当たりのエネルギー密度を増加させることができる。 A pressing step may be further performed between the coating step and the electrode active material layer forming step or after the electrode active material layer forming step. The said press process can be implemented by drying the said coating film for electrode active material layer formation formed on the electrical power collector as needed, removing a solvent, and pressing it after that. Therefore, when performing an electrode active material layer formation process after a press process, a part or all of the solvent in a coating film may be removed beforehand before this electrode active material layer formation process. The pressing method can be carried out in the same manner as the press performed by applying a slurry-like electrode active material layer forming liquid containing a conventional resin binder on the current collector and drying it. However, it is not limited to this. As described above, the method for producing the electrode plate of the present invention adjusts the porosity of the electrode active material layer in the finally produced electrode plate and increases the energy density per volume by performing the pressing step. Can be made.
次に、上記塗布工程において形成された塗膜から電極活物質層を形成するための電極活物質層形成工程について、該塗膜を加熱する加熱工程を例に説明する。本加熱工程は、上記塗膜中に存在する金属元素含有化合物を熱分解するとともに酸化させ、且つ、該塗膜中に含まれる溶媒を除去することを目的に行われる（ただし、加熱工程前にプレス工程を実施する場合には、溶媒は実質的にはプレスにおける乾燥で予め除去されている）。加熱方法としては、後述する加熱温度で、塗膜を加熱することができる加熱方法あるいは加熱装置であれば、特に限定されず、適宜選択して実施することができる。具体的な例としては、ホットプレート、オーブン、加熱炉、赤外線ヒーター、ハロゲンヒーター、熱風送風機等のいずれかを使用するか、あるいは２以上を組み合わせて使用する方法を挙げることができる。用いられる集電体が平面状である場合には、加熱工程は、ホットプレート等を使用することが好ましい。尚、ホットプレートを用いて加熱する場合には、塗膜面側が、ホットプレート面と接しない向きに設置して加熱することが好ましい。上記加熱温度は用いられる金属元素含有化合物の種類によって異なるが、上記塗膜を通常１５０℃〜８００℃の温度範囲において加熱することにより良好に金属元素含有化合物の熱分解が行われ、速やかに金属酸化物粒子が生成される。 Next, the electrode active material layer forming step for forming the electrode active material layer from the coating film formed in the coating step will be described by taking a heating step for heating the coating film as an example. This heating step is carried out for the purpose of thermally decomposing and oxidizing the metal element-containing compound present in the coating film, and removing the solvent contained in the coating film (but before the heating step) When carrying out the pressing step, the solvent is substantially removed beforehand by drying in the press). The heating method is not particularly limited as long as it is a heating method or a heating apparatus capable of heating the coating film at a heating temperature described later, and can be appropriately selected and carried out. Specific examples include a method of using a hot plate, an oven, a heating furnace, an infrared heater, a halogen heater, a hot air blower, or the like, or a combination of two or more. When the current collector to be used is planar, it is preferable to use a hot plate or the like for the heating step. In addition, when heating using a hot plate, it is preferable to install and heat the coating film surface side in a direction not in contact with the hot plate surface. The heating temperature varies depending on the type of the metal element-containing compound used. However, the metal element-containing compound is favorably thermally decomposed by heating the coating film in a temperature range of 150 ° C. to 800 ° C. Oxide particles are produced.
ここで一般的に、結晶性の金属酸化物粒子を生成する場合には、少なくとも約８００℃以上の温度で上記塗膜を加熱する必要がある。これに対し、本発明電極板の製造方法において、７００℃以下、さらには６００℃以下、特には、４００℃以下という低い加熱温度においても、結晶性あるいは微結晶性の金属酸化物粒子が生成されるのは、本発明電極板を製造する方法の特徴的な点の１つといえ、このような低い温度でも結晶性の金属酸化物粒子を生成できることは特筆すべき有利な点である。尚、上記結晶性の金属酸化物には、微結晶状態のものも含まれる。上述する加熱温度と、生成される金属酸化物粒子の結晶性の発達との関係は、以下のとおり推測される。即ち、電極活物質層形成液中に、活物質粒子が含有されているため、生成される金属酸化物粒子は、該活物質粒子の結晶性に追従して、７００℃以下、さらには６００℃以下、特には、４００℃以下の加熱温度であっても結晶性の高い金属酸化物粒子になるものと推測される。 Here, generally, when producing crystalline metal oxide particles, it is necessary to heat the coating film at a temperature of at least about 800 ° C. or higher. In contrast, in the method for producing an electrode plate of the present invention, crystalline or microcrystalline metal oxide particles are generated even at a heating temperature of 700 ° C. or lower, further 600 ° C. or lower, particularly 400 ° C. or lower. This is one of the characteristic points of the method for producing the electrode plate of the present invention, and it is a remarkable advantage that crystalline metal oxide particles can be produced even at such a low temperature. Note that the crystalline metal oxide includes a microcrystalline state. The relationship between the heating temperature described above and the development of crystallinity of the generated metal oxide particles is estimated as follows. That is, since the active material particles are contained in the electrode active material layer forming liquid, the generated metal oxide particles follow the crystallinity of the active material particles and are 700 ° C. or lower, and further 600 ° C. In particular, it is presumed that metal oxide particles having high crystallinity are obtained even at a heating temperature of 400 ° C. or less.
上記加熱工程は、加熱温度を４００℃以下で実施することにより、集電体の選択範囲が広がり、種々の集電体上に電極活物質層を直接に形成することができる点、および、実施温度が低いということによりコストメリットが向上する点など種々の効果が発揮されるため、好ましい。 The heating step is performed at a heating temperature of 400 ° C. or less, so that the selection range of the current collector is widened, and the electrode active material layer can be directly formed on various current collectors. Since various effects, such as the point that cost merit improves by having low temperature, are preferable.
上記したように加熱工程における加熱温度が、比較的低い温度であっても結晶性の金属酸化物粒子を生成することができるが、結晶性の金属酸化物粒子を生成する場合の加熱温度は、結着物質生成材料の熱分解開始温度以上であり、且つ生成される金属酸化物の結晶化温度以上の温度であり、非晶質の金属酸化物を生成する場合の加熱温度は、結着物質生成材料の熱分解開始温度以上であり、且つ生成される金属酸化物の結晶化温度未満の温度である。本発明の電極板を製造する方法において、上記加熱工程を経て形成される電極物質活物質層は、活物質粒子と、該活物質粒子の平均粒径よりも小さい平均粒径を有する金属酸化物粒子よりなる結着物質粒子とを含有するが、活物質の平均粒径が結着物質粒子の平均粒径の３倍以上となるように粒成長させるために、１時間〜１０時間の長時間の加熱が好ましい。尚、炭素成分を含む場合には、炭素成分源となる有機物や有機金属化合物に含有される炭素が、電極活物質層中に導電材とは区別される炭素成分として残存可能な温度範囲とする。 As described above, the crystalline metal oxide particles can be produced even when the heating temperature in the heating step is relatively low, but the heating temperature in the case of producing crystalline metal oxide particles is: The heating temperature in the case of producing an amorphous metal oxide that is not lower than the thermal decomposition start temperature of the binding substance generating material and is not lower than the crystallization temperature of the generated metal oxide is the binding substance. The temperature is equal to or higher than the thermal decomposition start temperature of the generated material and lower than the crystallization temperature of the generated metal oxide. In the method for producing an electrode plate of the present invention, the electrode material active material layer formed through the heating step includes active material particles and a metal oxide having an average particle size smaller than the average particle size of the active material particles In order to grow the particles so that the average particle diameter of the active material is three times or more than the average particle diameter of the binder material particles, Is preferred. In addition, when a carbon component is included, the carbon contained in the organic substance or organometallic compound serving as the carbon component source has a temperature range in which it can remain as a carbon component that is distinguished from the conductive material in the electrode active material layer. .
結着物質生成材料の熱分解開始温度は、個々の化合物の種類によって異なる。
上記塗膜中に含有される金属元素含有化合物は、加熱されて熱分解すると、一般的には、速やかに酸化し、これによって金属酸化物が形成される。したがって予備試験として、金属元素含有化合物が配合される溶液を基板上に塗布して加熱し、基板上に積層される積層膜を削って試料とし、組成分析を行い、金属元素と酸素の含有比率を測定することによって、金属酸化物が形成されているかどうかを判断することができ、また、金属酸化物が生成されていた場合には、用いられた金属元素含有化合物が、基板上で熱分解開始温度以上の温度で加熱されたことが確認される。尚、上記予備試験における加熱は、本製造方法において予定される加熱雰囲気と同様の雰囲気で実施する。即ち、本発明において「金属元素含有化合物の熱分解開始温度」とは、加熱により金属元素含有化合物が熱分解され、これに含まれる金属元素の酸化が開始する温度、と理解することができる。
The thermal decomposition onset temperature of the binding substance generating material varies depending on the type of each compound.
When the metal element-containing compound contained in the coating film is heated and thermally decomposed, in general, it is rapidly oxidized to form a metal oxide. Therefore, as a preliminary test, a solution containing a metal element-containing compound is applied on a substrate and heated, and the laminated film laminated on the substrate is cut to obtain a sample, which is subjected to composition analysis and the content ratio of the metal element and oxygen. It is possible to determine whether or not a metal oxide is formed, and when the metal oxide is formed, the metal element-containing compound used is thermally decomposed on the substrate. It is confirmed that heating was performed at a temperature higher than the start temperature. The heating in the preliminary test is performed in an atmosphere similar to the heating atmosphere planned in the manufacturing method. That is, in the present invention, the “thermal decomposition start temperature of the metal element-containing compound” can be understood as a temperature at which the metal element-containing compound is thermally decomposed by heating and oxidation of the metal element contained therein starts.
また、本発明において「結晶化温度」というときには、電極活物質層形成溶液中に含有される金属原子が、金属酸化物となった後、当該金属酸化物が結晶化する温度を意味する。当該結晶化温度において金属酸化物は結晶化し、当該温度を上回ると結晶化度が増大するが、本発明において「結晶化」というときには、結晶化度によらず、Ｘ線回折装置において結晶状態を示すピークが確認される場合をいう。本発明における「結晶化温度」は、金属酸化物の固有の結晶化温度とは必ずしも一致するとは限らず、電極活物質層形成溶液中の状態により、これらの固有の結晶化温度と若干相違する場合があり、また加熱時間の長短によって、固有の結晶化温度と相違する場合がある。したがって、この点を勘案し、予め、電極活物質層形成用塗膜中において金属酸化物粒子が形成される加熱温度、加熱時間を確認しておくことが望ましい。例えば金属元素含有化合物として硝酸鉄を用いて結晶性の酸化鉄からなる結着物質粒子を生成する場合、加熱温度は、４００〜５５０℃程度である。 In the present invention, the term “crystallization temperature” means a temperature at which a metal atom contained in the electrode active material layer forming solution becomes a metal oxide and then crystallizes. The metal oxide crystallizes at the crystallization temperature, and the crystallinity increases when the temperature exceeds the temperature. In the present invention, the term “crystallization” refers to the crystal state in the X-ray diffractometer regardless of the crystallinity. This refers to the case where the peak shown is confirmed. The “crystallization temperature” in the present invention does not necessarily coincide with the intrinsic crystallization temperature of the metal oxide, and is slightly different from the intrinsic crystallization temperature depending on the state in the electrode active material layer forming solution. In some cases, it may differ from the intrinsic crystallization temperature depending on the length of the heating time. Therefore, in consideration of this point, it is desirable to confirm in advance the heating temperature and heating time at which the metal oxide particles are formed in the electrode active material layer-forming coating film. For example, when producing binder particles composed of crystalline iron oxide using iron nitrate as the metal element-containing compound, the heating temperature is about 400 to 550 ° C.
一方、非晶質の金属酸化物が形成するための「結晶化温度未満」の温度とは、集電体上に形成される電極活物質層中に含有される金属酸化物が、非晶質の状態で存在することを可能とする温度である。当該温度は、予備的に、金属元素含有化合物が配合される溶液を基板上に塗布し、金属元素含有化合物の熱分解開始温度以上の温度で加熱し、基板上に金属酸化物からなる膜を形成し、当該膜を削って試料とし、Ｘ線回折装置を用いて、その結晶性について評価し、結晶のピークが確認されなければ、結晶化温度未満の温度で加熱された、と理解することができ、このような予備試験により非晶質の金属酸化物粒子を形成し得る加熱温度、加熱時間を確認しておくことが好ましい。例えば金属元素含有化合物として硝酸鉄を用いて非晶質の酸化鉄からなる結着物質粒子を生成する場合、加熱温度は、２５０〜４００℃程度である。 On the other hand, the temperature “below the crystallization temperature” for forming an amorphous metal oxide means that the metal oxide contained in the electrode active material layer formed on the current collector is amorphous. It is a temperature that makes it possible to exist in the state of The temperature is preliminarily applied on a substrate with a solution containing a metal element-containing compound, heated at a temperature equal to or higher than the thermal decomposition start temperature of the metal element-containing compound, and a film made of a metal oxide on the substrate. After forming and scraping the film to make a sample, the crystallinity is evaluated using an X-ray diffractometer, and if the peak of the crystal is not confirmed, it is understood that the film is heated at a temperature lower than the crystallization temperature. It is preferable to confirm the heating temperature and heating time at which amorphous metal oxide particles can be formed by such a preliminary test. For example, when producing binder particles made of amorphous iron oxide using iron nitrate as the metal element-containing compound, the heating temperature is about 250 to 400 ° C.
また、上記加熱工程において、加熱温度を決定する際には、さらに、用いられる集電体、活物質粒子、導電材などの耐熱性も勘案することが望ましい。たとえば、一般的に正極板の集電体として用いられるアルミ箔の耐熱性は、６６０℃前後であるため、上記加熱温度が６６０℃を超える場合には、集電体を損傷するおそれがある。したがって、用いられる集電体、活物質粒子などを先に決定し、これらの耐熱性を勘案して、これらの耐熱温度と熱分解開始温度とを勘案して、金属元素含有化合物を選択してもよい。また、活物質粒子の平均粒径よりも、生成される金属酸化物粒子の平均粒径が小さくなるよう、予備実験を行い、適宜加熱温度を決定してよい。尚、本発明の製造方法に関し、「加熱温度」とは、加熱工程における最高温度を意味する。また加熱工程における加温の態様は、例えば、除々に昇温し、あるいは、一定の温度で加熱し、あるいは、段階的な温度で加熱してよく、任意に決定することができる。 In the heating step, when determining the heating temperature, it is desirable to further consider the heat resistance of the current collector, active material particles, conductive material, and the like used. For example, since the heat resistance of an aluminum foil generally used as a current collector for a positive electrode plate is around 660 ° C., the current collector may be damaged if the heating temperature exceeds 660 ° C. Therefore, the current collector, active material particles, etc. to be used are determined first, taking into account their heat resistance, taking into account their heat resistant temperature and thermal decomposition starting temperature, and selecting a metal element-containing compound. Also good. In addition, a preliminary experiment may be performed to appropriately determine the heating temperature so that the average particle size of the metal oxide particles to be generated is smaller than the average particle size of the active material particles. In the production method of the present invention, “heating temperature” means the highest temperature in the heating step. The heating mode in the heating step may be arbitrarily determined, for example, by gradually increasing the temperature, heating at a constant temperature, or heating at a stepped temperature.
尚、上記加熱工程における加熱雰囲気は、特に限定されない。上記加熱雰囲気は、生成される金属酸化物や用いられる集電体の種類などを勘案して、適宜、決定される。上記加熱雰囲気は、例えば、空気、酸素、水素、不活性ガス（窒素・アルゴン）などのいずれかのガスを使用するか、あるいはこれらから選択される２種以上のガスを組み合わせてなるガスを用いて調整することができるが、これに限定されない。任意の加熱雰囲気で加熱工程を実施するために、雰囲気焼成炉が好適に使用される。 In addition, the heating atmosphere in the said heating process is not specifically limited. The heating atmosphere is appropriately determined in consideration of the generated metal oxide and the type of current collector used. For the heating atmosphere, for example, any gas such as air, oxygen, hydrogen, inert gas (nitrogen / argon), or a combination of two or more gases selected from these gases is used. However, the present invention is not limited to this. In order to carry out the heating step in an arbitrary heating atmosphere, an atmosphere firing furnace is preferably used.
本発明の電極板は、上述のとおり製造された電極活物質層に、さらに樹脂成分を含有させてもよい。電極活物質層にさらに樹脂成分を含有させる方法は、例えば、樹脂混合液を、電極活物質層の表面に塗布し、あるいは、樹脂混合液槽に電極板を浸漬させて、該樹脂混合液を電極活物質層の空隙に浸透させ、次いで、乾燥させることによって、電極活物質層に含浸する上記樹脂混合液の溶媒を除去し、樹脂成分だけを、電極活物質層の内部に残留させる方法が挙げられる。このように、電極活物質層中に更に樹脂成分を含有する本発明の電極板であれば、樹脂成分の存在により、電極板の曲げ耐性が向上し、加工特性を向上させることが可能である。また、特に上記樹脂成分が、従来使用されていた樹脂製結着材である場合には、集電体に対する電極活物質層の膜密着性をより向上させることができる。 The electrode plate of the present invention may further contain a resin component in the electrode active material layer produced as described above. For example, the electrode active material layer may further contain a resin component by, for example, applying a resin mixed solution to the surface of the electrode active material layer or immersing an electrode plate in a resin mixed solution tank, A method of removing the solvent of the resin mixed solution impregnated in the electrode active material layer by infiltrating the gaps in the electrode active material layer and then drying, and leaving only the resin component inside the electrode active material layer. Can be mentioned. Thus, if the electrode plate of the present invention further contains a resin component in the electrode active material layer, the presence of the resin component can improve the bending resistance of the electrode plate and improve the processing characteristics. . In particular, when the resin component is a conventionally used resin binder, the film adhesion of the electrode active material layer to the current collector can be further improved.
上記樹脂混合液に含まれる樹脂材料として、例えば、ＰＶＤＦなどの従来の樹脂製結着材、スチレンブタジエンゴム（ＳＢＲ）、カルボキシメトキシセルロース（ＣＭＣ）や、上記粘度調整剤に挙げるものなどを選択することができるが、これに限定されない。また上記樹脂材料は、電極活物質層における空隙内に浸透可能なサイズを適宜選択する。また、樹脂混合液の溶媒としては、例えば、メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、ノルマルブチルアルコール、イソブチルアルコール、セカンダリーブチルアルコール、ターシャリーブチルアルコール等の総炭素数が５以下の低級アルコール、アセチルアセトン、ジアセチル、ベンゾイルアセトン等のジケトン類、アセト酢酸エチル、ピルビン酸エチル、ベンゾイル酢酸エチル、ベンゾイル蟻酸エチル等のケトエステル類、Ｎーメチルピロリドン（ＮＭＰ）などのピロリドン類、トルエン、およびこれらの混合溶媒、水等などを用いることができ、該溶媒に、樹脂材料を混合させて、樹脂混合液を調製することができる。 As the resin material contained in the resin mixed solution, for example, a conventional resin binder such as PVDF, styrene butadiene rubber (SBR), carboxymethoxy cellulose (CMC), or those listed in the viscosity modifier are selected. However, the present invention is not limited to this. The resin material is appropriately selected to have a size that can penetrate into the voids in the electrode active material layer. Examples of the solvent for the resin mixture include lower alcohols having a total carbon number of 5 or less, such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, secondary butyl alcohol, and tertiary butyl alcohol. Diketones such as alcohol, acetylacetone, diacetyl, benzoylacetone, ketoesters such as ethyl acetoacetate, ethyl pyruvate, ethyl benzoylacetate, ethyl benzoylformate, pyrrolidones such as N-methylpyrrolidone (NMP), toluene, and these A mixed solvent, water, or the like can be used, and a resin mixed solution can be prepared by mixing a resin material with the solvent.
電極活物質層中に含有される樹脂成分の量は、電極板の出入力性能などを低下させない程度に調整することが望ましい。即ち、本発明の趣旨を逸脱しない範囲において、樹脂成分を電極活物質層中に含ませてよい。 The amount of the resin component contained in the electrode active material layer is desirably adjusted to such an extent that the input / output performance of the electrode plate is not deteriorated. That is, the resin component may be included in the electrode active material layer without departing from the spirit of the present invention.
［非水電解液二次電池］
本発明の非水電解液二次電池の一実施態様としては、図２に示すように、集電体５５の一方面側に電極活物質層５４が設けられてなる正極板５０及びこれに組み合わされる集電体１の一方面側に電極活物質層２が設けられてなる電極板１０（即ち、図２中、電極板１０は負極板である）と、これらの間にポリエチレン製多孔質フィルムのようなセパレータ７０とが設けられる。そして、これらが外装８１、８２内に収納され、且つ、外装８１、８２内に非水電解液９０が充填された状態で密封されて製造されて、非水電解液二次電池１００が構成される。
[Nonaqueous electrolyte secondary battery]
As one embodiment of the nonaqueous electrolyte secondary battery of the present invention, as shown in FIG. 2, a positive electrode plate 50 in which an electrode active material layer 54 is provided on one side of a current collector 55 and a combination thereof. An electrode plate 10 in which an electrode active material layer 2 is provided on one side of the current collector 1 (that is, in FIG. 2, the electrode plate 10 is a negative electrode plate), and a polyethylene porous film therebetween The separator 70 is provided. These are housed in the outer casings 81 and 82 and sealed and manufactured in a state where the outer casings 81 and 82 are filled with the non-aqueous electrolyte 90, thereby forming the non-aqueous electrolyte secondary battery 100. The
（電極板）
本発明の非水電解液二次電池は、特に、正極板及び負極板の少なくとも一方に、上述する本発明の非水電解液二次電池用電極板を用いることを特徴とする。
(Electrode plate)
The nonaqueous electrolyte secondary battery of the present invention is characterized in that, in particular, the electrode plate for a nonaqueous electrolyte secondary battery of the present invention described above is used for at least one of the positive electrode plate and the negative electrode plate.
特に、従来、負極板が炭素質材料より構成される場合には、これにあわせて正極板の導電性を上げるために正極板に導電材料を多量に添加することが一般的であったが、このために正極板の空隙率が低下し、電解液の浸透性が低下することにより電池の出入力を増大させることが困難であった。しかしながら本発明の電極板は高出入力可能な電極板であるので、これを正極板として用いた場合には、従来のように導電材を多量に用いることなく、あるいは導電材を全く用いることなく、良好な導電性及び高出入力化を可能とする。 In particular, conventionally, when the negative electrode plate is composed of a carbonaceous material, it has been common to add a large amount of conductive material to the positive electrode plate in order to increase the conductivity of the positive electrode plate accordingly. For this reason, the porosity of the positive electrode plate is lowered, and the permeability of the electrolytic solution is lowered, so that it is difficult to increase the input / output of the battery. However, since the electrode plate of the present invention is an electrode plate capable of high input / output, when this is used as a positive electrode plate, a large amount of conductive material is not used as in the prior art, or no conductive material is used at all. Good electrical conductivity and high input / output can be achieved.
また非水電解液二次電池は、負極板に用いられる負極活物質として、グラファイトなどの炭素質材料ではなく、金属リチウム及びその合金、スズ、ケイ素、及びそれらの合金等、リチウムイオンを挿入脱離可能な材料を用い、負極板を構成する態様も含む。かかる態様の電池においては、本発明の電極板を負極として積極的に使用して、非水電解液二次電池を製造することができる。 In addition, non-aqueous electrolyte secondary batteries do not insert and remove lithium ions, such as metallic lithium and its alloys, tin, silicon, and their alloys, rather than carbonaceous materials such as graphite, as the negative electrode active material used in the negative electrode plate. The aspect which comprises a negative electrode plate using the material which can be separated is also included. In such a battery, a nonaqueous electrolyte secondary battery can be produced by positively using the electrode plate of the present invention as a negative electrode.
また本発明の電極板を、正極板および負極板の両方に用いて非水電解液二次電池を構成することもできる。 Moreover, a nonaqueous electrolyte secondary battery can also be comprised using the electrode plate of this invention for both a positive electrode plate and a negative electrode plate.
尚、本発明の非水電解液二次電池において、正極板または負極板のいずれか一方において、本発明の電極板を用いる場合には、他方の電極板は、非水電解液二次電池において使用される従来公知の電極板を適宜使用することができる。 In the nonaqueous electrolyte secondary battery of the present invention, when the electrode plate of the present invention is used in either the positive electrode plate or the negative electrode plate, the other electrode plate is used in the nonaqueous electrolyte secondary battery. The conventionally well-known electrode plate used can be used suitably.
従来公知の正極板としては、一般的には本発明の電極板において用いられる集電体と同様の集電体表面上の少なくとも一部に、正極活物質粒子、導電材、樹脂製結着材などが添加された正極活物質層形成液を塗布して、乾燥し、必要に応じてプレスすることにより形成されたものが使用される。 As a conventionally well-known positive electrode plate, in general, at least part of the current collector surface similar to the current collector used in the electrode plate of the present invention, positive electrode active material particles, conductive material, resin binder A positive electrode active material layer-forming solution to which is added is applied, dried, and pressed as necessary.
一方、従来公知の負極板としては、集電体として厚み５〜５０μｍ程度の電解銅箔や圧延銅箔等の銅箔を用い、上記集電体表面の少なくとも一部に、負極活物質層形成液を塗布して、乾燥し、必要に応じてプレスすることにより形成されたものが使用される。上記負極活物質層形成液には、一般的に、天然グラファイト、人造グラファイト、アモルファス炭素、カーボンブラック、またはこれらの成分に異種元素を添加したもののような炭素質材料からなる活物質粒子、あるいは、金属リチウム及びその合金、スズ、ケイ素、及びそれらの合金等の、リチウムイオン挿入脱離可能な材料などからなる活物質粒子、および樹脂製結着材、必要に応じて導電材などの他の添加剤が混合されることが一般的である。 On the other hand, as a conventionally known negative electrode plate, a copper foil such as an electrolytic copper foil or a rolled copper foil having a thickness of about 5 to 50 μm is used as a current collector, and a negative electrode active material layer is formed on at least a part of the current collector surface. What was formed by apply | coating a liquid, drying, and pressing as needed is used. In the negative electrode active material layer forming liquid, generally active material particles made of carbonaceous material such as natural graphite, artificial graphite, amorphous carbon, carbon black, or those obtained by adding different elements to these components, or Active material particles made of lithium ion insertion / desorption materials such as metallic lithium and alloys thereof, tin, silicon, and alloys thereof, and other additives such as resin binders and conductive materials as required It is common for agents to be mixed.
（非水電解液）
本発明に用いられる非水電解液は、一般的に、非水電解液二次電池用の非水電解液として用いられるものであれば、特に限定されないが、リチウム塩を有機溶媒に溶解させた非水電解液が好ましく用いられる。
(Non-aqueous electrolyte)
The non-aqueous electrolyte used in the present invention is not particularly limited as long as it is generally used as a non-aqueous electrolyte for a non-aqueous electrolyte secondary battery, but a lithium salt is dissolved in an organic solvent. A non-aqueous electrolyte is preferably used.
上記非水電解液として用いられるリチウム塩の例としては、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＣｌ、及びＬｉＢｒ等の無機リチウム塩；ＬｉＢ（Ｃ６Ｈ５）４、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＣ（ＳＯ２ＣＦ３）３、ＬｉＯＳＯ２ＣＦ３、ＬｉＯＳＯ２Ｃ２Ｆ５、ＬｉＯＳＯ２Ｃ４Ｆ９、ＬｉＯＳＯ２Ｃ５Ｆ１１、ＬｉＯＳＯ２Ｃ６Ｆ１３、及びＬｉＯＳＯ２Ｃ７Ｆ１５等の有機リチウム塩；等が代表的に挙げられる。 Examples of the lithium salt used as the non-aqueous electrolyte include inorganic lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCl, and LiBr; LiB (C 6 H 5 ) 4 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiOSO 2 CF 3 , LiOSO 2 C 2 F 5 , LiOSO 2 C 4 F 9 , LiOSO 2 C 5 F 11 , LiOSO 2 C 6 F 13 , and LiOSO 2 An organic lithium salt such as C 7 F 15 ;
リチウム塩の溶解に用いられる有機溶媒としては、プロピレンカーボネート、ブチレンカーボネートなどの環状エステル類、ジメチルカーボネート、ジエチルカーボネートなどの鎖状エステル類、テトラヒドロフラン、アルキルテトラヒドロフランなどの環状エーテル類、及び１，２−ジメトキシエタン、１，２−ジエトキシエタンなどの鎖状エーテル類等が挙げられるが、これに限定されない。 Examples of the organic solvent used for dissolving the lithium salt include cyclic esters such as propylene carbonate and butylene carbonate, chain esters such as dimethyl carbonate and diethyl carbonate, cyclic ethers such as tetrahydrofuran and alkyltetrahydrofuran, and 1,2- Examples include, but are not limited to, chain ethers such as dimethoxyethane and 1,2-diethoxyethane.
上記正極板、負極板、セパレータ、非水電解液を用いて製造される本発明の非水電解液二次電池の構造としては、従来公知の構造を適宜選択して採用することができる。例えば、正極板及び負極板を、ポリエチレン製多孔質フィルムのようなセパレータを介して渦巻状に巻き回して、電池容器内に収納する構造が挙げられる。また別の態様としては、所定の形状に切り出した正極板及び負極板がセパレータを介して積層されて固定され、これを電池容器内に収納する構造を採用してもよい。いずれの構造においても、例えば、正極板及び負極板を電池容器内に収納後、正極板に取り付けられたリード線を外装容器に設けられた正極端子に接続し、一方、負極板に取り付けられたリード線を外装容器内に設けられた負極端子に接続し、さらに電池容器内に非水電化液を充填した後、密閉することによって非水電解液二次電池が製造される。 As a structure of the non-aqueous electrolyte secondary battery of the present invention produced using the positive electrode plate, the negative electrode plate, the separator, and the non-aqueous electrolyte solution, a conventionally known structure can be appropriately selected and adopted. For example, the structure which winds a positive electrode plate and a negative electrode plate in the shape of a spiral via the separator like a polyethylene porous film, and accommodates in a battery container is mentioned. As another aspect, a structure may be employed in which a positive electrode plate and a negative electrode plate cut into a predetermined shape are stacked and fixed via a separator, and are accommodated in a battery container. In any structure, for example, after the positive electrode plate and the negative electrode plate are accommodated in the battery container, the lead wire attached to the positive electrode plate is connected to the positive electrode terminal provided in the outer container, while being attached to the negative electrode plate. A non-aqueous electrolyte secondary battery is manufactured by connecting the lead wire to a negative electrode terminal provided in the exterior container, and further filling the battery container with a non-aqueous electrification solution and then sealing the battery container.
［電池パック］
本発明の電極板を正極板および／または負極板として用いる非水電解液二次電池は、所謂、電池パックに用いられる非水電解液二次電池として使用することができる。即ち、本発明の電池パックは、本発明の電極板を正極板および／または負極板として用い、且つ、正極端子および負極端子を備える非水電解液二次電池と過放電保護機能を有する保護回路とが収納ケースに収納されて構成される。本発明の電池パックは、例えば、過充電、過放電、過電流、電池周辺回路の短絡、正負電極間の短絡などから電池を保護するための保護機能を非水電解液二次電池自体に装備するとともに、過充電や過放電を防止するための保護回路を該非水電解液二次電池と共に収納ケースに収容して一体化されてなる電池パックであってよい。本発明の電池パックは、ノートパソコン、カメラ、携帯電話等の携帯機器など、装置の規模に対して消費電力が大きい装置の電池電源装置として好適に使用することができる。
[Battery pack]
The nonaqueous electrolyte secondary battery using the electrode plate of the present invention as a positive electrode plate and / or a negative electrode plate can be used as a so-called nonaqueous electrolyte secondary battery used in a battery pack. That is, the battery pack of the present invention uses the electrode plate of the present invention as a positive electrode plate and / or a negative electrode plate, and includes a nonaqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal, and a protection circuit having an overdischarge protection function Are housed in a storage case. The battery pack of the present invention is equipped with a protection function for protecting the battery from, for example, overcharge, overdischarge, overcurrent, a short circuit of the battery peripheral circuit, a short circuit between the positive and negative electrodes, etc., in the nonaqueous electrolyte secondary battery itself. In addition, it may be a battery pack in which a protection circuit for preventing overcharge and overdischarge is housed and integrated in a storage case together with the non-aqueous electrolyte secondary battery. The battery pack of the present invention can be suitably used as a battery power supply device for a device that consumes a large amount of power relative to the scale of the device, such as a portable device such as a notebook computer, a camera, or a mobile phone.
図３に、本発明の電池パックの一態様として、本発明の電極板が用いられて構成されるリチウムイオン二次電池３１を用いた本発明の電池パック３０の概略分解図を示す。電池パック３０は、リチウムイオン二次電池３１が樹脂容器３６ａ、樹脂容器３６ｂ、および端部ケース３７に収納されて構成される。このとき、リチウムイオン二次電池３１の一端面であって、正極端子３２および負極端子３３を備える面と、端部ケース３７との間には、過充電や過放電を防止するための保護回路基板３４が、設けられる。保護回路基板３４は、外部接続コネクタ３５を備えており、外部接続コネクタ３５は、樹脂容器３６ａに設けられた外部接続用窓３８ａおよび、端部ケース３７に設けられた外部接続用窓３８ｂに挿入され、外部端子と接続される。また、保護回路基板３４には、図示しない、充放電を制御するための充放電安全回路、外部接続端子とリチウムイオン二次電池３１とを導通させるための配線回路などが搭載されている。尚、電池パック３０は、本発明の電極板が用いられたリチウムイオン二次電池３１を用いること以外は、従来公知の電池パックの構成を適宜採用することができる。図示省略するが、電池パック３０は、リチウムイオン二次電池３１と端部ケース３７との間に、正極端子３２と接続する正極リード板、負極端子３３と接続する負極リード板、絶縁体などを、適宜備えてよい。 FIG. 3 shows a schematic exploded view of a battery pack 30 of the present invention using a lithium ion secondary battery 31 configured using the electrode plate of the present invention as an embodiment of the battery pack of the present invention. The battery pack 30 includes a lithium ion secondary battery 31 housed in a resin container 36a, a resin container 36b, and an end case 37. At this time, a protection circuit for preventing overcharge and overdischarge between one end face of the lithium ion secondary battery 31 and a face including the positive electrode terminal 32 and the negative electrode terminal 33 and the end case 37. A substrate 34 is provided. The protection circuit board 34 includes an external connection connector 35. The external connection connector 35 is inserted into an external connection window 38a provided in the resin container 36a and an external connection window 38b provided in the end case 37. Connected to an external terminal. The protection circuit board 34 includes a charge / discharge safety circuit (not shown) for controlling charge / discharge, a wiring circuit for connecting the external connection terminal and the lithium ion secondary battery 31, and the like. In addition, the battery pack 30 can employ | adopt the structure of a conventionally well-known battery pack suitably except using the lithium ion secondary battery 31 in which the electrode plate of this invention was used. Although not shown, the battery pack 30 includes a positive electrode lead plate connected to the positive electrode terminal 32, a negative electrode lead plate connected to the negative electrode terminal 33, an insulator, and the like between the lithium ion secondary battery 31 and the end case 37. , May be provided as appropriate.
尚、本発明の電極板を用いた本発明の非水電解液二次電池は、電池パックへの使用態様以外に、上記保護回路に、さらに、過大電流の遮断、電池温度モニター等の機能を備え、且つ、該保護回路を二次電池自体に一体化させて取り付けられる態様に用いられてもよい。かかる態様では、電池パックを構成することなく、保護機能および保護回路を備える二次電池として使用することができ、汎用性が高い。尚、上述するいくつかの態様は、例示に過ぎず、本発明の電極板、あるいは本発明の非水電解液二次電池の使用を何ら限定するものではない。 In addition, the non-aqueous electrolyte secondary battery of the present invention using the electrode plate of the present invention has functions such as overcurrent blocking and battery temperature monitoring in addition to the above-described protection circuit, in addition to the usage mode for battery packs. And the protection circuit may be used by being integrated with the secondary battery itself. In such an embodiment, the battery pack can be used as a secondary battery having a protection function and a protection circuit without constituting a battery pack, and is highly versatile. In addition, some aspects mentioned above are only illustrations, and do not limit use of the electrode plate of this invention, or the nonaqueous electrolyte secondary battery of this invention at all.
（実施例１）
＜非水電解液二次電池用正極板の作製＞
非水電解液二次電池用正極板における電極活物質層を形成するための正極活物質層形成液を以下のとおり調製した。
まず金属元素含有化合物として、Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ［分子量：４０４］４．０ｇをエチルアルコール５ｇに加え、更に樹脂としてポリエチレングリコール２００（関東化学株式会社製）を５ｇ混合し、リチウムイオン挿入脱離反応を示さない金属酸化物を生成する原料溶液（金属酸化物生成原料溶液）とした。次いで上記原料液に、平均粒径４μｍの正極活物質粒子（ＬｉＭｎ２Ｏ４）１０ｇと、導電材としてアセチレンブラック（電気化学工業株式会社製、デンカブラック）１．０ｇ、炭素繊維（昭和電工株式会社製、ＶＧＣＦ）０．２ｇを混合し、エクセルオートホモジナイザー（株式会社日本精機製作所製）で７０００ｒｐｍの回転数で２０分間、攪拌することによって正極活物質層形成液を得た。正極活物質層形成液の組成を表１にまとめて示す。
Example 1
<Preparation of positive electrode plate for non-aqueous electrolyte secondary battery>
A positive electrode active material layer forming liquid for forming an electrode active material layer in a positive electrode plate for a non-aqueous electrolyte secondary battery was prepared as follows.
First, as the metal element-containing compound, Fe (NO 3) 3 · 9H 2 O [ molecular weight: 404] 4.0 g was added to ethyl alcohol 5g, polyethylene glycol 200 (manufactured by Kanto Chemical Co., Inc.) was 5g mixed as further resin, A raw material solution that produces a metal oxide that does not exhibit lithium ion insertion / release reaction (metal oxide production raw material solution) was used. Next, 10 g of positive electrode active material particles (LiMn 2 O 4 ) having an average particle diameter of 4 μm, 1.0 g of acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive material, carbon fiber (Showa Denko Co., Ltd.) A positive electrode active material layer forming liquid was obtained by mixing 0.2 g of company-made VGCF and stirring with an Excel auto homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) at a rotation speed of 7000 rpm for 20 minutes. Table 1 summarizes the composition of the positive electrode active material layer forming liquid.
次に、正極集電体である厚さ１５μｍのアルミ箔を準備し、当該正極集電体の一面側に、乾燥後の電極活物質層の重さが４５ｇ/ｍ２となるように、上記にて調製した正極活物質層形成液をアプリケーターで塗布して電極活物質形成用塗膜を形成した。 Next, an aluminum foil having a thickness of 15 μm as a positive electrode current collector is prepared, and the weight of the dried electrode active material layer is 45 g / m 2 on one surface side of the positive electrode current collector. The positive electrode active material layer forming liquid prepared in (1) was applied with an applicator to form a coating film for forming an electrode active material.
次に、表面に電極活物質層形成用塗膜が形成された集電体を、常温の電気炉（マッフル炉、デンケン社製、Ｐ９０）内に設置し、１時間かけて３５０℃まで加熱し、その後、３５０℃に維持したまま３時間加熱し、集電体上に正極活物質層として適切な電極活物質層が積層された本発明の非水電解液二次電池用正極板を得た。得られた正極板を室温になるまで室温下で放置した後、所定の大きさ（１５ｍｍφ）に裁断し、これを実施例１の試験用正極板とした。マイクロメーターを用いて上記正極活物質層の厚みを、任意の箇所で１０点測定し、平均値を算出したところ、４０μｍであった。また、使用した活物質粒子量などから、実施例１の正極板における電極活物質層の単位面積当たりの活物質粒子の含有量を算出したところ、６．２ｍｇ／１．７７ｃｍ２であった。電極活物質層の単位面積当たりの活物質粒子含有量を表３に示す。得られた正極板の物性について、下記試験により評価を行った。 Next, the current collector with the electrode active material layer-forming coating film formed on the surface was placed in a normal temperature electric furnace (Muffle furnace, manufactured by Denken, P90) and heated to 350 ° C. over 1 hour. Then, heating was performed for 3 hours while maintaining the temperature at 350 ° C. to obtain a positive electrode plate for a non-aqueous electrolyte secondary battery according to the present invention in which an appropriate electrode active material layer was laminated on the current collector as a positive electrode active material layer. . The obtained positive electrode plate was allowed to stand at room temperature until it reached room temperature, and then cut into a predetermined size (15 mmφ), which was used as a test positive electrode plate of Example 1. The thickness of the positive electrode active material layer was measured at 10 points using a micrometer, and the average value was calculated to be 40 μm. Moreover, it was 6.2 mg / 1.77 cm < 2 > when content of the active material particle per unit area of the electrode active material layer in the positive electrode plate of Example 1 was computed from the amount of active material particles used. Table 3 shows the active material particle content per unit area of the electrode active material layer. The physical property of the obtained positive electrode plate was evaluated by the following test.
膜形成性評価：
実施例１の試験用正極板を作成するにあたり、上述で得られた正極板を所望のサイズの円板形状に繰り抜く加工を行ったが、当該加工作業において、正極活物質層が剥離するなどの不具合なく、加工することができた。このことから、正極活物質層の膜形成性が良好であることを確認した。以下に示す実施例および比較例においても、上述するように、不具合なく電極板を円板状に繰り抜く加工ができた場合には、電極活物質層の膜形成性が良好であると評価する。一方、上記繰り抜き加工において電極活物質層の一部が剥がれ、あるいは活物質粒子が集電体上から落下するなどして、加工が不良であり、後述する三極式コインセルの作用極として使用に耐える円板が形成されなかった場合には、電極活物質層の膜形成性が不良であると評価する。膜成形性の評価を表２に示す。
Film formation evaluation:
In preparing the test positive electrode plate of Example 1, the positive electrode plate obtained above was processed into a disk shape having a desired size. In this processing operation, the positive electrode active material layer was peeled off, etc. It was possible to process without any problems. From this, it was confirmed that the film forming property of the positive electrode active material layer was good. Also in the following examples and comparative examples, as described above, when the electrode plate can be pulled out into a disk shape without any defects, it is evaluated that the film forming property of the electrode active material layer is good. . On the other hand, part of the electrode active material layer is peeled off in the above-mentioned punching process, or the active material particles fall from the current collector, etc., and the processing is poor, and it is used as a working electrode of a tripolar coin cell to be described later In the case where a disk that can withstand the above is not formed, it is evaluated that the film forming property of the electrode active material layer is poor. Table 2 shows the evaluation of film formability.
組成分析試験：
正極板の電極活物質層を削って得た試料を、Ｘ線光電子分光法（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）によって組成分析したところ、Ｆｅ元素が６Ａｔｏｍｉｃ％、Ｍｎ元素が１１Ａｔｏｍｉｃ％、Ｃ元素が５０Ａｔｏｍｉｃ％、Ｏ元素が３３Ａｔｏｍｉｃ％検出された。一方、Ｎ元素は検出されなかった。この結果、電極活物質形成用塗膜中に含有されていた硝酸鉄が、熱分解されて酸化鉄が生成されたことが確認された。
Composition analysis test:
A sample obtained by scraping the electrode active material layer of the positive electrode plate was subjected to composition analysis by X-ray photoelectron spectroscopy (Electron Spectroscopy for Chemical Analysis). , O element was detected at 33 atomic%. On the other hand, N element was not detected. As a result, it was confirmed that the iron nitrate contained in the coating film for forming an electrode active material was thermally decomposed to produce iron oxide.
結晶性評価：
金属酸化物を生成する原料溶液（正極物質を添加する前の溶液）をガラス板にミヤバー４番で塗布し、正極板作成時と同じ加熱条件で加熱し、得られた積層膜を削り取り、Ｘ線回折装置（ＸＲＤ）を用いて結晶性を評価した。その結果、生成された金属酸化物は、非結晶であることがわかった。即ち、原料溶液中の酸化鉄のＸ線回折と一致せず、ピークが確認されないかブロードな非晶質の酸化鉄の山が現れている、酸化鉄が非晶質であることが確認された。結晶性評価の結果を表２に示す。
Crystallinity evaluation:
A raw material solution for producing a metal oxide (a solution before adding a positive electrode material) is applied to a glass plate with a Miyabar No. 4 and heated under the same heating conditions as in the preparation of the positive electrode plate. Crystallinity was evaluated using a line diffractometer (XRD). As a result, the produced metal oxide was found to be amorphous. That is, it was confirmed that the iron oxide was amorphous because it did not coincide with the X-ray diffraction of the iron oxide in the raw material solution, and no peak was observed or a broad pile of amorphous iron oxide appeared. . Table 2 shows the results of the crystallinity evaluation.
電極活物質層の密着性評価：
正極板における電極活物質層の密着性を以下のようにして評価した。即ち、得られた正極板の電極活物質層表面にセロハンテープ（ニチバン株式会社製、ＣＴ２４）を、指の腹で密着させ、次いで密着させたテープを剥離し、テープを剥がした後の電極活物質層表面を観察し、以下の通り評価した。結果を表２に示す。
電極活物質層の剥がれが全く観察されなかった。・・・・○
電極活物質層の表面の一部が凝集破壊し、セロハンテープ側に張り付いたが、集電体表面が露出することはなかった。・・・・・・・・・・・・・△
電極活物質層の表面の一部が凝集破壊し、セロハンテープ側に張り付き、集電体表面の一部が露出した・・・・・・・・・・・・・・・・・・・・×
Evaluation of adhesion of electrode active material layer:
The adhesion of the electrode active material layer in the positive electrode plate was evaluated as follows. That is, a cellophane tape (Nichiban Co., Ltd., CT24) was closely attached to the surface of the electrode active material layer of the obtained positive electrode plate, then the attached tape was peeled off, and the electrode activity after peeling the tape was removed. The surface of the material layer was observed and evaluated as follows. The results are shown in Table 2.
No peeling of the electrode active material layer was observed.・ ・ ・ ・ ○
A part of the surface of the electrode active material layer was agglomerated and adhered to the cellophane tape side, but the current collector surface was not exposed. ...
Part of the surface of the electrode active material layer was agglomerated and stuck to the cellophane tape, and part of the current collector surface was exposed. ×
結着物質中の炭素成分の有無：
結着物質中に、炭素成分が含有されているか否かを、透過型電子顕微鏡を用い、走査透過型電子顕微鏡法（ＳＴＥＭ法）によって、ＥＤＸ検出器でナノオーダーの元素分析により示される元素マッピングによって炭素元素を確認した。
Presence or absence of carbon component in the binder:
Elemental mapping of whether or not a carbon component is contained in the binding substance, using a transmission electron microscope, scanning electron microscope (STEM), and nano-order elemental analysis using an EDX detector The carbon element was confirmed by.
サイクリックボルタンメトリー試験（ＣＶ試験）：
得られた正極板を用いてＣＶ試験を行った。具体的には、まず電極電位を３．０Ｖから４．３Ｖまで、掃引したのち、再び３．０Ｖまで戻す作業を３度繰り返した。走査速度は１ｍＶ/秒とした。２回目のサイクル結果を示すサイクリックボルタモグラムには３．９Ｖ付近にＬｉＭｎ２Ｏ４のＬｉ脱離反応に相当する酸化ピークが、４．１Ｖ付近にＬｉ挿入反応に相当する還元ピークが確認された。一方、正極板に使用したと同様の金属酸化物を生成する原料溶液（正極活物質を添加する前の溶液）を厚さ１５μｍのアルミ箔にミヤバー４番で塗布し、正極板作成時と同じ加熱条件で加熱し、得られた積層体について上記と同様のＣＶ試験を行った。２回目のサイクル試験結果を示すサイクリックボルタモグラムには、電気的な反応が示されず、電極活物質層中の結着物質である酸化鉄がリチウム挿入脱離反応を示さないことが確認された。尚、上記ＣＶ試験は、Ｂｉｏ Ｌｏｇｉｃ社製のＶＭＰ３を用いて実施した。電極活物質のリチウムイオン挿入脱離反応の有無をＣＶ試験により確認した結果を表２に示す。
Cyclic voltammetry test (CV test):
A CV test was performed using the obtained positive electrode plate. Specifically, the operation of first sweeping the electrode potential from 3.0 V to 4.3 V and then returning it to 3.0 V was repeated three times. The scanning speed was 1 mV / sec. In the cyclic voltammogram showing the result of the second cycle, an oxidation peak corresponding to the Li elimination reaction of LiMn 2 O 4 was observed near 3.9 V, and a reduction peak corresponding to the Li insertion reaction was confirmed near 4.1 V. . On the other hand, a raw material solution (a solution before adding the positive electrode active material) that produces the same metal oxide as used for the positive electrode plate was applied to aluminum foil with a thickness of 15 μm with a Miyabar No. 4 and the same as that for forming the positive electrode plate. The CV test similar to the above was performed about the obtained laminated body after heating on heating conditions. In the cyclic voltammogram showing the results of the second cycle test, no electrical reaction was shown, and it was confirmed that the iron oxide as the binding material in the electrode active material layer did not show a lithium insertion / release reaction. The CV test was performed using VMP3 manufactured by Bio Logic. Table 2 shows the results of confirming the presence or absence of lithium ion insertion / extraction reaction of the electrode active material by the CV test.
活物質粒子および結着物質粒子の平均粒径の算出：
実施例１の正極板を、集電体面に略垂直に切断した切断面を走査型電子顕微鏡で観察した。倍率１万倍の写真を図５（Ａ）に、倍率５万倍の写真を図５（Ｂ）に示す。図５（Ａ）から、実施例１の電極板における電極活物質層が、核体である活物質粒子と、活物質粒子表面の少なくとも一部を被覆する包囲体を構成する金属酸化物粒子とにより、二重構造をなしていることが確認された。図５（Ｂ）に示す電子顕微鏡写真に写される金属酸化物粒子をランダムに３０個選択して、電子顕微鏡観察結果を画像解析式粒度分布測定ソフトウェア（株式会社マウンテック製、ＭＡＣ ＶＩＥＷ）を用いて、その最長径を測定し、算術平均により、実施例１における結着物質粒子である金属酸化物粒子の平均粒径を求めた。また図５（Ａ）を用いたこと以外は上記結着物質粒子の粒径測定方法と同様に、使用した活物質粒子の平均粒径を確認的に測定した。結果は、表２に示す。尚、図５（Ｂ）からは、電極活物質層における結着物質粒子と導電材粒子および導電材繊維が視認された。
Calculation of average particle size of active material particles and binder material particles:
The cut surface obtained by cutting the positive electrode plate of Example 1 substantially perpendicularly to the current collector surface was observed with a scanning electron microscope. A photograph at a magnification of 10,000 times is shown in FIG. 5 (A), and a photograph at a magnification of 50,000 times is shown in FIG. 5 (B). From FIG. 5 (A), the electrode active material layer in the electrode plate of Example 1 has active material particles that are nuclei, and metal oxide particles that constitute an enclosure that covers at least part of the surface of the active material particles. Thus, a double structure was confirmed. Randomly select 30 metal oxide particles shown in the electron micrograph shown in FIG. 5B, and use the image analysis type particle size distribution measurement software (MAC VIEW, manufactured by Mount Tech Co., Ltd.) for the electron microscope observation results. Then, the longest diameter was measured, and the average particle diameter of the metal oxide particles as the binder particles in Example 1 was determined by arithmetic mean. Moreover, the average particle diameter of the used active material particle was confirmed in the same manner as in the particle diameter measuring method of the binder material particle except that FIG. 5A was used. The results are shown in Table 2. In FIG. 5B, the binder material particles, the conductive material particles, and the conductive material fibers in the electrode active material layer were visually recognized.
＜三極式コインセルの作製＞
エチレンカーボネート（ＥＣ）／ジメチルカーボネート（ＤＭＣ）混合溶媒（体積比＝１：１）に、溶質として六フッ化リン酸リチウム（ＬｉＰＦ６）を加えて、当該溶質であるＬｉＰＦ６の濃度が、１ｍｏｌ／Ｌとなるように濃度調整して、非水電解液を調製した。上述のとおり作製した実施例１の試験用正極板を作用極板として用い、対極板及び参照極板として金属リチウム板を用い、電解液として上記にて作製した非水電解液を用い、三極式コインセルを組み立て、これを実施例試験セル１とした。そして実施例試験セル１を下記充放電試験に供した。
<Production of tripolar coin cell>
Lithium hexafluorophosphate (LiPF 6 ) is added as a solute to a mixed solvent of ethylene carbonate (EC) / dimethyl carbonate (DMC) (volume ratio = 1: 1), and the concentration of LiPF 6 as the solute is 1 mol. The non-aqueous electrolyte was prepared by adjusting the concentration to be / L. Using the test positive electrode plate of Example 1 prepared as described above as a working electrode plate, using a metal lithium plate as a counter electrode plate and a reference electrode plate, and using the non-aqueous electrolyte prepared above as an electrolyte, three electrodes A type coin cell was assembled, and this was designated as Example Test Cell 1. The example test cell 1 was subjected to the following charge / discharge test.
＜充放電試験＞
上述のとおり作成した三極式コインセルである実施例試験セル１において、作用極板の放電試験を実施するために、まず実施例試験セル１を下記充電試験のとおり満充電させた。
<Charge / discharge test>
In the example test cell 1, which is a tripolar coin cell created as described above, the example test cell 1 was first fully charged as shown in the following charging test in order to conduct a discharge test of the working electrode plate.
（充電試験）
実施例試験セル１を、２５℃の環境下で、電圧が４．３Ｖに達するまで定電流（５６０μＡ）で定電流充電し、当該電圧が４．３Ｖ（満充電電圧）に達した後は、電圧が４．３Ｖを上回らないように、当該電流（放電レート：１Ｃ）が５％以下となるまで減らしていき、定電圧で充電を行ない、満充電させた後、１０分間休止させた。尚、ここで、上記「１Ｃ」とは、上記三極式コインセルを用いて定電流放電して、１時間で放電終了となる電流値（放電終止電圧に達する電流値）のことを意味する。また上記定電流は、実施例試験セル１における作用極板において、活物質であるマンガン酸リチウムの理論放電値９０ｍＡｈ／ｇが１時間で放電されるように設定された電流値である。
(Charge test)
Example Test cell 1 was charged at a constant current (560 μA) under a 25 ° C. environment until the voltage reached 4.3 V, and after the voltage reached 4.3 V (full charge voltage), The current (discharge rate: 1 C) was reduced until the voltage became 5% or less so that the voltage did not exceed 4.3 V, the battery was charged at a constant voltage, fully charged, and then rested for 10 minutes. Here, the “1C” means a current value (current value reaching the discharge end voltage) at which constant current discharge is performed using the tripolar coin cell and discharge is completed in one hour. Further, the constant current is a current value set so that a theoretical discharge value of 90 mAh / g of lithium manganate as an active material is discharged in one hour on the working electrode plate in the example test cell 1.
（放電試験）
その後、満充電された実施例試験セル１を、２５℃の環境下で、電圧が４．３Ｖ（満充電電圧）から３．０Ｖ（放電終止電圧）になるまで、定電流（５６０μＡ）（放電レート：１Ｃ）で定電流放電し、縦軸にセル電圧（Ｖ）、横軸に放電時間（ｈ）をとり、放電曲線を作成し、正極用電極板の放電容量（ｍＡｈ）を求め、作用極である実施例１の正極板の放電容量（ｍＡｈ）を求めた。結果を表３に示す。
(Discharge test)
Thereafter, the fully charged example test cell 1 was subjected to a constant current (560 μA) (discharge) in an environment of 25 ° C. until the voltage changed from 4.3 V (full charge voltage) to 3.0 V (discharge end voltage). A constant current discharge at a rate of 1 C), the cell voltage (V) on the vertical axis and the discharge time (h) on the horizontal axis, a discharge curve is created, and the discharge capacity (mAh) of the electrode plate for the positive electrode is obtained. The discharge capacity (mAh) of the positive electrode plate of Example 1 which is a pole was determined. The results are shown in Table 3.
直流抵抗値の測定：
実施例試験セル１を用い、放電レート１Ｃと５Ｃで放電試験を行って求めた、放電開始１０秒後の電圧値Ｖ１、Ｖ５と、放電レートに対応する定電流値Ｉ１、Ｉ５とから、前記（１）式により実施例１の電極板の直流抵抗（Ω）を求めた。結果は、表３に示す。
DC resistance measurement:
From the voltage values V1 and V5 10 seconds after the start of discharge and the constant current values I1 and I5 corresponding to the discharge rate obtained by conducting a discharge test at discharge rates 1C and 5C using the example test cell 1, The direct-current resistance (Ω) of the electrode plate of Example 1 was determined from the equation (1). The results are shown in Table 3.
初期充放電効率：
実施例１の初期充放電効率を下記のとおり求めた。即ち、上記充電試験において、縦軸に印加電流（ｍＡ）、横軸に充電時間（ｈ）をとり、充電曲線を作成し、その面積（電流×時間の計算により求めた面積）から正極用電極板の充電容量（μＡｈ）を求め、また上記放電試験において同様に正極用電極板の放電容量（μＡｈ）の実測値を求め、（正極板の実測放電容量（μＡｈ））／（正極板の実測充電容量（μＡｈ））×１００なる式から、初期充放電効率を算出した。結果を表３に示す。
Initial charge / discharge efficiency:
The initial charge / discharge efficiency of Example 1 was determined as follows. That is, in the above charging test, the vertical axis represents the applied current (mA), the horizontal axis represents the charging time (h), and a charging curve was prepared. The charge capacity (μAh) of the plate was obtained, and the measured value of the discharge capacity (μAh) of the positive electrode plate was similarly obtained in the above discharge test, and the (measured discharge capacity (μAh) of the positive plate) / (actual measurement of the positive plate) The initial charge and discharge efficiency was calculated from the equation: charge capacity (μAh)) × 100. The results are shown in Table 3.
（サイクル特性試験）
実施例試験セル１を用いて、サイクル特性試験を行なった。サイクル特性試験は、放電レートが１０Ｃ（定電流：１３．９５ｍＡ）である場合についての充放電試験によって実施された。充放電試験は、１回の充電試験および放電試験の組み合わせを１サイクルとして、これを１００サイクル繰り返して実施した。そして、実施例１のサイクル特性を、１００サイクル放電容量維持率（％）の値に基づき次のような評価基準で評価した。なお、１００サイクル放電容量維持率（％）は、１００サイクル後の放電容量（ｍＡｈ）を１サイクル後の放電容量（ｍＡｈ）で除して１００を掛けることで算出される値である。結果を表３に示す。
(Cycle characteristic test)
Using the example test cell 1, a cycle characteristic test was conducted. The cycle characteristic test was carried out by a charge / discharge test when the discharge rate was 10 C (constant current: 13.95 mA). The charge / discharge test was performed by repeating one cycle of a combination of a charge test and a discharge test as one cycle and repeating this for 100 cycles. Then, the cycle characteristics of Example 1 were evaluated according to the following evaluation criteria based on the value of 100 cycle discharge capacity retention rate (%). The 100-cycle discharge capacity retention rate (%) is a value calculated by dividing the discharge capacity (mAh) after 100 cycles by the discharge capacity (mAh) after 1 cycle and multiplying by 100. The results are shown in Table 3.
（サイクル特性の評価基準）
１００サイクル容量維持率が８０％以上１００％以下・・・・◎（極めて良好）
１００サイクル容量維持率が５０％以上８０％未満・・・・・○（良好）
１００サイクル容量維持率が５０％未満・・・・・・・・・・×（不良）
(Evaluation criteria for cycle characteristics)
100 cycle capacity maintenance rate is 80% or more and 100% or less ... (very good)
100 cycle capacity maintenance rate is 50% or more and less than 80%.
100 cycle capacity maintenance rate is less than 50%.
（実施例２乃至５）
表１に示す正極活物質粒子、金属元素含有化合物、および溶媒、樹脂を含む正極活物質層形成液を、実施例１と同様にして集電体に塗布して集電体表面に電極活物質層形成用と膜を形成した後、電気炉内で１時間かけて表２に示す加熱温度まで加熱し、同表に示す時間加熱して正極板を得た。この正極板を直径１５ｍｍの円板状に裁断して試験用正極板とした。実施例１と同様にして、電極活物質層の膜厚、膜形成性、結着物質の組成及び結晶性、電極活物質中の炭素成分、結着物質のリチウムイオン挿入脱離反応の有無等を測定した結果を表２にあわせて示す。また、得られた試験用の正極板を用いて実施例１と同様に三極式コインセルを作製し、同様の性能試験を行った。結果を表３に示す。集電体面に略垂直に切断した切断面を走査型電子顕微鏡で観察した結果、実施例２〜５の電極板も、実施例１の電極板と同様、核体である活物質粒子と、活物質粒子表面の少なくとも一部を被覆する包囲体を構成する金属酸化物粒子とにより、二重構造をなしていることが確認された。
(Examples 2 to 5)
A positive electrode active material layer-forming liquid containing positive electrode active material particles, a metal element-containing compound, a solvent, and a resin shown in Table 1 was applied to a current collector in the same manner as in Example 1, and the electrode active material was applied to the surface of the current collector. After forming the film for forming the layer and the film, it was heated to the heating temperature shown in Table 2 in an electric furnace over 1 hour, and heated for the time shown in the same table to obtain a positive electrode plate. The positive electrode plate was cut into a disk shape having a diameter of 15 mm to obtain a test positive electrode plate. In the same manner as in Example 1, the film thickness of the electrode active material layer, the film forming property, the composition and crystallinity of the binder material, the carbon component in the electrode active material, the presence or absence of the lithium ion insertion / release reaction of the binder material, etc. The results of measuring are also shown in Table 2. In addition, a tripolar coin cell was prepared in the same manner as in Example 1 using the obtained positive electrode plate for testing, and the same performance test was performed. The results are shown in Table 3. As a result of observing the cut surface cut substantially perpendicularly to the current collector surface with a scanning electron microscope, the electrode plates of Examples 2 to 5 also had active material particles as cores and active plates, like the electrode plate of Example 1. It was confirmed that the metal oxide particles constituting the enclosure covering at least a part of the surface of the substance particles formed a double structure.
（実施例６）
実施例５と同様に正極板を作成した。そして、以下のとおり調製した樹脂混合液の満たされた浸漬槽に実施例５を浸漬させ、実施例５の空隙に上記樹脂混合液を充分に浸透させた。その後、実施例５と上記浸漬層から取りだし、１４０℃に加温したオーブン内に設置して１５分間乾燥させて、樹脂混合液の溶媒を除去し、さらに１４０℃にて５分間、真空乾燥させた。これによって、電極活物質層中に、樹脂製結着材が残留する正極板を作成し、これを実施例５とした。尚、上記樹脂混合液は、樹脂材料として、ＰＶＤＦ樹脂を用い、ＰＶＤＦの濃度が０．１％となるようＮＭＰ溶媒に混合させて調製した。集電体面に略垂直に切断した切断面を走査型電子顕微鏡で観察した結果、実施例６の電極板も、実施例１の電極板と同様、核体である活物質粒子と、活物質粒子表面の少なくとも一部を被覆する包囲体を構成する金属酸化物粒子とにより、二重構造をなしていることが確認された。
(Example 6)
A positive electrode plate was prepared in the same manner as in Example 5. And Example 5 was immersed in the immersion tank with which the resin mixed solution prepared as follows was filled, and the said resin mixed solution was fully osmose | permeated in the space | gap of Example 5. FIG. Then, it took out from Example 5 and the said immersion layer, installed in the oven heated at 140 degreeC, it was made to dry for 15 minutes, the solvent of the resin liquid mixture was removed, and also it was made to vacuum-dry at 140 degreeC for 5 minutes. It was. Thus, a positive electrode plate in which the resin binder remained in the electrode active material layer was prepared, and this was designated as Example 5. The resin mixed solution was prepared by using PVDF resin as a resin material and mixing it with an NMP solvent so that the concentration of PVDF was 0.1%. As a result of observing the cut surface cut substantially perpendicularly to the current collector surface with a scanning electron microscope, the electrode plate of Example 6 was also active core particles and active material particles as in the case of the electrode plate of Example 1. It was confirmed that the metal oxide particles constituting the enclosure covering at least a part of the surface formed a double structure.
（実施例７）
ＰＶＤＦ樹脂の濃度が１０％となるよう調整したこと以外は実施例６と同様に正極板を作成し、これを実施例７とした。集電体面に略垂直に切断した切断面を走査型電子顕微鏡で観察した結果、実施例７の電極板も、実施例１の電極板と同様、核体である活物質粒子と、活物質粒子表面の少なくとも一部を被覆する包囲体を構成する金属酸化物粒子とにより、二重構造をなしていることが確認された。
(Example 7)
A positive electrode plate was prepared in the same manner as in Example 6 except that the concentration of the PVDF resin was adjusted to 10%. As a result of observing the cut surface cut substantially perpendicularly to the current collector surface with a scanning electron microscope, the electrode plate of Example 7 was also active core particles and active material particles as in the case of the electrode plate of Example 1. It was confirmed that the metal oxide particles constituting the enclosure covering at least a part of the surface formed a double structure.
（比較例１）
非水電解液二次電池用正極板における正極活物質層を形成するための正極活物質層形成液を以下のとおり調製した。まず、正極活物質粒子である平均粒径４μｍのＬｉＭｎＯ４粉末９ｇ、導電材としてアセチレンブラック（電気化学工業株式会社製、デンカブラック）を１．５ｇ、樹脂製結着材としてＰＶＤＦ（クレハ社製、ＫＦ＃１１００）を１．０ｇに、溶媒としてＮＭＰ（三菱化学社製）９ｇを加えて混練、分散させてスラリー状の正極活物質層形成液を得た。
(Comparative Example 1)
A positive electrode active material layer forming liquid for forming a positive electrode active material layer in a positive electrode plate for a non-aqueous electrolyte secondary battery was prepared as follows. First, 9 g of LiMnO 4 powder having an average particle size of 4 μm as positive electrode active material particles, 1.5 g of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Black) as a conductive material, and PVDF (manufactured by Kureha Co., Ltd.) as a resin binder , KF # 1100) and 1.0 g of NMP (manufactured by Mitsubishi Chemical Corporation) as a solvent were added and kneaded and dispersed to obtain a slurry-like positive electrode active material layer forming liquid.
上記にて調製した正極活物質層形成液を、正極集電体である厚さ１５μｍのアルミ箔上に、乾燥後の正極活物質層形成液の塗工量が４５ｇ／ｍ２となるように塗布し、その後、１２０℃のオーブン内で乾燥を行ない、正極活物質層を形成した。さらに、正極活物質層の塗工密度が２．０ｇ／ｃｍ３（正極活物質層の厚さ：４０μｍ）となるように、ロールプレス機を用いてプレスした後、所定の大きさ（１５ｍｍφ）に裁断し、１４０℃にて５分間、真空乾燥させて比較例１の試験用正極板とした。実施例１と同様にして、電極活物質層の膜厚、膜形成性、結着物質の組成及び結晶性、電極活物質中の炭素成分、結着物質のリチウムイオン挿入脱離反応の有無等を測定した結果を表２にあわせて示す。また、得られた試験用の正極板を用いて実施例１と同様に三極式コインセルを作製し、同様の性能試験を行った。結果を表３に示す。また集電体面に対し略垂直に切断した際の電極活物質層の断面の走査型電子顕微鏡写真を図６（倍率１万倍）、図７（倍率５万倍）に示す。 The coating amount of the positive electrode active material layer forming liquid after drying is adjusted to 45 g / m 2 on the 15 μm thick aluminum foil as the positive electrode current collector. After coating, drying was performed in an oven at 120 ° C. to form a positive electrode active material layer. Furthermore, after pressing using a roll press machine so that the coating density of the positive electrode active material layer becomes 2.0 g / cm 3 (thickness of the positive electrode active material layer: 40 μm), a predetermined size (15 mmφ) And vacuum-dried at 140 ° C. for 5 minutes to obtain a test positive electrode plate of Comparative Example 1. In the same manner as in Example 1, the film thickness of the electrode active material layer, the film forming property, the composition and crystallinity of the binder material, the carbon component in the electrode active material, the presence or absence of the lithium ion insertion / release reaction of the binder material, etc. The results of measuring are also shown in Table 2. In addition, a tripolar coin cell was prepared in the same manner as in Example 1 using the obtained positive electrode plate for testing, and the same performance test was performed. The results are shown in Table 3. Further, scanning electron micrographs of the cross section of the electrode active material layer when cut substantially perpendicular to the current collector surface are shown in FIG. 6 (magnification 10,000 times) and FIG. 7 (magnification 50,000 times).
（比較例２）
金属酸化物の前駆体である金属元素含有化合物を加えなかった以外、実施例１と同様にして電極活物質層形成溶液調整した。この電極活物質層形成溶液を用い実施例１と同様にして正極板を作製した。しかしながら、この正極板は膜形成性が不良であり、所定の大きさ（１５ｍｍφ）に裁断する際に電極活物質層が剥がれてしまい、試験用正極板を形成することができなかった。
(Comparative Example 2)
An electrode active material layer forming solution was prepared in the same manner as in Example 1 except that the metal element-containing compound that was a precursor of the metal oxide was not added. A positive electrode plate was produced in the same manner as in Example 1 using this electrode active material layer forming solution. However, this positive electrode plate was poor in film formability, and the electrode active material layer was peeled off when it was cut into a predetermined size (15 mmφ), and a test positive electrode plate could not be formed.
（実施例考察）
表２に示すとおり、実施例１乃至７は、いずれも樹脂製結着材を用いずに電極活物質層を形成したが、いずれも膜形成性が良好であり、樹脂製結着材を使用した比較例１と同等に集電体との密着性が良好であることが確認された。したがって、電極活物質層中に形成された金属酸化物粒子が結着物質粒子として作用していることが確認された。また、実施例１乃至７について、活物質粒子を除いて作成した参考例が、いずれもリチウムイオン挿入脱離反応を示さないことが確認され、電極活物質層中に存在する結着物質粒子である金属酸化物粒子が、リチウムイオン挿入脱離反応を示さないものであることが確認された。
(Example consideration)
As shown in Table 2, in Examples 1 to 7, all of the electrode active material layers were formed without using the resin binder, but all of the film forming properties were good and the resin binder was used. It was confirmed that the adhesion to the current collector was as good as that of Comparative Example 1. Therefore, it was confirmed that the metal oxide particles formed in the electrode active material layer acted as binder material particles. In addition, for Examples 1 to 7, it was confirmed that all of the reference examples prepared by removing the active material particles did not show a lithium ion insertion / release reaction, and the binder material particles present in the electrode active material layer It was confirmed that a certain metal oxide particle does not show a lithium ion insertion / release reaction.
また、表３に示すとおり、実施例１乃至７の正極板の電極活物質層における単位面積当たりの活物質粒子の量と、比較例１の正極板の電極活物質層における単位面積当たりの活物質粒子の量が、ほぼ同等であるにもかかわらず、電極板の出入力性能を示す直流抵抗値において、実施例１乃至７は、比較例１に対し、いずれも小さい値を示しており、出入力性能が向上していた。 Further, as shown in Table 3, the amount of active material particles per unit area in the electrode active material layers of the positive electrode plates of Examples 1 to 7 and the activity per unit area in the electrode active material layer of the positive electrode plate of Comparative Example 1 Despite the fact that the amount of the substance particles is almost the same, in the DC resistance value indicating the input / output performance of the electrode plate, each of Examples 1 to 7 shows a smaller value than Comparative Example 1, I / O performance was improved.
また、実施例１乃至７の正極板の電極活物質中における活物質粒子の単位面積当たりの量と、比較例１の正極板の電極活物質中における活物質粒子の単位面積当たりの量は、ほぼ同等量であるにもかかわらず、電極板の出入力特性を示す直流抵抗値が実施例１乃至７では、比較例１に対していずれも低い値を示しており、出入力性能が向上しており、放電容量も比較例１と同等以上の値を示していた。実施例１乃至７は、電極板自体の出入力特性等を評価したものであるが、いずれも出入力性能等が高いことから、これらの電極板のどちらか一方、あるいは両方を用いてリチウムイオン二次電池を作成した場合には、当然に、電池の出入力性能、初期充放電効率などが向上することが示唆された。また、上記実施例１乃至７の電極板を正極板および／または負極板として用いる非水電解液二次電池および電池パックについても、出入力特性が向上し、することが示唆された。 Further, the amount per unit area of the active material particles in the electrode active material of the positive electrode plate of Examples 1 to 7 and the amount per unit area of the active material particles in the electrode active material of the positive electrode plate of Comparative Example 1 are: In spite of almost the same amount, the DC resistance values indicating the input / output characteristics of the electrode plates are lower than those of Comparative Example 1 in Examples 1 to 7, and the input / output performance is improved. The discharge capacity was also equal to or greater than that of Comparative Example 1. In Examples 1 to 7, the input / output characteristics and the like of the electrode plate itself were evaluated. However, since all of the input / output performance and the like are high, lithium ion can be obtained using either one or both of these electrode plates. It was suggested that when a secondary battery was prepared, the battery input / output performance, initial charge / discharge efficiency, and the like were naturally improved. In addition, it was suggested that the non-aqueous electrolyte secondary battery and the battery pack using the electrode plates of Examples 1 to 7 as the positive electrode plate and / or the negative electrode plate also improved the input / output characteristics.
１、１’、１’’、５５ 集電体
２、５４ 電極活物質層
３ 集電基材
４ 導電性層
５ 断続層
６ 核体
７ 包囲体
１０、２０、２０’、２０’’、２０’’’ 非水電解液二次電池用電極板
２１ 活物質粒子
２２ 結着物質粒子
３０ 電池パック
３１ リチウムイオン二次電池
３２ 正極端子
３３ 負極端子
３４ 保護回路基板
３５ 外部接続コネクタ
３６ａ、３６ｂ 樹脂容器
３７ 端部ケース
３８ａ、３８ｂ 外部接続用窓
５０ 非水電解液二次電池用電極板（正極板）
７０ セパレータ
８１、８２ 外装
９０ 非水電解液
１００ リチウムイオン二次電池
１０１、１０２、１０３、１０３’ 表面
1, 1 ′, 1 ″, 55 Current collector 2, 54 Electrode active material layer 3 Current collecting base material 4 Conductive layer 5 Intermittent layer 6 Core body 7 Enclosure 10, 20, 20 ′, 20 ″, 20 '''Electrode plate 21 for non-aqueous electrolyte secondary battery 21 Active material particle 22 Binder material particle 30 Battery pack 31 Lithium ion secondary battery 32 Positive electrode terminal 33 Negative electrode terminal 34 Protective circuit board 35 External connector 36a, 36b Resin container 37 End case 38a, 38b Window 50 for external connection Electrode plate for non-aqueous electrolyte secondary battery (positive electrode plate)
70 Separator 81, 82 Exterior 90 Non-aqueous electrolyte 100 Lithium ion secondary battery 101, 102, 103, 103 'Surface
Claims (9)
上記電極活物質層が、活物質粒子および結着物質粒子を含有しており、
上記結着物質粒子が、リチウムイオン挿入脱離反応を示さない金属酸化物粒子であり、
上記結着物質粒子の平均粒径が、上記活物質粒子の平均粒径より小さいことを特徴とする非水電解液二次電池用電極板。 An electrode plate for a nonaqueous electrolyte secondary battery comprising a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer contains active material particles and binder material particles,
The binder material particles are metal oxide particles that do not exhibit lithium ion insertion / release reaction,
An electrode plate for a non-aqueous electrolyte secondary battery, wherein an average particle size of the binder material particles is smaller than an average particle size of the active material particles.
上記正極板または負極板のいずれか一方、あるいは両方が、請求項１から７のいずれか１項に記載の非水電解液二次電池用電極板であることを特徴とする非水電解液二次電池。 A non-aqueous electrolyte secondary battery comprising at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte containing a non-aqueous solvent,
Either one or both of the positive electrode plate and the negative electrode plate is the electrode plate for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 7, wherein the non-aqueous electrolyte solution 2 Next battery.
上記非水電解液二次電池が、正極板と、負極板と、上記正極板と上記負極板との間に設けられるセパレータと、非水溶媒を含む電解液とを少なくとも備えた非水電解液二次電池であり、
上記正極板または負極板のいずれか一方、あるいは両方が、請求項１から７のいずれか１項に記載の非水電解液二次電池用電極板であることを特徴とする電池パック。 A storage case; a non-aqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal; and a protection circuit having an overcharge and over-discharge protection function, wherein the storage case includes the non-aqueous electrolyte secondary battery and the In a battery pack configured to contain a protection circuit,
The non-aqueous electrolyte secondary battery includes at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a non-aqueous solvent. A secondary battery,
Either one of the said positive electrode plate or a negative electrode plate, or both are the electrode plates for nonaqueous electrolyte secondary batteries of any one of Claim 1 to 7, The battery pack characterized by the above-mentioned.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021508160A (en) * | 2018-07-16 | 2021-02-25 | エルジー・ケム・リミテッド | Positive electrode for lithium secondary battery containing iron oxide and lithium secondary battery equipped with this |
| JP2021508919A (en) * | 2018-07-10 | 2021-03-11 | エルジー・ケム・リミテッド | A method for producing iron oxyhydroxide nitrate, a positive electrode for a lithium secondary battery containing iron oxyhydroxide produced thereby, and a lithium secondary battery provided with the positive electrode. |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021508919A (en) * | 2018-07-10 | 2021-03-11 | エルジー・ケム・リミテッド | A method for producing iron oxyhydroxide nitrate, a positive electrode for a lithium secondary battery containing iron oxyhydroxide produced thereby, and a lithium secondary battery provided with the positive electrode. |
| JP7062067B2 (en) | 2018-07-10 | 2022-05-02 | エルジー エナジー ソリューション リミテッド | A method for producing iron oxyhydroxide, a positive electrode for a lithium secondary battery containing iron oxyhydroxide produced thereby, and a lithium secondary battery provided with the positive electrode. |
| US11417880B2 (en) | 2018-07-10 | 2022-08-16 | Lg Energy Solution, Ltd. | Method for preparing iron nitrate oxyhydroxide, cathode containing iron nitrate oxyhydroxide prepared thereby for lithium secondary battery, and lithium secondary battery comprising same |
| JP2021508160A (en) * | 2018-07-16 | 2021-02-25 | エルジー・ケム・リミテッド | Positive electrode for lithium secondary battery containing iron oxide and lithium secondary battery equipped with this |
| JP7046194B2 (en) | 2018-07-16 | 2022-04-01 | エルジー エナジー ソリューション リミテッド | Positive electrode for lithium secondary battery containing iron oxide and lithium secondary battery equipped with this |
| US11942633B2 (en) | 2018-07-16 | 2024-03-26 | Lg Energy Solution, Ltd. | Cathode of lithium secondary battery comprising iron oxide, and lithium secondary battery comprising same |
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