JP5444543B2 - Lithium ion secondary battery electrode and lithium ion secondary battery - Google Patents
Lithium ion secondary battery electrode and lithium ion secondary battery Download PDFInfo
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- JP5444543B2 JP5444543B2 JP2011199020A JP2011199020A JP5444543B2 JP 5444543 B2 JP5444543 B2 JP 5444543B2 JP 2011199020 A JP2011199020 A JP 2011199020A JP 2011199020 A JP2011199020 A JP 2011199020A JP 5444543 B2 JP5444543 B2 JP 5444543B2
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- glass ceramic
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- lithium ion
- ion secondary
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- 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
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Description
本発明は、良好な充放電サイクル特性を有するリチウムイオン二次電池と、該リチウムイオン二次電池を構成し得る電極に関するものである。 The present invention relates to a lithium ion secondary battery having good charge / discharge cycle characteristics and an electrode that can constitute the lithium ion secondary battery.
リチウムイオン二次電池は、携帯用電子機器やハイブリッド自動車などに用いるための電池として、急速に開発が進められている。このようなリチウムイオン二次電池では、負極活物質には主に炭素材料が用いられ、正極活物質には、金属酸化物、金属硫化物、各種ポリマーなどが用いられている。特に、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウムなどのリチウム複合酸化物は、高エネルギー密度で高電圧の電池を実現できることから、現在、リチウムイオン二次電池の正極活物質として一般的に用いられている。 Lithium ion secondary batteries are being rapidly developed as batteries for use in portable electronic devices and hybrid vehicles. In such a lithium ion secondary battery, a carbon material is mainly used as the negative electrode active material, and metal oxides, metal sulfides, various polymers, and the like are used as the positive electrode active material. In particular, lithium composite oxides such as lithium cobaltate, lithium nickelate, and lithium manganate can be used as a positive electrode active material for lithium ion secondary batteries because they can realize high energy density and high voltage batteries. It has been.
また、現在では、使用機器の高機能化などに伴って、例えば、電池の充放電サイクル特性向上が求められている。 Further, at present, for example, improvement in charge / discharge cycle characteristics of a battery is demanded with the enhancement of functions of used devices.
例えば、特許文献１には、固体電解質材料として用いられるガラスセラミックスで被覆した正極活物質を使用することで、リチウムイオン二次電池の充放電サイクル特性が向上することが記載されている。 For example, Patent Document 1 describes that the charge / discharge cycle characteristics of a lithium ion secondary battery are improved by using a positive electrode active material coated with glass ceramics used as a solid electrolyte material.
しかしながら、特許文献１に記載の技術では、リチウムイオン二次電池の充放電サイクル特性は向上するものの、不可逆容量を増大させ容量の低下を引き起こすという問題もある。よって、こうした問題の発生を抑えつつ、リチウムイオン二次電池の充放電サイクル特性を高め得る技術の開発が求められる。 However, although the technology described in Patent Document 1 improves the charge / discharge cycle characteristics of the lithium ion secondary battery, there is also a problem that the irreversible capacity is increased and the capacity is reduced. Therefore, development of a technique capable of improving the charge / discharge cycle characteristics of the lithium ion secondary battery while suppressing the occurrence of such problems is required.
本発明は、前記事情に鑑みてなされたものであり、その目的は、良好な充放電サイクル特性を有し、かつ不可逆容量の増大を抑制したリチウムイオン二次電池と、該リチウムイオン二次電池を構成し得る電極とを提供することにある。 The present invention has been made in view of the above circumstances, and an object thereof is a lithium ion secondary battery having favorable charge / discharge cycle characteristics and suppressing an increase in irreversible capacity, and the lithium ion secondary battery. It is providing the electrode which can comprise.
前記目的を達成し得た本発明のリチウムイオン二次電池用電極は、ガラスセラミックス粒子、Ｌｉを吸蔵放出可能な活物質粒子および樹脂製バインダを含む電極合剤層を有するリチウムイオン二次電池用電極であって、前記ガラスセラミックス粒子は、Ｌｉイオン伝導性を有していて、一次粒子の平均粒子径が５〜５０ｎｍであり、粉末Ｘ線回折スペクトルにおける２θ＝２０〜７０°の範囲内において、ピークを有していないか、または最も強度の大きなピークの半値幅が１．０°以上であり、前記活物質粒子と前記ガラスセラミックス粒子の合計を１００質量％としたとき、前記ガラスセラミックス粒子の割合が０．１〜１０質量％であることを特徴とするものである。 The electrode for a lithium ion secondary battery of the present invention that can achieve the above object is for a lithium ion secondary battery having an electrode mixture layer containing glass ceramic particles, active material particles capable of occluding and releasing Li, and a resin binder. In the electrode, the glass ceramic particles have Li ion conductivity, the primary particles have an average particle diameter of 5 to 50 nm, and in the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum. The glass ceramic particles have no peak or the peak width at half maximum of 1.0 ° or more, and the total of the active material particles and the glass ceramic particles is 100% by mass. The ratio is 0.1 to 10% by mass.
また、本発明のリチウムイオン二次電池は、正極、負極、非水電解液およびセパレータを有しており、前記正極および／または前記負極が、本発明に記載のリチウムイオン二次電池用電極であることを特徴とするものである。 The lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, and the positive electrode and / or the negative electrode is an electrode for a lithium ion secondary battery according to the present invention. It is characterized by being.
本発明によれば、良好な充放電サイクル特性を有し、かつ不可逆容量の増大を抑制したリチウムイオン二次電池と、該リチウムイオン二次電池を構成し得る電極とを提供することができる。 According to the present invention, it is possible to provide a lithium ion secondary battery having good charge / discharge cycle characteristics and suppressing an increase in irreversible capacity, and an electrode that can constitute the lithium ion secondary battery.
本発明のリチウムイオン二次電池用電極（以下、単に「電極」という場合がある）は、ガラスセラミックス粒子、Ｌｉを吸蔵放出可能な活物質粒子および樹脂製バインダを含む電極合剤層を有するものであり、この電極合剤層が、例えば、集電体の片面または両面に形成された構造を有している。本発明の電極は、リチウムイオン二次電池の正極または負極に使用される。 An electrode for a lithium ion secondary battery of the present invention (hereinafter sometimes simply referred to as “electrode”) has an electrode mixture layer containing glass ceramic particles, active material particles capable of occluding and releasing Li, and a resin binder. The electrode mixture layer has a structure formed on one side or both sides of the current collector, for example. The electrode of the present invention is used for a positive electrode or a negative electrode of a lithium ion secondary battery.
本発明の電極に係る電極合剤層に含有させる前記ガラスセラミックス粒子は、Ｌｉイオン伝導性を有しており、微細で、かつ結晶性の低いものである。 The glass ceramic particles contained in the electrode mixture layer according to the electrode of the present invention have Li ion conductivity, are fine, and have low crystallinity.
本発明の電極において、前記ガラスセラミックス粒子を使用することで、このガラスセラミックス粒子の表面特性の影響によってリチウムイオンの脱溶媒和反応が促進される結果、拡散分極が低減される。また、添加したガラスセラミックス粒子が取り込まれることによって電極の活物質の表面に緻密で安定な被膜が形成され、かつガラスセラミックス粒子がＬｉイオン伝導性を有しているため、形成された被膜のＬｉイオン伝導性を向上されることができる。従って、この電極を用いた電池において、この電極（そこに含まれる活物質）と非水電解液との間の界面抵抗を下げることができる。本発明の電極を用いた電池（本発明のリチウムイオン二次電池）では、前記ガラスセラミックス粒子によるこれらの作用によって、比較的高負荷でも充放電サイクル特性を向上させることができる。 In the electrode of the present invention, the use of the glass ceramic particles promotes the desolvation reaction of lithium ions due to the influence of the surface characteristics of the glass ceramic particles, thereby reducing diffusion polarization. Further, since the added glass ceramic particles are taken in, a dense and stable film is formed on the surface of the active material of the electrode, and the glass ceramic particles have Li ion conductivity. The ion conductivity can be improved. Therefore, in the battery using this electrode, the interface resistance between this electrode (the active material contained therein) and the non-aqueous electrolyte can be lowered. In a battery using the electrode of the present invention (lithium ion secondary battery of the present invention), charge and discharge cycle characteristics can be improved even at a relatively high load by these actions of the glass ceramic particles.
また、本発明の電極では、前記ガラスセラミックス粒子の表面極性により、電池の有する非水電解液の電極合剤層への導入がスムーズとなる。そのため、例えば、電極合剤層を厚くしても、電極の活物質の利用効率が低下しないことから、本発明の電極を用いた電池において、充放電サイクル特性を高めつつ、より一層の高容量化を図ることもできる。 Moreover, in the electrode of this invention, the non-aqueous electrolyte which a battery has into the electrode mixture layer becomes smooth by the surface polarity of the glass ceramic particles. Therefore, for example, even if the electrode mixture layer is thickened, the utilization efficiency of the active material of the electrode does not decrease. Therefore, in the battery using the electrode of the present invention, the charge / discharge cycle characteristics are improved and the capacity is further increased. Can also be achieved.
前記ガラスセラミックス粒子は、一次粒子の平均粒子径が、５０ｎｍ以下、好ましくは５０ｎｍ未満、より好ましくは３０ｎｍ以下である。このような微細なガラスセラミックス粒子であれば、前記の電池の高負荷での充放電サイクル特性を高める作用が良好に発揮される。ガラスセラミックス粒子のサイズが５０ｎｍより大きくても、結晶性が低い場合には、例えば、非水電解液の電極合剤層へのスムーズな導入については一定の効果がある。しかし、ガラスセラミックス粒子のサイズがあまり大きくなると、活物質表面に形成される被膜に取り込まれ難くなり、良好なＬｉイオン伝導性を有する安定な被膜を形成することができない。 The glass ceramic particles have an average primary particle size of 50 nm or less, preferably less than 50 nm, more preferably 30 nm or less. With such fine glass ceramic particles, the effect of enhancing the charge / discharge cycle characteristics of the battery at a high load is exhibited well. Even if the size of the glass ceramic particles is larger than 50 nm, if the crystallinity is low, for example, smooth introduction of the non-aqueous electrolyte into the electrode mixture layer has a certain effect. However, when the size of the glass ceramic particles becomes too large, it becomes difficult to be incorporated into the film formed on the surface of the active material, and a stable film having good Li ion conductivity cannot be formed.
ただし、あまりにサイズの小さな前記ガラスセラミックス粒子の場合には、製造が困難であり、また、取り扱い性が低下する。よって、前記ガラスセラミックス粒子の一次粒子の平均粒子径は、１ｎｍ以上であり、１．５ｎｍ以上であることが好ましい。 However, in the case of the glass ceramic particles having a too small size, the production is difficult and the handleability is lowered. Therefore, the average particle diameter of the primary particles of the glass ceramic particles is 1 nm or more, and preferably 1.5 nm or more.
なお、本明細書でいうガラスセラミックス粒子の一次粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）観察したガラスセラミックス粒子の一次粒子３００個について、粒子の直径（粒子が球形の場合）または長軸長さの径（粒子が球形以外の形状の場合）を求め、これらの粒子径の合計値を個数（３００個）で除して求められる平均値である。ただし、ガラスセラミックス粒子のサイズがあまりに微細で、前記の方法による測定が難しい場合には、小角Ｘ線散乱法により、一次粒子の平均粒子径を求めればよい。 In addition, the average particle diameter of the primary particle of the glass ceramic particle as used in the present specification is the particle diameter (when the particle is spherical) or the length of 300 primary particles of the glass ceramic particle observed with a transmission electron microscope (TEM). This is an average value obtained by determining the diameter of the axial length (when the particles have a shape other than a sphere) and dividing the total value of these particle diameters by the number (300). However, when the size of the glass ceramic particles is too fine and measurement by the above method is difficult, the average particle diameter of the primary particles may be obtained by a small angle X-ray scattering method.
また、前記ガラスセラミックス粒子は、粉末Ｘ線回折スペクトルにおける２θ＝２０〜７０°の範囲内において、ピークを有していないか、または最も強度の大きなピークの半値幅が、１．０°以上、好ましくは１．５°以上である。このように結晶性の低いガラスセラミックス粒子であれば、前記の電池の充放電サイクル特性を高める作用が良好に発揮される。ガラスセラミックス粒子の結晶性が高くなると、ガラスセラミックス粒子結晶内の空いているＬｉサイトを補完するためにＬｉを吸蔵し、一旦ガラスセラミックス粒子内に吸蔵されたＬｉは放出され難いため、電池の不可逆容量が大きくなる虞がある。更に、ガラスセラミックス粒子の結晶性が高い場合には、微細な形態であっても、電極と非水電解液との間の界面抵抗を低減する作用が小さくなるため、電池特性の大きな向上が見込めなくなる。 Further, the glass ceramic particles do not have a peak within the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum, or the half width of the peak with the largest intensity is 1.0 ° or more, Preferably, it is 1.5 ° or more. Thus, if it is a glass ceramic particle with low crystallinity, the effect | action which improves the charging / discharging cycling characteristics of the said battery will be exhibited favorably. When the crystallinity of the glass ceramic particles becomes high, Li is occluded to supplement the vacant Li sites in the glass ceramic particle crystal, and Li once occluded in the glass ceramic particle is difficult to be released. The capacity may increase. Furthermore, when the crystallinity of the glass ceramic particles is high, the effect of reducing the interfacial resistance between the electrode and the non-aqueous electrolyte is reduced even in a fine form, so that significant improvement in battery characteristics can be expected. Disappear.
更に、前記ガラスセラミックス粒子は、窒素ガス吸着により測定される比表面積が、２０ｍ２／ｇ以上であることが好ましく、３０ｍ２／ｇ以上であることがより好ましく、また、３００ｍ２／ｇ以下であることが好ましい。前記ガラスセラミックス粒子の比表面積が前記のような値の場合には、電池の充放電サイクル特性を高める作用がより向上する。これは、結晶性が低く、かつ比表面積が前記のような大きな構造のガラスセラミックス粒子であれば、例えば、最表面に未結合手が多く残存するため、これらによって非水電解液中のリチウムイオンの解離が促され、リチウムイオンの拡散分極がより低減するためであると考えられる。 Further, the glass ceramic particles preferably have a specific surface area measured by nitrogen gas adsorption of 20 m 2 / g or more, more preferably 30 m 2 / g or more, and 300 m 2 / g or less. Preferably there is. When the specific surface area of the glass ceramic particles is as described above, the effect of improving the charge / discharge cycle characteristics of the battery is further improved. This is because, if the glass ceramic particles have a low crystallinity and a large surface area as described above, for example, many dangling bonds remain on the outermost surface. This is probably because the dissociation of lithium is promoted and the diffusion polarization of lithium ions is further reduced.
本明細書でいうガラスセラミックス粒子の比表面積は、多分子層吸着の理論式であるＢＥＴ式を用いて、表面積を測定、計算したもので、ガラスセラミックス粒子の表面と微細孔の比表面積である。具体的には、日本ベル社製の自動比表面積／細孔分布測定装置（装置型番：ＢＥＬＳＯＲＰ−ｍｉｎｉ）を用い、飽和蒸気圧に対する相対圧０．９９まで測定を行い、ＢＥＴ比表面積として得た値である。また、飽和蒸気圧は測定開始時圧力を用い、死容積は実測値とし、測定前乾燥条件は、窒素ガスフロー中８０℃で２時間とする。 The specific surface area of the glass ceramic particles referred to in the present specification is the specific surface area of the surface of the glass ceramic particles and the fine pores, which is obtained by measuring and calculating the surface area using the BET equation, which is a theoretical formula of multimolecular layer adsorption. . Specifically, using an automatic specific surface area / pore distribution measuring apparatus (apparatus model number: BELSORP-mini) manufactured by Nippon Bell Co., Ltd., measurement was performed up to a relative pressure of 0.99 with respect to the saturated vapor pressure, and the BET specific surface area was obtained. Value. The saturated vapor pressure is the pressure at the start of measurement, the dead volume is an actual measurement value, and the pre-measurement drying conditions are 80 ° C. for 2 hours in a nitrogen gas flow.
本発明に係るガラスセラミックス粒子は、Ｌｉイオン伝導性を有している。結晶構造中にＬｉイオンを有するガラスセラミックスであればＬｉイオン伝導性を有しているので、本発明に係るガラスセラミックス粒子は、このようなガラスセラミックスで構成すればよい。 The glass ceramic particles according to the present invention have Li ion conductivity. Since glass ceramics having Li ions in the crystal structure have Li ion conductivity, the glass ceramic particles according to the present invention may be composed of such glass ceramics.
本発明に係るガラスセラミックス粒子を構成するガラスセラミックスは、Ｌｉと、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、ＢａおよびＳｒよりなる群から選択される少なくとも１種の元素とを含み、ＮＡＳＩＣＯＮ構造を有するガラスセラミックスであることが好ましい。 The glass ceramic constituting the glass ceramic particle according to the present invention includes Li and at least one element selected from the group consisting of Si, Al, Zr, Ti, Ba, and Sr, and has a NASICON structure. It is preferable that
このようなガラスセラミックスの具体例としては、例えば、Ｌｉ１＋ｘＡｌｘＴｉ２−ｘ（ＰＯ４）３（ただし、０≦ｘ≦１．０）、Ｌｉ１＋ｙＭｙＺｒ２−ｙ（ＰＯ４）３（ただし、ＭはＣｒ、ＬａまたはＩｎであり、０≦ｙ≦１．０）などが挙げられる。 Specific examples of such glass ceramics include, for example, Li 1 + x Al x Ti 2-x (PO 4 ) 3 (where 0 ≦ x ≦ 1.0), Li 1 + y My Zr 2-y (PO 4 ). 3 (wherein M is Cr, La or In, and 0 ≦ y ≦ 1.0).
また、前記の各ガラスセラミックスについては、それぞれの結合を壊すことなく金属元素サイトに置換され得る元素であれば、ガラスセラミックスは、前記の各元素以外の元素を含有する他元素置換体であってもよい。前記の置換元素としては、３価または４価の元素が挙げられ、具体的には、Ｃｒ、Ｌａ、Ｙ、Ｉｎ、Ｍｎ、Ｇａ、Ｍｏ、Ｓｉなどが例示できる。前記例示のガラスセラミックスの代表的な置換体としては、例えば、Ｌｉ１＋ｚＡｌｚＴｉ２−ｚ（Ｐ１−ｓＳｉｓＯ４）３（０≦ｚ≦１．０、０≦ｓ≦０．５）、Ｌｉ１＋ｔＡｌｔＭ’ｕＴｉ２−ｔ−ｕ（ＰＯ４）３（ただし、Ｍ’はＧａまたはＩｎ、０≦ｔ≦１．０、０≦ｕ≦０．５）などが挙げられる。 For each of the glass ceramics described above, the glass ceramic is an other element substitute containing an element other than each of the elements as long as the element can be replaced with a metal element site without breaking the bond. Also good. Examples of the substitution element include trivalent or tetravalent elements, and specific examples include Cr, La, Y, In, Mn, Ga, Mo, and Si. As typical substitutes of the above-described exemplary glass ceramics, for example, Li 1 + z Al z Ti 2-z (P 1-s Si s O 4 ) 3 (0 ≦ z ≦ 1.0, 0 ≦ s ≦ 0. 5), Li 1 + t Al t M ′ u Ti 2- tu (PO 4 ) 3 (where M ′ is Ga or In, 0 ≦ t ≦ 1.0, 0 ≦ u ≦ 0.5), etc. It is done.
ガラスセラミックス粒子には、例えば、前記例示のガラスセラミックスにより構成される粒子の１種のみを使用してもよく、２種以上を併用してもよい。 For the glass ceramic particles, for example, only one kind of particles constituted by the glass ceramics exemplified above may be used, or two or more kinds may be used in combination.
本発明の電極に係るガラスセラミックス粒子は、例えば、これを構成する元素を含む化合物の混合物を熱処理（焼成）することによって合成することができる。原料化合物の混合物を熱処理する際の温度は、８００〜１５００℃とすることが好ましく、また、熱処理時間は、１〜１５時間とすることが好ましい。 The glass-ceramic particles according to the electrode of the present invention can be synthesized by, for example, heat-treating (firing) a mixture of compounds containing the elements constituting the glass-ceramic particles. The temperature at which the mixture of the raw material compounds is heat-treated is preferably 800 to 1500 ° C., and the heat treatment time is preferably 1 to 15 hours.
ガラスセラミックス粒子を合成するための原料化合物には、各元素の酸化物、水酸化物、硝酸塩、炭酸塩、シュウ酸塩など、目的とする元素の他に、Ｃ、Ｎ、ＯおよびＨ以外の元素は含まないものが好ましく、このような原料化合物を使用することで、前記の熱処理時に目的とする元素以外のものの残存を防止することができる。 The raw material compounds for synthesizing the glass ceramic particles include oxides, hydroxides, nitrates, carbonates, oxalates, and other elements other than the target element other than C, N, O and H. Those containing no element are preferable, and by using such a raw material compound, it is possible to prevent the remaining of the elements other than the target element during the heat treatment.
また、ガラスセラミックス粒子の合成に際しては、ガラスセラミックス粒子を構成する元素のうち、Ｌｉ、ＰおよびＰサイトに置換される元素を除く全ての金属元素を含む化合物（前駆体）を水熱合成法によって合成し、この前駆体と、Ｌｉ、ＰおよびＰサイトに置換される元素を含む原料化合物とを混合した混合物について、例えば前記の条件で熱処理する方法を採用することがより好ましい。この合成法によれば、ガラスセラミックス粒子を構成する各元素同士がより微細かつ均一に混合されるため、各粒子同士の組成の均一性がより向上し、また、粒子径の小さなものを合成しやすいことから、ガラスセラミックス粒子の一次粒子の平均粒子径を前記の値に制御することが容易となる。 In synthesizing glass ceramic particles, a compound (precursor) containing all metal elements except elements substituted for Li, P and P sites among elements constituting glass ceramic particles is obtained by a hydrothermal synthesis method. It is more preferable to employ a method of synthesizing and heat-treating the precursor and a raw material compound containing an element substituted for Li, P, and P sites, for example, under the above-mentioned conditions. According to this synthesis method, the elements constituting the glass ceramic particles are mixed more finely and uniformly, so that the uniformity of the composition of each particle is further improved, and a small particle diameter is synthesized. Since it is easy, it becomes easy to control the average particle diameter of the primary particle of a glass ceramic particle to the said value.
水熱合成法による前駆体の合成は、例えば、以下の手順で実施することができる。前記のようなガラスセラミックス粒子の原料化合物（水溶性の塩）の複数を含む水溶液に、アンモニア水、水酸化ナトリウムなどのアルカリ金属の水酸化物の水溶液などのアルカリ水溶液を投入して中和させ、共沈法にて沈殿物を得た後、この沈殿物（沈殿物を含む水溶液）を密閉容器中で加熱することによって加圧下で熱処理する。その後に前記懸濁液をよく洗浄してから濾過して沈殿物を取り出し、これを乾燥するなどして前駆体を得る。 The synthesis | combination of the precursor by a hydrothermal synthesis method can be implemented in the following procedures, for example. An aqueous solution containing a plurality of raw material compounds (water-soluble salts) of glass ceramic particles as described above is neutralized by introducing an aqueous alkali solution such as aqueous solution of alkali metal hydroxide such as ammonia water or sodium hydroxide. After the precipitate is obtained by the coprecipitation method, the precipitate (aqueous solution containing the precipitate) is heat-treated under pressure by heating in a sealed container. Thereafter, the suspension is thoroughly washed and filtered to take out a precipitate, which is dried to obtain a precursor.
水熱合成法における前記懸濁液は、添加するアルカリ水溶液の量を調節することにより、そのｐＨを４〜１１とすることが好ましく、このような範囲の中で、目的とするガラスセラミックス粒子の前駆体が析出し得るｐＨを選択すればよい。 The suspension in the hydrothermal synthesis method preferably has a pH of 4 to 11 by adjusting the amount of the aqueous alkali solution to be added. What is necessary is just to select pH which a precursor can precipitate.
水熱合成法における加熱温度は、６０℃以上とすることが好ましく、８０℃以上とすることがより好ましく、また、２００℃以下とすることが好ましく、１５０℃以下とすることがより好ましく、１２０℃以下とすることが更に好ましい。 The heating temperature in the hydrothermal synthesis method is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, 200 ° C. or lower, more preferably 150 ° C. or lower, 120 More preferably, the temperature is set to not more than ° C.
また、水熱合成法における加熱時間は、１時間以上とすることが好ましく、また、４０時間以下とすることが好ましく、６時間以下とすることがより好ましい。 The heating time in the hydrothermal synthesis method is preferably 1 hour or longer, more preferably 40 hours or shorter, and more preferably 6 hours or shorter.
本発明の電極においては、前記ガラスセラミックス粒子の使用による前記の効果を良好に確保する観点から、電極合剤層の含有する前記ガラスセラミックス粒子と活物質粒子との合計を１００質量％としたとき、前記ガラスセラミックス粒子の割合を、０．１質量％以上、好ましくは０．５質量％以上とする。ただし、電極合剤層中の前記ガラスセラミックス粒子の含有量が多くなり過ぎると、ガラスセラミックス粒子に吸蔵されるＬｉ量が多くなって、電池の不可逆容量が増大する虞がある。よって、電極合剤層の含有する前記ガラスセラミックス粒子と活物質粒子との合計を１００質量％としたとき、前記ガラスセラミックス粒子の割合は、１０質量％以下、好ましくは５質量％以下とする。 In the electrode of the present invention, from the viewpoint of ensuring the above-mentioned effect due to the use of the glass ceramic particles, when the total of the glass ceramic particles and the active material particles contained in the electrode mixture layer is 100% by mass The ratio of the glass ceramic particles is 0.1% by mass or more, preferably 0.5% by mass or more. However, when the content of the glass ceramic particles in the electrode mixture layer is excessively large, the amount of Li occluded in the glass ceramic particles increases, which may increase the irreversible capacity of the battery. Therefore, when the total of the glass ceramic particles and the active material particles contained in the electrode mixture layer is 100% by mass, the ratio of the glass ceramic particles is 10% by mass or less, preferably 5% by mass or less.
本発明の電極においては、例えば、この電極を有するリチウムイオン二次電池の高容量化を図る観点から、電極合剤層の厚み（集電体の両面に電極合剤層を有する電極の場合は、集電体の片面当たりの厚み。電極合剤層の厚みについて、以下同じ。）を、８０μｍ以上とすることが好ましく、１００μｍ以上とすることがより好ましい。 In the electrode of the present invention, for example, from the viewpoint of increasing the capacity of a lithium ion secondary battery having this electrode, the thickness of the electrode mixture layer (in the case of an electrode having electrode mixture layers on both sides of the current collector) The thickness per one side of the current collector, the same applies to the thickness of the electrode mixture layer) is preferably 80 μm or more, and more preferably 100 μm or more.
なお、電池の高容量化を図るために電極合剤層を厚くすると、非水電解液が電極合剤層の全体に十分に浸透せず、例えば集電体の近傍では非水電解液が不足して、想定した電池容量が十分に引き出せなくなったり、電池の充放電サイクル特性や負荷特性が低下したりする虞がある。しかしながら、本発明の電極では、前記の通り、ガラスセラミックス粒子の作用によって、電極合剤層内への非水電解液の導入をスムーズにすることができ、非水電解液が不足する領域の発生を抑制できるため、活物質の利用効率の低下を抑えることができる。よって、本発明の電極では、電極合剤層を厚くして電池の高容量化を図りつつ、電池の充放電サイクル特性や負荷特性も高く維持することができる。 If the electrode mixture layer is made thicker in order to increase the capacity of the battery, the nonaqueous electrolyte does not sufficiently penetrate the entire electrode mixture layer. For example, the nonaqueous electrolyte is insufficient in the vicinity of the current collector. As a result, the assumed battery capacity may not be sufficiently extracted, and the charge / discharge cycle characteristics and load characteristics of the battery may be degraded. However, in the electrode of the present invention, as described above, the introduction of the nonaqueous electrolyte into the electrode mixture layer can be smoothly performed by the action of the glass ceramic particles, and a region where the nonaqueous electrolyte is insufficient is generated. Therefore, a decrease in utilization efficiency of the active material can be suppressed. Therefore, in the electrode of the present invention, the charge / discharge cycle characteristics and load characteristics of the battery can be maintained high while increasing the capacity of the battery by increasing the electrode mixture layer.
ただし、電極合剤層が厚すぎると、ガラスセラミックス粒子による電極合剤層内への非水電解液の浸透性の向上効果が小さくなる虞がある。よって、本発明の電極においては、電極合剤層の厚みを、２００μｍ以下とすることが好ましく、１８０μｍ以下とすることがより好ましい。 However, if the electrode mixture layer is too thick, the effect of improving the permeability of the nonaqueous electrolytic solution into the electrode mixture layer by the glass ceramic particles may be reduced. Therefore, in the electrode of the present invention, the thickness of the electrode mixture layer is preferably 200 μm or less, and more preferably 180 μm or less.
本発明の電極がリチウムイオン二次電池用負極として使用される場合、活物質粒子には、従来から知られているリチウムイオン二次電池の負極に使用されている活物質粒子、すなわち、Ｌｉを吸蔵放出可能な活物質の粒子を用いることができる。このような活物質粒子の具体例としては、例えば、黒鉛［天然黒鉛；熱分解炭素類、メソフェーズカーボンマイクロビーズ（ＭＣＭＢ）、炭素繊維などの易黒鉛化炭素を２８００℃以上で黒鉛化処理した人造黒鉛；など］、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、ＭＣＭＢ、炭素繊維、活性炭などの炭素材料；リチウムと合金化可能な金属（Ｓｉ、Ｓｎなど）や、これらの金属を含む材料（合金、酸化物など）；などの粒子が挙げられる。本発明の電極をリチウムイオン二次電池用負極とする場合、これらの活物質粒子は、１種のみを使用してもよく、２種以上を併用してもよい。 When the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery, the active material particles include active material particles used for a negative electrode of a conventionally known lithium ion secondary battery, that is, Li. Active material particles that can be occluded and released can be used. Specific examples of such active material particles include, for example, graphite [natural graphite; artificial carbon obtained by graphitizing graphitized carbon such as graphite, pyrolytic carbons, mesophase carbon microbeads (MCMB), carbon fiber, etc. at 2800 ° C. or higher. Graphite; etc.], pyrolytic carbons, cokes, glassy carbons, organic polymer compound fired bodies, MCMB, carbon fibers, activated carbon and other carbon materials; metals that can be alloyed with lithium (Si, Sn, etc.) And particles containing these metals (alloys, oxides, etc.). When the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery, these active material particles may be used alone or in combination of two or more.
前記の負極活物質の中でも、特に電池の高容量化を図るには、ＳｉとＯとを構成元素に含む材料（ただし、Ｓｉに対するＯの原子比ｐは、０．５≦ｐ≦１．５である。以下、当該材料を「ＳｉＯｐ」という）を用いることが好ましい。 Among the negative electrode active materials, in order to increase the capacity of the battery, in particular, a material containing Si and O as constituent elements (provided that the atomic ratio p of O to Si is 0.5 ≦ p ≦ 1.5 Hereinafter, the material is preferably referred to as “SiO p ”.
ＳｉＯｐは、Ｓｉの微結晶または非晶質相を含んでいてもよく、この場合、ＳｉとＯの原子比は、Ｓｉの微結晶または非晶質相のＳｉを含めた比率となる。すなわち、ＳｉＯｐには、非晶質のＳｉＯ２マトリックス中にＳｉ（例えば、微結晶Ｓｉ）が分散した構造のものが含まれ、この非晶質のＳｉＯ２と、その中に分散しているＳｉを合わせて、前記の原子比ｐが０．５≦ｐ≦１．５を満足していればよい。例えば、非晶質のＳｉＯ２マトリックス中にＳｉが分散した構造で、ＳｉＯ２とＳｉのモル比が１：１の材料の場合、ｐ＝１であるので、構造式としてはＳｉＯで表記される。このような構造の材料の場合、例えば、Ｘ線回折分析では、Ｓｉ（微結晶Ｓｉ）の存在に起因するピークが観察されない場合もあるが、透過型電子顕微鏡で観察すると、微細なＳｉの存在が確認できる。 The SiO p may contain a microcrystalline or amorphous phase of Si. In this case, the atomic ratio of Si and O is a ratio including Si microcrystalline or amorphous phase Si. That is, the SiO p includes a structure in which Si (for example, microcrystalline Si) is dispersed in an amorphous SiO 2 matrix, and is dispersed in the amorphous SiO 2 . In combination with Si, it is sufficient that the atomic ratio p satisfies 0.5 ≦ p ≦ 1.5. For example, in the case of a structure in which Si is dispersed in an amorphous SiO 2 matrix and the material has a molar ratio of SiO 2 to Si of 1: 1, p = 1, so the structural formula is represented by SiO. . In the case of a material having such a structure, for example, in X-ray diffraction analysis, a peak due to the presence of Si (microcrystalline Si) may not be observed, but when observed with a transmission electron microscope, the presence of fine Si Can be confirmed.
なお、ＳｉＯｐは導電性が低いことから、例えば、ＳｉＯｐの表面を炭素で被覆して用いてもよく、これにより負極における導電ネットワークを、より良好に形成することができる。 In addition, since SiO p has low conductivity, for example, the surface of SiO p may be coated with carbon, so that a conductive network in the negative electrode can be formed better.
ＳｉＯｐの表面を被覆するための炭素には、例えば、低結晶性炭素、カーボンナノチューブ、気相成長炭素繊維などを使用することができる。 As the carbon for coating the surface of SiO p , for example, low crystalline carbon, carbon nanotube, vapor grown carbon fiber, or the like can be used.
なお、炭化水素系ガスを気相中で加熱し、炭化水素系ガスの熱分解により生じた炭素を、ＳｉＯｐ粒子の表面上に堆積する方法［気相成長（ＣＶＤ）法］で、ＳｉＯｐの表面を炭素で被覆すると、炭化水素系ガスがＳｉＯｐ粒子の隅々にまで行き渡り、粒子の表面や表面の空孔内に、導電性を有する炭素を含む薄くて均一な皮膜（炭素被覆層）を形成できることから、少量の炭素によってＳｉＯｐ粒子に均一性よく導電性を付与できる。 Incidentally, the hydrocarbon gas is heated in the gas phase, the carbon generated by thermal decomposition of hydrocarbon gas, a method of depositing on the surface of SiO p particles [vapor deposition (CVD) method], SiO p When the surface of carbon is coated with carbon, the hydrocarbon-based gas spreads to every corner of the SiO p particle, and a thin and uniform film (carbon coating layer) containing conductive carbon is present in the surface of the particle and in the pores of the surface. ) Can be imparted with good uniformity to the SiO p particles with a small amount of carbon.
ＣＶＤ法で使用する炭化水素系ガスの液体ソースとしては、トルエン、ベンゼン、キシレン、メシチレンなどを用いることができるが、取り扱いやすいトルエンが特に好ましい。これらを気化させる（例えば、窒素ガスでバブリングする）ことにより炭化水素系ガスを得ることができる。また、メタンガスやエチレンガス、アセチレンガスなどを用いることもできる。 As the liquid source of the hydrocarbon gas used in the CVD method, toluene, benzene, xylene, mesitylene and the like can be used, but toluene that is easy to handle is particularly preferable. A hydrocarbon-based gas can be obtained by vaporizing them (for example, bubbling with nitrogen gas). Moreover, methane gas, ethylene gas, acetylene gas, etc. can also be used.
ＣＶＤ法の処理温度としては、例えば、６００〜１２００℃であることが好ましい。また、ＣＶＤ法に供するＳｉＯｐは、公知の手法で造粒した造粒体（複合粒子）であることが好ましい。 As processing temperature of CVD method, it is preferable that it is 600-1200 degreeC, for example. Further, SiO p subjected to CVD method is preferably granulated material was granulated by a known method (composite particles).
ＳｉＯｐの表面を炭素で被覆する場合、炭素の量は、ＳｉＯｐ：１００質量部に対して、５質量部以上であることが好ましく、１０質量部以上であることがより好ましく、また、９５質量部以下であることが好ましく、９０質量部以下であることがより好ましい。 When the surface of SiO p is coated with carbon, the amount of carbon is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, with respect to SiO p : 100 parts by mass, and 95 The amount is preferably at most part by mass, more preferably at most 90 parts by mass.
なお、ＳｉＯｐは、他の高容量負極材料と同様に電池の充放電に伴う体積変化が大きいため、負極活物質には、ＳｉＯｐと黒鉛とを併用することが好ましい。これにより、ＳｉＯｐの使用による高容量化を図りつつ、電池の充放電に伴う負極の膨張収縮を抑えて、充放電サイクル特性をより高く維持することが可能となる。 In addition, since SiO p has a large volume change accompanying charging / discharging of the battery like other high-capacity negative electrode materials, it is preferable to use SiO p and graphite in combination for the negative electrode active material. This makes it possible to maintain the charge / discharge cycle characteristics higher while suppressing the expansion and contraction of the negative electrode accompanying the charge / discharge of the battery while increasing the capacity by using SiO p .
負極活物質にＳｉＯｐと黒鉛とを併用する場合、負極活物質全量中におけるＳｉＯｐの割合は、ＳｉＯｐの使用による高容量化効果を良好に確保する観点から０．５質量％以上とすることが好ましく、また、ＳｉＯｐによる負極の膨張収縮を抑制する観点から１０質量％以下とすることが好ましい。 When SiO p and graphite are used in combination for the negative electrode active material, the proportion of SiO p in the total amount of the negative electrode active material is 0.5 mass% or more from the viewpoint of favorably securing a high capacity effect by using SiO p. In view of suppressing expansion and contraction of the negative electrode due to SiO p , the content is preferably 10% by mass or less.
また、本発明の電極がリチウムイオン二次電池用正極として使用される場合、活物質粒子には、従来から知られているリチウムイオン二次電池の正極に使用されている活物質粒子、すなわち、Ｌｉを吸蔵放出可能な活物質の粒子を用いることができる。このような活物質粒子の具体例としては、例えば、Ｌｉ１＋ｃＭ１Ｏ２（−０．１＜ｃ＜０．１、Ｍ１：Ｃｏ、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇなど）で表される層状構造のリチウム含有遷移金属酸化物、ＬｉＭｎ２Ｏ４やその元素の一部を他元素で置換したスピネル構造のリチウムマンガン酸化物、ＬｉＭ２ＰＯ４（Ｍ２：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅなど）で表されるオリビン型化合物などの粒子を用いることが可能である。前記層状構造のリチウム含有遷移金属酸化物の具体例としては、ＬｉＣｏＯ２やＬｉＮｉ１−ｄＣｏｄ−ｅＡｌｅＯ２（０．１≦ｄ≦０．３、０．０１≦ｅ≦０．２）などの他、少なくともＣｏ、ＮｉおよびＭｎを含む酸化物（ＬｉＭｎ１／３Ｎｉ１／３Ｃｏ１／３Ｏ２、ＬｉＭｎ５／１２Ｎｉ５／１２Ｃｏ１／６Ｏ２、ＬｉＭｎ３／５Ｎｉ１／５Ｃｏ１／５Ｏ２など）などを例示することができる。本発明の電極をリチウムイオン二次電池用正極とする場合、これらの活物質粒子は、１種のみを使用してもよく、２種以上を併用してもよい。 In addition, when the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, the active material particles include active material particles used for a positive electrode of a conventionally known lithium ion secondary battery, that is, Active material particles capable of occluding and releasing Li can be used. Specific examples of such active material particles are represented by, for example, Li 1 + c M 1 O 2 (−0.1 <c <0.1, M 1 : Co, Ni, Mn, Al, Mg, etc.). Lithium-containing transition metal oxide having a layered structure, LiMn 2 O 4 and a spinel-structured lithium manganese oxide obtained by substituting some of its elements with other elements, LiM 2 PO 4 (M 2 : Co, Ni, Mn, Fe, etc. It is possible to use particles such as olivine type compounds represented by Specific examples of the lithium-containing transition metal oxide having a layered structure include LiCoO 2 and LiNi 1-d Co d e Al e O 2 (0.1 ≦ d ≦ 0.3, 0.01 ≦ e ≦ 0. 2) and other oxides containing at least Co, Ni and Mn (LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiMn 3 / 5 Ni 1/5 Co 1/5 O 2 etc.). When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, these active material particles may be used alone or in combination of two or more.
なお、本発明の電極をリチウムイオン二次電池用負極とする場合の前記活物質粒子や、リチウムイオン二次電池用正極とする場合の前記活物質粒子は、前記ガラスセラミックス粒子と同じ方法で測定される一次粒子（焼結体の場合には、焼結体粒子）の平均粒子径が、１００ｎｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。また、５００μｍ以下であることが好ましく、１０μｍ以下であることがより好ましい。なお、本発明においては、活物質表面に形成される被膜中にガラスセラミックス粒子が取り込まれることによって、前記被膜の物性を向上させるため、活物質粒子の粒子径は、前記ガラスセラミックス粒子の粒子径に対して、５０倍以上のものを選定することが特に好ましい。 The active material particles when the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery and the active material particles when used as a positive electrode for a lithium ion secondary battery are measured by the same method as the glass ceramic particles. The average particle diameter of the primary particles (in the case of a sintered body, sintered body particles) is preferably 100 nm or more, and more preferably 0.5 μm or more. Moreover, it is preferable that it is 500 micrometers or less, and it is more preferable that it is 10 micrometers or less. In the present invention, the particle diameter of the active material particles is the particle diameter of the glass ceramic particles in order to improve the physical properties of the film by incorporating the glass ceramic particles into the film formed on the active material surface. On the other hand, it is particularly preferable to select a material 50 times or more.
本発明の電極の電極合剤層に係る樹脂製バインダには、従来から知られているリチウムイオン二次電池用の正極に係る正極合剤層や、負極に係る負極合剤層で使用されている樹脂製バインダと同じものが使用できる。具体的には、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレンブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロース（ＣＭＣ）などが好ましいものとして挙げられる。 The resin binder according to the electrode mixture layer of the electrode of the present invention is used in a conventionally known positive electrode mixture layer related to a positive electrode for a lithium ion secondary battery and a negative electrode mixture layer related to a negative electrode. The same resin binder can be used. Specifically, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC) and the like are preferable.
また、本発明の電極に係る電極合剤層には、必要に応じて導電性助剤を含有させることもできる。導電性助剤の具体例としては、例えば、天然黒鉛（鱗片状黒鉛など）、人造黒鉛などの黒鉛；アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカ−ボンブラック；炭素繊維；などが挙げられる。 Moreover, the electrode mixture layer which concerns on the electrode of this invention can also be made to contain a conductive support agent as needed. Specific examples of conductive aids include, for example, graphite such as natural graphite (such as flake graphite) and artificial graphite; carbon such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Black; carbon fiber; and the like.
本発明の電極をリチウムイオン二次電池用負極とする場合、電極合剤層（負極合剤層）における各成分の組成としては、例えば、活物質粒子を８５〜９９質量％とし、樹脂製バインダを１．０〜１０質量％とすることが好ましい。また、導電性助剤を用いる場合には、電極合剤層中における導電性助剤の量を０．５〜１０質量％とすることが好ましい。 When the electrode of the present invention is a negative electrode for a lithium ion secondary battery, the composition of each component in the electrode mixture layer (negative electrode mixture layer) is, for example, 85 to 99% by mass of active material particles, and a resin binder. Is preferably 1.0 to 10% by mass. Moreover, when using a conductive support agent, it is preferable that the quantity of the conductive support agent in an electrode mixture layer shall be 0.5-10 mass%.
本発明の電極を、集電体を有するリチウムイオン二次電池用負極とする場合、集電体には、銅製やニッケル製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、銅箔が用いられる。集電体の厚みは、５〜３０μｍであることが好ましい。 When the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery having a current collector, the current collector can be made of copper or nickel foil, punched metal, net, expanded metal, etc. Copper foil is used. The thickness of the current collector is preferably 5 to 30 μm.
本発明の電極をリチウムイオン二次電池用正極とする場合、電極合剤層（正極合剤層）における各成分の組成としては、例えば、活物質粒子を７５〜９５質量％とし、樹脂製バインダを２〜１５質量％とし、導電性助剤を２〜１５質量％とすることが好ましい。 When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, the composition of each component in the electrode mixture layer (positive electrode mixture layer) is, for example, 75 to 95% by mass of active material particles, and a resin binder. Is preferably 2 to 15% by mass, and the conductive auxiliary is preferably 2 to 15% by mass.
本発明の電極を、集電体を有するリチウムイオン二次電池用正極とする場合、集電体には、アルミニウム製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、アルミニウム箔が用いられる。集電体の厚みは、１０〜３０μｍであることが好ましい。 When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery having a current collector, an aluminum foil, punching metal, net, expanded metal, or the like can be used as the current collector. Is used. The thickness of the current collector is preferably 10 to 30 μm.
本発明の電極は、例えば、前記ガラスセラミックス粒子、活物質粒子および樹脂製バインダ、更には必要に応じて導電性助剤を含有する電極合剤を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）などの有機溶剤や水といった溶剤に分散させて調製した電極合剤含有組成物（ペースト、スラリーなど）を、集電体の片面または両面などに塗布して乾燥し、必要に応じてプレス処理を施す工程を経て製造することができる。 The electrode of the present invention includes, for example, the above-mentioned glass ceramic particles, active material particles and resin binder, and an electrode mixture containing a conductive auxiliary agent as necessary, such as N-methyl-2-pyrrolidone (NMP). An electrode mixture-containing composition (paste, slurry, etc.) prepared by dispersing in a solvent such as organic solvent or water is applied to one side or both sides of the current collector, dried, and subjected to press treatment as necessary. It can be manufactured through a process.
なお、前記ガラスセラミックス粒子による前記の効果をより良好に確保する観点から、電極合剤層中においては、前記ガラスセラミックス粒子の凝集が抑制されていることが好ましく、具体的には、電極合剤層中における前記ガラスセラミックス粒子の分散粒子径は、２００ｎｍ以下であることが好ましい。ここでいう前記ガラスセラミックス粒子の分散粒子径は、電極の断面を走査型電子顕微鏡（ＳＥＭ）で観察し、ガラスセラミックス粒子（一次粒子の状態で分散しているガラスセラミックス粒子、および二次粒子の状態で凝集しつつ分散しているガラスセラミックス粒子を含む）１００個のうちの最も大きい粒子の直径を測定して得られる値である。 In addition, it is preferable that aggregation of the glass ceramic particles is suppressed in the electrode mixture layer from the viewpoint of ensuring the above-mentioned effect by the glass ceramic particles better, specifically, the electrode mixture. The dispersed particle size of the glass ceramic particles in the layer is preferably 200 nm or less. The dispersed particle diameter of the glass ceramic particles referred to here is obtained by observing the cross section of the electrode with a scanning electron microscope (SEM), and the glass ceramic particles (glass ceramic particles dispersed in a primary particle state and secondary particles). It is a value obtained by measuring the diameter of the largest particle of 100 particles (including glass ceramic particles dispersed while being aggregated in a state).
このように、電極合剤層中での前記ガラスセラミックス粒子の凝集を抑制するには、下記の方法によって調製された電極合剤含有組成物を用いて電極合剤層を形成することが好ましい。まず、前記ガラスセラミックス粒子を、電極合剤含有組成物に使用する溶剤と同じ溶剤中に分散させて、ガラスセラミックス粒子分散体を調製する。このガラスセラミックス粒子分散体には、樹脂製バインダや分散剤などの有機物は含有させないことが好ましい。 Thus, in order to suppress aggregation of the glass ceramic particles in the electrode mixture layer, it is preferable to form the electrode mixture layer using the electrode mixture-containing composition prepared by the following method. First, the glass ceramic particles are dispersed in the same solvent as the solvent used for the electrode mixture-containing composition to prepare a glass ceramic particle dispersion. The glass ceramic particle dispersion preferably does not contain an organic substance such as a resin binder or a dispersant.
ガラスセラミックス粒子分散体の調製には、ボールミル、ナノミル、ピコミル、ペイントシェーカー、ディゾルバーなどのナノ粒子分散体の調製に好適な公知の分散機を用いることができる。 For the preparation of the glass ceramic particle dispersion, a known disperser suitable for the preparation of the nanoparticle dispersion such as a ball mill, nanomill, picomill, paint shaker, or dissolver can be used.
ガラスセラミックス粒子分散体の分散条件や、ガラスセラミックス粒子分散体における前記ガラスセラミックス粒子の濃度（固形分濃度）は、後に形成される電極合剤層中において、前記ガラスセラミックス粒子の分散粒子径が２００ｎｍ以下となるような条件、固形分濃度を選択すればよい。具体的には、ガラスセラミックス粒子分散体の固形分濃度は、例えば、後に電極合剤含有組成物とすることや、分散安定性など、取り扱いが容易であることなども考慮して、５〜５０質量％とすることが好ましい。また、ガラスセラミックス粒子分散体の分散条件としては、例えば、ペイントシェーカーを使用し、ジルコニアビーズを用いて、前記の固形分濃度のガラスセラミックス粒子分散体を調製する場合、分散時間を５分〜２時間程度とすることが好ましい。 The dispersion conditions of the glass ceramic particle dispersion and the concentration (solid content concentration) of the glass ceramic particles in the glass ceramic particle dispersion are such that the dispersed particle diameter of the glass ceramic particles is 200 nm in the electrode mixture layer to be formed later. What is necessary is just to select the conditions and solid content concentration which become the following. Specifically, the solid content concentration of the glass ceramic particle dispersion is, for example, 5 to 50 in consideration of the electrode mixture-containing composition later and the ease of handling such as dispersion stability. It is preferable to set it as the mass%. Further, as a dispersion condition of the glass ceramic particle dispersion, for example, when a glass ceramic particle dispersion having the above-mentioned solid content concentration is prepared using a paint shaker and zirconia beads, the dispersion time is 5 minutes to 2 minutes. It is preferable to set it to about time.
前記のように調製したガラスセラミックス粒子分散体に、活物質粒子および樹脂製バインダ、更には、必要に応じて導電性助剤や溶剤を加えて混合し、電極合剤含有組成物を調製する。なお、活物質粒子および樹脂製バインダ、導電性助剤は、あらかじめ溶剤に分散させて分散液（樹脂製バインダは溶剤に溶解していてもよい）を調製しておき、この分散液とガラスセラミックス粒子分散体とを混合して電極合剤含有組成物を調製してもよい。 To the glass ceramic particle dispersion prepared as described above, active material particles and a resin binder, and further, if necessary, a conductive aid and a solvent are added and mixed to prepare an electrode mixture-containing composition. The active material particles, the resin binder, and the conductive auxiliary agent are previously dispersed in a solvent to prepare a dispersion (the resin binder may be dissolved in the solvent). An electrode mixture-containing composition may be prepared by mixing with a particle dispersion.
ガラスセラミックス粒子分散体と、活物質粒子や樹脂製バインダ、導電性助剤などとを混合する際には、ジルコニアビーズなどの分散メディアを使用する分散機を使用することもできるが、分散メディアが活物質粒子にダメージを与える虞があることから、メディアレス分散機を使用することがより好ましい。メディアレス分散機としては、例えば、ハイブリッドミキサー、ナノマイザー、ジェットミルなどの汎用の分散機が挙げられる。 When mixing the glass ceramic particle dispersion with the active material particles, the resin binder, the conductive auxiliary agent, etc., a disperser using a dispersion medium such as zirconia beads can be used. Since there is a possibility of damaging the active material particles, it is more preferable to use a medialess disperser. Examples of the medialess disperser include general-purpose dispersers such as a hybrid mixer, a nanomizer, and a jet mill.
例えば前記のようにして調製された電極合剤含有組成物を使用して電極合剤層を形成し、更に必要に応じてプレス処理を施した電極には、常法に従って電池内の端子と接続するためのリード部を形成することができる。 For example, an electrode mixture layer is formed using the electrode mixture-containing composition prepared as described above, and the electrodes subjected to press treatment as necessary are connected to terminals in the battery according to a conventional method. The lead part for doing can be formed.
本発明のリチウムイオン二次電池（以下、単に「電池」という場合がある）は、正極、負極、非水電解液およびセパレータを備えており、正極および負極のうちの少なくとも一方が本発明のリチウムイオン二次電池用電極であればよく、その他の構成および構造については特に制限されず、従来から知られているリチウムイオン二次電池で採用されている各種構成および構造を適用することができる。 The lithium ion secondary battery of the present invention (hereinafter sometimes simply referred to as “battery”) includes a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, and at least one of the positive electrode and the negative electrode is the lithium of the present invention. Any other configuration and structure may be used as long as it is an electrode for an ion secondary battery, and various configurations and structures employed in conventionally known lithium ion secondary batteries can be applied.
本発明の電池は、正極および負極のいずれか一方のみが本発明の電極であればよく、正極および負極の両方が本発明の電極であってもよい。本発明の電池に係る負極のみが本発明の電極である場合、正極には、前記ガラスセラミックス粒子を含有しない以外は、本発明の電極（正極）と同じ構成の正極を使用することができる。また、本発明の電池に係る正極のみが本発明の電極である場合、負極には、前記ガラスセラミックス粒子を含有しない以外は、本発明の電極（負極）と同じ構成の負極を使用することができる。 In the battery of the present invention, only one of the positive electrode and the negative electrode may be the electrode of the present invention, and both the positive electrode and the negative electrode may be the electrode of the present invention. When only the negative electrode according to the battery of the present invention is the electrode of the present invention, a positive electrode having the same configuration as the electrode (positive electrode) of the present invention can be used as the positive electrode except that the glass ceramic particles are not contained. In addition, when only the positive electrode according to the battery of the present invention is the electrode of the present invention, a negative electrode having the same configuration as the electrode (negative electrode) of the present invention may be used for the negative electrode, except that the glass ceramic particles are not included. it can.
本発明の電池に係るセパレータは、８０℃以上（より好ましくは１００℃以上）１７０℃以下（より好ましくは１５０℃以下）において、その孔が閉塞する性質（すなわちシャットダウン機能）を有していることが好ましく、通常のリチウムイオン二次電池などで使用されているセパレータ、例えば、ポリエチレン（ＰＥ）やポリプロピレン（ＰＰ）などのポリオレフィン製の微多孔膜を用いることができる。セパレータを構成する微多孔膜は、例えば、ＰＥのみを使用したものやＰＰのみを使用したものであってもよく、また、ＰＥ製の微多孔膜とＰＰ製の微多孔膜との積層体であってもよい。セパレータの厚みは、例えば、１０〜３０μｍであることが好ましい。 The separator according to the battery of the present invention has a property (that is, a shutdown function) that the pores are blocked at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower). Preferably, separators used in ordinary lithium ion secondary batteries, for example, microporous membranes made of polyolefin such as polyethylene (PE) and polypropylene (PP) can be used. The microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be. The thickness of the separator is preferably 10 to 30 μm, for example.
前記の正極と前記の負極と前記のセパレータとは、正極と負極との間にセパレータを介在させて重ねた積層電極体や、更にこれを渦巻状に巻回した巻回電極体の形態で本発明の電池に使用することができる。 The positive electrode, the negative electrode, and the separator are formed in the form of a laminated electrode body in which a separator is interposed between the positive electrode and the negative electrode, or a wound electrode body in which the separator is wound in a spiral shape. It can be used for the battery of the invention.
本発明の電池に係る非水電解液には、例えば、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、プロピオン酸メチル、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ガンマーブチロラクトン、エチレングリコールサルファイト、１，２−ジメトキシエタン、１，３−ジオキソラン、テトラヒドロフラン、２−メチル−テトラヒドロフラン、ジエチルエーテルなどの有機溶媒に、例えば、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＣＦ３ＣＯ２、Ｌｉ２Ｃ２Ｆ４（ＳＯ３）２、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｎＦ２ｎ＋１ＳＯ３（ｎ≧２）、ＬｉＮ（ＲｆＯＳＯ２）２［ここでＲｆはフルオロアルキル基］などのリチウム塩から選ばれる少なくとも一種を溶解させることによって調製したものが使用される。このリチウム塩の非水電解液中の濃度としては、０．５〜１．５ ｍｏｌ／ｌ、特に０．９〜１．２５ ｍｏｌ／ｌが好ましい。また、これらの電解液に安全性や充放電サイクル性、高温貯蔵性といった特性を向上させる目的で、ビニレンカーボネート類、１，３−プロパンサルトン、ジフェニルジスルフィド、シクロヘキシルベンゼン、ビフェニル、フルオロベンゼン、ｔ−ブチルベンゼンなどの添加剤を適宜加えることもできる。 Examples of the nonaqueous electrolytic solution according to the battery of the present invention include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate, ethylene carbonate, propylene carbonate, butylene carbonate, gamma-butyrolactone, ethylene glycol sulfite, 1,2- dimethoxyethane, 1,3-dioxolane, tetrahydrofuran, 2-methyl - tetrahydrofuran, organic solvents such as diethyl ether, for example, LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ≧ 2), LiN (R f OSO 2 ) 2 [wherein R f is a fluoroalkyl group] or the like prepared by dissolving at least one selected from lithium salts is used. The concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, particularly 0.9 to 1.25 mol / l. In addition, vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, biphenyl, fluorobenzene, t are used for the purpose of improving safety, charge / discharge cycleability, and high-temperature storage properties of these electrolytes. -Additives such as butylbenzene can be added as appropriate.
また、前記の非水電解液は、ポリマーなどの公知のゲル化剤を加えてゲル状（ゲル状電解質）として用いてもよい。 The non-aqueous electrolyte may be used as a gel (gel electrolyte) by adding a known gelling agent such as a polymer.
本発明のリチウムイオン二次電池の形態としては、スチール缶やアルミニウム缶などを外装缶として使用した筒形（角筒形や円筒形など）などが挙げられる。また、金属を蒸着したラミネートフィルムを外装体としたソフトパッケージ電池とすることもできる。 Examples of the form of the lithium ion secondary battery of the present invention include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
本発明のリチウムイオン二次電池は、従来汎用されている充電装置、例えば、定電流定電圧充電装置や、パルス充電装置などに設置して用いることができる。この場合、充電装置の充電終止電圧を４．３〜４．６Ｖの範囲に設定することにより、電池の充電終止電圧が規定された範囲に設定される。 The lithium ion secondary battery of the present invention can be used by being installed in a conventional charging device, for example, a constant current constant voltage charging device or a pulse charging device. In this case, by setting the end-of-charge voltage of the charging device in the range of 4.3 to 4.6 V, the end-of-charge voltage of the battery is set in the specified range.
電池の高容量化には、前記の電極合剤層を厚くする方法以外にも、充電終止電圧を従来の値（４．２Ｖ）よりも高くすることなどが挙げられる。 In order to increase the capacity of the battery, in addition to the method of increasing the electrode mixture layer, increasing the end-of-charge voltage from the conventional value (4.2 V) can be mentioned.
ところが、電池の充電電圧を高くする場合、電極内での充放電反応が不均一であると、活物質の利用効率にばらつきが生じ、電池の充放電サイクル特性が低下するなどの問題が生じやすくなる。しかしながら、前記ガラスセラミックス粒子を含む本発明の電極を有する本発明の電池では、前記ガラスセラミックス粒子の作用によって、電極内の充放電反応の均一化を図ることができ、電池の充電終止電圧が４．３〜４．６Ｖの範囲にまで高められた場合であっても、活物質全体の利用効率を向上させることができる。よって、本発明によれば、高容量化を図りながら、高負荷でも充放電サイクル特性が良好で、かつ信頼性の高いリチウムイオン二次電池を実現することができる。 However, when the charge voltage of the battery is increased, if the charge / discharge reaction in the electrode is not uniform, there is a variation in the utilization efficiency of the active material, and problems such as deterioration of the charge / discharge cycle characteristics of the battery are likely to occur. Become. However, in the battery of the present invention having the electrode of the present invention containing the glass ceramic particles, the charge / discharge reaction in the electrode can be made uniform by the action of the glass ceramic particles, and the charge end voltage of the battery is 4 Even if it is a case where it raises to the range of .3-4.6V, the utilization efficiency of the whole active material can be improved. Therefore, according to the present invention, it is possible to realize a lithium ion secondary battery having good charge / discharge cycle characteristics and high reliability even at high loads while increasing the capacity.
本発明のリチウムイオン二次電池は、優れた充放電サイクル特性や負荷特性を有しており、こうした特性が特に求められる用途をはじめとして、従来から知られているリチウムイオン二次電池が適用されている各種用途と同じ用途に用いることができる。 The lithium ion secondary battery of the present invention has excellent charge / discharge cycle characteristics and load characteristics, and conventionally known lithium ion secondary batteries are used, including applications where such characteristics are particularly required. It can be used for the same applications as various applications.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.
実施例１
＜負極合剤含有組成物の調製＞
Ｌｉイオン伝導性を有するガラスセラミックス粒子として、一次粒子の平均粒子径が１２ｎｍのＬｉ１．２Ａｌ０．２Ｔｉ１．８Ｐ３Ｏ１２粒子を、以下のようにして合成した。
Example 1
<Preparation of negative electrode mixture-containing composition>
As glass ceramic particles having Li ion conductivity, Li 1.2 Al 0.2 Ti 1.8 P 3 O 12 particles having an average primary particle size of 12 nm were synthesized as follows.
塩化アルミニウム六水和物と塩化チタンとを、それぞれ０．０３ｍｏｌ％濃度および０．２７ｍｏｌ％濃度で溶解している水溶液に、２８質量％濃度のアンモニア水を添加することで水酸化アルミニウムおよび水酸化チタンを共沈させ、これら２種の元素の前駆体が均一にナノレベルで混合された懸濁液を得た。更に、この懸濁液を１８０℃で４時間の水熱処理を行った後、水洗、濾過し、湿潤状態の前駆体粉末を得た。この前駆体粉末２８．５ｇに、水酸化リチウム６．２ｇおよびリン酸水素アンモニウム８０ｇを加え、ボールミルを用いて１時間混練した後、９０℃で乾燥させてから、空気中８５０℃で１０時間焼成することにより、前記のガラスセラミックス粒子を合成した。 Aluminum hydroxide and hydroxide are added by adding 28 mass% ammonia water to an aqueous solution in which aluminum chloride hexahydrate and titanium chloride are dissolved at a concentration of 0.03 mol% and 0.27 mol%, respectively. Titanium was coprecipitated to obtain a suspension in which the precursors of these two elements were uniformly mixed at the nano level. Further, the suspension was hydrothermally treated at 180 ° C. for 4 hours, then washed with water and filtered to obtain a wet precursor powder. To 28.5 g of this precursor powder, 6.2 g of lithium hydroxide and 80 g of ammonium hydrogen phosphate were added, kneaded for 1 hour using a ball mill, dried at 90 ° C., and then fired at 850 ° C. in air for 10 hours. Thus, the glass ceramic particles were synthesized.
この粒子について粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０〜７０°の範囲内において非常にブロードなピークを有しており、このピークの半値幅は１．７８°であった。また、前記粒子の窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は１６０ｍ２／ｇであった。 As a result of measuring the powder X-ray diffraction spectrum of this particle, it had a very broad peak in the range of 2θ = 20 to 70 °, and the half width of this peak was 1.78 °. Moreover, the specific surface area (BET specific surface area) calculated | required by nitrogen gas adsorption | suction of the said particle | grains was 160 m < 2 > / g.
１０質量％となる量の前記ガラスセラミックス粒子を水に加え、φ０．３ｍｍのジルコニアビーズを用いてペイントシェーカーで１時間混合して、ガラスセラミックス粒子の水分散体を調製した。この分散体におけるガラスセラミックス粒子の分散粒子径は１２６ｎｍであった。 The glass ceramic particles in an amount of 10% by mass were added to water and mixed with a paint shaker for 1 hour using φ0.3 mm zirconia beads to prepare an aqueous dispersion of glass ceramic particles. The dispersion particle diameter of the glass ceramic particles in this dispersion was 126 nm.
鱗片状黒鉛（日立化成工業社製、一次粒子径の平均粒子径：約４５０μｍ）：９７．８質量部、ＣＭＣ：１．２質量部およびＳＢＲ：１質量部を、水：１００質量部に分散させて分散体を調製した。この分散体：１００質量部に、前記のガラスセラミックス粒子の水分散体：１．０質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を０．２質量％の量で含有する負極合剤含有組成物を調製した。 Scale-like graphite (manufactured by Hitachi Chemical Co., Ltd., average particle diameter of primary particle diameter: about 450 μm): 97.8 parts by mass, CMC: 1.2 parts by mass and SBR: 1 part by mass dispersed in water: 100 parts by mass To prepare a dispersion. Add 100 parts by weight of the above dispersion: 1.0 part by weight of water dispersion of glass ceramic particles, and mix for about 15 minutes using a paint shaker without using beads for dispersion. A negative electrode mixture-containing composition containing glass ceramic particles in an amount of 0.2% by mass in a total of 100% by mass with the particles was prepared.
＜リチウムイオン二次電池（テストセル）の作製＞
前記の負極合剤含有組成物を、集電体となる厚みが８μｍの銅箔の片面にアプリケーターを用いて塗布して乾燥し、プレス処理した後、３５×３５ｍｍのサイズにカットして、負極を作製した。得られた負極の負極合剤層の厚みは９８μｍであった。
<Production of lithium ion secondary battery (test cell)>
The negative electrode mixture-containing composition is applied to one side of a copper foil having a thickness of 8 μm as a current collector using an applicator, dried, pressed, cut into a size of 35 × 35 mm, and the negative electrode Was made. The thickness of the negative electrode mixture layer of the obtained negative electrode was 98 μm.
また、正極活物質であるＬｉ１．０２Ｎｉ０．５Ｍｎ０．２Ｃｏ０．３Ｏ３（一次粒子の平均粒子径：１５μｍ）：９３．７質量部、アセチレンブラック：４質量部、ＰＶＤＦ：２質量部およびポリビニルピロリドン：０．３質量部を、ＮＭＰに分散させて正極合剤含有組成物を調製し、これを集電体となる厚みが１５μｍのアルミニウム箔の片面に、正極活物質の量が２０ｍｇ／ｃｍ２となるようにアプリケーターを用いて塗布して乾燥し、プレス処理した後、３０×３０ｍｍのサイズにカットして、正極を作製した。得られた正極の正極合剤層の厚みは７５μｍであった。 Further, Li 1.02 Ni 0.5 Mn 0.2 Co 0.3 O 3 (average particle diameter of primary particles: 15 μm) as a positive electrode active material: 93.7 parts by mass, acetylene black: 4 parts by mass, PVDF : 2 parts by mass and polyvinyl pyrrolidone: 0.3 parts by mass are dispersed in NMP to prepare a positive electrode mixture-containing composition, and this is applied to one side of an aluminum foil having a thickness of 15 μm serving as a current collector. After applying and drying using an applicator so that the amount of the resin became 20 mg / cm 2 , press treatment was performed, and then cut into a size of 30 × 30 mm to produce a positive electrode. The thickness of the positive electrode mixture layer of the obtained positive electrode was 75 μm.
前記の正極と前記の負極とを、セパレータ（厚みが１６μｍのＰＥ製微多孔膜）を介して積層してラミネートフィルム外装体内に挿入し、非水電解液（エチレンカーボネートとジエチルカーボネートとの体積比３：７の混合溶媒に、ＬｉＰＦ６を１．２Ｍの濃度で溶解した溶液）を注入した後にラミネートフィルム外装体を封止して、テストセルを作製した。得られたテストセルの設計容量は２６ｍＡｈである（後記の実施例２〜４、および比較例１〜３の各テストセルも同様である）。 The positive electrode and the negative electrode are laminated via a separator (PE microporous film having a thickness of 16 μm) and inserted into a laminate film exterior, and a non-aqueous electrolyte (volume ratio of ethylene carbonate and diethyl carbonate) After injecting LiPF 6 at a concentration of 1.2 M into a 3: 7 mixed solvent, the laminate film outer package was sealed to prepare a test cell. The design capacity of the obtained test cell is 26 mAh (the same applies to each test cell in Examples 2 to 4 and Comparative Examples 1 to 3 described later).
実施例２
Ｌｉイオン伝導性を有するガラスセラミックス粒子として、一次粒子の平均粒子径が４８ｎｍのＬｉ１．２Ａｌ０．２１Ｙ０．０６Ｔｉ１．７３Ｐ３Ｏ１２粒子を、以下のようにして合成した。
Example 2
As glass ceramic particles having Li ion conductivity, Li 1.2 Al 0.21 Y 0.06 Ti 1.73 P 3 O 12 particles having an average primary particle size of 48 nm were synthesized as follows. .
塩化アルミニウム六水和物と塩化チタンと硝酸イットリウム六水和物を、それぞれ０．０３ｍｏｌ％濃度、０．２６ｍｏｌ％濃度および０．００９ｍｏｌ％濃度で溶解している水溶液に、２８質量％濃度のアンモニア水を添加することで水酸化アルミニウム、水酸化チタンおよび水酸化イットリウムを共沈させ、これら３種の元素の前駆体が均一にナノレベルで混合された懸濁液を得た。更に、この懸濁液を１８０℃で４時間の水熱処理を行った後、水洗、濾過し、湿潤状態の前駆体粉末を得た。この前駆体粉末３９ｇに、水酸化リチウム６．２ｇおよびリン酸水素アンモニウム８０ｇを加え、ボールミルを用いて１時間混練した後、９０℃で乾燥させてから、空気中１０００℃で７時間焼成することにより、前記のガラスセラミックス粒子を合成した。 28 mass% ammonia in an aqueous solution in which aluminum chloride hexahydrate, titanium chloride, and yttrium nitrate hexahydrate are dissolved at a concentration of 0.03 mol%, 0.26 mol%, and 0.009 mol%, respectively. By adding water, aluminum hydroxide, titanium hydroxide and yttrium hydroxide were co-precipitated to obtain a suspension in which the precursors of these three elements were uniformly mixed at the nano level. Further, the suspension was hydrothermally treated at 180 ° C. for 4 hours, then washed with water and filtered to obtain a wet precursor powder. To 39 g of this precursor powder, 6.2 g of lithium hydroxide and 80 g of ammonium hydrogen phosphate are added, kneaded for 1 hour using a ball mill, dried at 90 ° C., and then fired at 1000 ° C. in air for 7 hours. Thus, the glass ceramic particles were synthesized.
この粒子について粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０〜７０°の範囲内において非常にブロードなピークを有しており、このピークの半値幅は１．５３°であった。また、前記粒子の窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は２４ｍ２／ｇであった。 As a result of measuring the powder X-ray diffraction spectrum of this particle, it had a very broad peak in the range of 2θ = 20 to 70 °, and the half width of this peak was 1.53 °. The specific surface area (BET specific surface area) determined by nitrogen gas adsorption of the particles was 24 m 2 / g.
３０質量％となる量の前記ガラスセラミックス粒子を水に加え、φ０．３ｍｍのジルコニアビーズを用いてペイントシェーカーで１時間混合して、ガラスセラミックス粒子の水分散体を調製した。この分散体におけるガラスセラミックス粒子の分散粒子径は１８９ｎｍであった。 The glass ceramic particles in an amount of 30% by mass were added to water and mixed with a paint shaker for 1 hour using φ0.3 mm zirconia beads to prepare an aqueous dispersion of glass ceramic particles. The dispersion particle diameter of the glass ceramic particles in this dispersion was 189 nm.
実施例１で調製したものと同じ鱗片状黒鉛などを含有する分散体：１００質量部に、前記のガラスセラミックス粒子の水分散体：１５．８質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を９．５質量％の量で含有する負極合剤含有組成物を調製し、この負極合剤含有組成物を用いた以外は、実施例１と同様にして負極を作製した。 Dispersion containing the same scaly graphite as prepared in Example 1: 100 parts by weight of water dispersion of glass ceramic particles: 15.8 parts by weight, without using beads for dispersion The mixture was mixed for about 15 minutes with a paint shaker to prepare a negative electrode mixture-containing composition containing 9.5% by mass of glass ceramic particles in a total of 100% by mass of flaky graphite and glass ceramic particles. A negative electrode was produced in the same manner as in Example 1 except that the mixture-containing composition was used.
そして、前記の負極を用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode.
実施例３
Ｌｉイオン伝導性を有するガラスセラミックス粒子として、一次粒子の平均粒子径が４３ｎｍのＬｉ１．２Ｌａ０．２Ｚｒ１．８Ｓｉ０．２１Ｐ２．７９Ｏ１２粒子を、以下のようにして合成した。
Example 3
As glass ceramic particles having Li ion conductivity, Li 1.2 La 0.2 Zr 1.8 Si 0.21 P 2.79 O 12 particles having an average primary particle size of 43 nm were prepared as follows. Synthesized.
硝酸ランタン六水和物と塩化酸化ジルコニウム八水和物とを、それぞれ０．０３ｍｏｌ％濃度および０．２７ｍｏｌ％濃度で溶解している水溶液１Ｌに、０．３ｍｏｌ％濃度のケイ酸ナトリウム水溶液１００ｇを加えた後、２８質量％濃度のアンモニア水を添加することで水酸化ランタン、水酸化ジルコニウムおよびケイ酸を共沈させ、これら３種の元素の前駆体が均一にナノレベルで混合された懸濁液を得た。さらに、この懸濁液を１８０℃で４時間の水熱処理を行った後、水洗、濾過し、湿潤状態の前駆体粉末を得た。この前駆体粉末３９．５ｇに、水酸化リチウム６．２ｇおよびリン酸水素アンモニウム７５ｇを加え、ボールミルを用いて１時間混練した後、９０℃で乾燥させてから、空気中１０００℃で７時間焼成することにより、前記のガラスセラミックス粒子を合成した。 To 1 L of an aqueous solution in which lanthanum nitrate hexahydrate and chlorinated zirconium oxide octahydrate are dissolved at 0.03 mol% concentration and 0.27 mol% concentration, respectively, 100 g of 0.3 mol% sodium silicate aqueous solution is added. After addition, lanthanum hydroxide, zirconium hydroxide and silicic acid are co-precipitated by adding 28% by weight ammonia water, and a suspension in which the precursors of these three elements are uniformly mixed at the nano level. A liquid was obtained. Further, the suspension was hydrothermally treated at 180 ° C. for 4 hours, then washed with water and filtered to obtain a wet precursor powder. After adding 6.2 g of lithium hydroxide and 75 g of ammonium hydrogen phosphate to 39.5 g of this precursor powder, kneading for 1 hour using a ball mill, drying at 90 ° C., and baking at 1000 ° C. in air for 7 hours Thus, the glass ceramic particles were synthesized.
この粒子について粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０〜７０°の範囲内において非常にブロードなピークを有しており、このピークの半値幅は１．５４°であった。また、前記粒子の窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は２６ｍ２／ｇであった。 As a result of measuring the powder X-ray diffraction spectrum of this particle, it had a very broad peak in the range of 2θ = 20 to 70 °, and the half width of this peak was 1.54 °. The specific surface area (BET specific surface area) determined by nitrogen gas adsorption of the particles was 26 m 2 / g.
このガラスセラミックス粒子を用いた以外は、実施例１と同様にしてガラスセラミックス粒子の水分散体を調製した。この分散体におけるガラスセラミックス粒子の分散粒子径は１７５ｎｍであった。 An aqueous dispersion of glass ceramic particles was prepared in the same manner as in Example 1 except that the glass ceramic particles were used. The dispersion particle diameter of the glass ceramic particles in this dispersion was 175 nm.
実施例１で調製したものと同じ鱗片状黒鉛などを含有する分散体：１００質量部に、前記のガラスセラミックス粒子の水分散体：２．５質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を０．５質量％の量で含有する負極合剤含有組成物を調製し、この負極合剤含有組成物を用いた以外は、実施例１と同様にして負極を作製した。 Dispersion containing the same scaly graphite as prepared in Example 1: 100 parts by mass Aqueous dispersion of the above glass ceramic particles: 2.5 parts by mass, without using beads for dispersion The negative electrode mixture-containing composition containing 0.5% by mass of glass ceramic particles in a total of 100% by mass of scaly graphite and glass ceramic particles was prepared by mixing with a paint shaker for about 15 minutes. A negative electrode was produced in the same manner as in Example 1 except that the mixture-containing composition was used.
そして、前記の負極を用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode.
実施例４
Ｌｉイオン伝導性を有するガラスセラミックス粒子として、一次粒子の平均粒子径が３５ｎｍのＬｉ１．２Ａｌ０．２１Ｙ０．０６Ｔｉ１．７３Ｓｉ０．２１Ｐ２．７９Ｏ１２粒子を以下のようにして合成した。
Example 4
As glass ceramic particles having Li ion conductivity, Li 1.2 Al 0.21 Y 0.06 Ti 1.73 Si 0.21 P 2.79 O 12 particles having an average primary particle size of 35 nm are as follows. In this way, it was synthesized.
塩化アルミニウム六水和物と塩化チタンと硝酸イットリウム六水和物とを、それぞれ０．０３ｍｏｌ％濃度、０．２６ｍｏｌ％濃度、および０．００９ｍｏｌ％濃度で溶解している水溶液１Ｌに、０．３ｍｏｌ％濃度のケイ酸ナトリウム水溶液１００ｇを加えた後、２８質量％濃度のアンモニア水を添加することで水酸化アルミニウム、水酸化チタン、水酸化イットリウムおよびケイ酸を共沈させ、これら４種の元素の前駆体が均一にナノレベルで混合された懸濁液を得た。更に、この懸濁液を１８０℃で４時間の水熱処理を行った後、水洗、濾過し、湿潤状態の前駆体粉末を得た。この前駆体粉末４０ｇに、水酸化リチウム６．２ｇおよびリン酸水素アンモニウム７５ｇを加え、ボールミルを用いて１時間混練した後、９０℃で乾燥させてから、空気中９００℃で１０時間焼成することにより、前記のガラスセラミックス粒子を合成した。 0.3 mol in 1 L of an aqueous solution in which aluminum chloride hexahydrate, titanium chloride, and yttrium nitrate hexahydrate are dissolved at a concentration of 0.03 mol%, 0.26 mol%, and 0.009 mol%, respectively. After adding 100 g of a sodium silicate aqueous solution with a concentration of 100%, ammonia water with a concentration of 28% by mass was added to coprecipitate aluminum hydroxide, titanium hydroxide, yttrium hydroxide and silicic acid. A suspension in which the precursor was uniformly mixed at the nano level was obtained. Further, the suspension was hydrothermally treated at 180 ° C. for 4 hours, then washed with water and filtered to obtain a wet precursor powder. After adding 6.2 g of lithium hydroxide and 75 g of ammonium hydrogen phosphate to 40 g of this precursor powder, kneading for 1 hour using a ball mill, drying at 90 ° C., and firing at 900 ° C. for 10 hours in air. Thus, the glass ceramic particles were synthesized.
前記のガラスセラミックス粒子の粉末Ｘ線回折スペクトルを図１に示す。図１から明らかなように、このガラスセラミックス粒子は、２θ＝２０〜７０°の範囲内においてブロードなピークを有しており、このピークの半値幅は１．６１°であった。また、前記粒子の窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は４３ｍ２／ｇであった。 The powder X-ray diffraction spectrum of the glass ceramic particles is shown in FIG. As apparent from FIG. 1, the glass ceramic particles had a broad peak in the range of 2θ = 20 to 70 °, and the half width of this peak was 1.61 °. The specific surface area (BET specific surface area) determined by nitrogen gas adsorption of the particles was 43 m 2 / g.
このガラスセラミックス粒子を用いた以外は、実施例１と同様にしてガラスセラミックス粒子の水分散体を調製した。この分散体におけるガラスセラミックス粒子の分散粒子径は１６９ｎｍであった。 An aqueous dispersion of glass ceramic particles was prepared in the same manner as in Example 1 except that the glass ceramic particles were used. The dispersion particle diameter of the glass ceramic particles in this dispersion was 169 nm.
実施例１で調製したものと同じ鱗片状黒鉛などを含有する分散体：１００質量部に、前記のガラスセラミックス粒子の水分散体：５．０質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を１．０質量％の量で含有する負極合剤含有組成物を調製し、この負極合剤含有組成物を用いた以外は、実施例１と同様にして負極を作製した。 Dispersion containing the same scaly graphite as prepared in Example 1: 100 parts by mass of water dispersion of glass ceramic particles: 5.0 parts by mass, without using beads for dispersion The mixture was mixed for about 15 minutes with a paint shaker to prepare a negative electrode mixture-containing composition containing 1.0% by mass of glass ceramic particles in a total of 100% by mass of flaky graphite and glass ceramic particles. A negative electrode was produced in the same manner as in Example 1 except that the mixture-containing composition was used.
そして、前記の負極を用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode.
比較例１
鱗片状黒鉛（日立化成工業社製、一次粒子径の平均粒子径：約４５０μｍ）：９７．８質量部、ＣＭＣ：１．２質量部およびＳＢＲ：１質量部を、水：１００質量部に分散させて負極合剤含有組成物を調製し、この負極合剤含有組成物を用いた以外は、実施例１と同様にして負極を作製した。
Comparative Example 1
Scale-like graphite (manufactured by Hitachi Chemical Co., Ltd., average particle diameter of primary particle diameter: about 450 μm): 97.8 parts by mass, CMC: 1.2 parts by mass and SBR: 1 part by mass dispersed in water: 100 parts by mass A negative electrode mixture-containing composition was prepared, and a negative electrode was produced in the same manner as in Example 1 except that this negative electrode mixture-containing composition was used.
そして、前記の負極を用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode.
比較例２
ガラスセラミックス粒子として、一次粒子の平均粒子径が１２４ｎｍのＬｉ１．２Ａｌ０．２Ｔｉ１．８Ｐ３Ｏ１２粒子を以下のように合成した。
Comparative Example 2
As glass ceramic particles, Li 1.2 Al 0.2 Ti 1.8 P 3 O 12 particles having an average primary particle size of 124 nm were synthesized as follows.
原料粉として、酸化アルミニウム２ｇ、酸化チタン２８．８ｇ、炭酸リチウム１９．２ｇおよびリン酸水素アンモニウム７９．２ｇ（いずれも和光純薬工業社製）を乳鉢で混合した後、１２００℃で１０時間焼成した。その後、φ３ｍｍのジルコニアビーズを用いてボールミルで乾式粉砕することにより作製した。 As raw material powder, 2 g of aluminum oxide, 28.8 g of titanium oxide, 19.2 g of lithium carbonate and 79.2 g of ammonium hydrogen phosphate (all manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in a mortar and then fired at 1200 ° C. for 10 hours. did. Then, it produced by carrying out dry grinding | pulverization with a ball mill using (phi) 3 mm zirconia bead.
前記のガラスセラミックス粒子の粉末Ｘ線回折スペクトルを図２に示す。図２から明らかなように、このガラスセラミックス粒子は、２θ＝２０〜７０°の範囲内においてピークを有しており、このピークの半値幅は０．７９°であった。また、前記粒子の窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は１４ｍ２／ｇであった。 FIG. 2 shows a powder X-ray diffraction spectrum of the glass ceramic particles. As apparent from FIG. 2, the glass ceramic particles had a peak in the range of 2θ = 20 to 70 °, and the half width of this peak was 0.79 °. The specific surface area (BET specific surface area) determined by nitrogen gas adsorption of the particles was 14 m 2 / g.
前記のガラスセラミックス粒子を用いた以外は、実施例１と同様にしてガラスセラミックス粒子の水分散体を調製した。この分散体におけるガラスセラミックス粒子の分散粒子径は３６６ｎｍであった。そして、このガラスセラミックス粒子の水分散体を用いた以外は実施例４と同様にして負極合剤含有組成物を調製し、この負極合剤含有組成物を用いた以外は実施例１と同様にして負極を作製した。 An aqueous dispersion of glass ceramic particles was prepared in the same manner as in Example 1 except that the glass ceramic particles were used. The dispersion particle diameter of the glass ceramic particles in this dispersion was 366 nm. Then, a negative electrode mixture-containing composition was prepared in the same manner as in Example 4 except that this water dispersion of glass ceramic particles was used, and in the same manner as in Example 1 except that this negative electrode mixture-containing composition was used. Thus, a negative electrode was produced.
そして、前記の負極を用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode.
比較例３
実施例１で調製したものと同じ鱗片状黒鉛などを含有する分散体：１００質量部に、実施例４で調製したものと同じガラスセラミックス粒子の水分散体：７５質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を１５．０質量％の量で含有する負極合剤含有組成物を調製し、この負極合剤含有組成物を用いた以外は、実施例１と同様にして負極を作製した。
Comparative Example 3
Dispersion containing the same scaly graphite as prepared in Example 1: 100 parts by mass The same glass ceramic particle aqueous dispersion as that prepared in Example 4: 75 parts by mass was added and dispersed. A composition containing a negative electrode mixture containing 15.0% by mass of glass ceramic particles in a total of 100% by mass of flaky graphite and glass ceramic particles by mixing with a paint shaker without using beads. A negative electrode was produced in the same manner as in Example 1 except that this negative electrode mixture-containing composition was prepared.
そして、前記の負極を用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode.
実施例１〜４および比較例１〜３のテストセルについて、以下の方法で負荷特性および充放電サイクル特性を評価した。 For the test cells of Examples 1 to 4 and Comparative Examples 1 to 3, load characteristics and charge / discharge cycle characteristics were evaluated by the following methods.
＜初回充放電効率＞
実施例１〜４および比較例１〜３のテストセルについて、０．１Ｃの電流値で電圧が４．２Ｖになるまで定電流充電を行い、続いて、４．２Ｖで定電圧充電を行った。なお、定電流充電および定電圧充電の総充電時間は２時間とした。その後、各テストセルを０．２Ｃの電流値で電圧が２．５Ｖになるまで放電させた。
<First charge / discharge efficiency>
For the test cells of Examples 1 to 4 and Comparative Examples 1 to 3, constant current charging was performed until the voltage reached 4.2 V at a current value of 0.1 C, and then constant voltage charging was performed at 4.2 V. . The total charging time for constant current charging and constant voltage charging was 2 hours. Thereafter, each test cell was discharged at a current value of 0.2 C until the voltage reached 2.5V.
各テストセルについて、前記の充放電における放電容量を充電容量で除した値を百分率で表して、初回充放電効率を求めた。 About each test cell, the value which remove | divided the discharge capacity in the said charging / discharging by charge capacity was represented by the percentage, and the first time charge / discharge efficiency was calculated | required.
＜充放電サイクル特性＞
実施例１〜４および比較例１〜３のテストセルについて、２Ｃの電流値で電圧が４．２Ｖになるまで定電流充電を行い、続いて、４．２Ｖで定電圧充電を行った。なお、定電流充電および定電圧充電の総充電時間は２時間とした。その後、各テストセルを２Ｃの電流値で電圧が２．５Ｖになるまで放電させた。この定電圧充電−定電流充電−放電の一連の操作を１サイクルとして、４００サイクルの充放電を行った。そして、４００サイクル目の放電容量を１サイクル目の放電容量で除した値を百分率で表して、容量維持率を求めた。この容量維持率が大きいほど、テストセルの充放電サイクル特性が良好であるといえる。
<Charge / discharge cycle characteristics>
For the test cells of Examples 1 to 4 and Comparative Examples 1 to 3, constant current charging was performed until the voltage reached 4.2 V at a current value of 2 C, and then constant voltage charging was performed at 4.2 V. The total charging time for constant current charging and constant voltage charging was 2 hours. Thereafter, each test cell was discharged at a current value of 2C until the voltage reached 2.5V. A series of operations of this constant voltage charge-constant current charge-discharge was taken as one cycle, and 400 cycles of charge / discharge were performed. And the value which divided | segmented the discharge capacity of 400th cycle by the discharge capacity of 1st cycle was represented by the percentage, and the capacity | capacitance maintenance factor was calculated | required. It can be said that the larger the capacity retention rate, the better the charge / discharge cycle characteristics of the test cell.
実施例１〜４および比較例１〜３のテストセルに使用した負極の構成を表１および表２に示し、前記の評価結果を表３に示す。 The structure of the negative electrode used for the test cell of Examples 1-4 and Comparative Examples 1-3 is shown in Table 1 and Table 2, and the said evaluation result is shown in Table 3.
表１における「半値幅」は、ガラスセラミックス粒子の粉末Ｘ線回折スペクトルにおける２θ＝２０〜７０°の範囲内に存在する最も強度の大きなピークの半値幅を意味している（後記の表４および表７も同様である）。 “Half width” in Table 1 means the half width of the strongest peak existing in the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum of the glass ceramic particles (see Table 4 and below). The same applies to Table 7).
表２におけるガラスセラミックス粒子の欄の「割合」は、活物質粒子とガラスセラミックス粒子との合計１００質量％中におけるガラスセラミックス粒子の割合を意味している（後記の表５および表８も同様である）。 The “ratio” in the column of glass ceramic particles in Table 2 means the ratio of glass ceramic particles in a total of 100 mass% of active material particles and glass ceramic particles (the same applies to Tables 5 and 8 below). is there).
表１〜表３から明らかなように、一次粒子の平均粒子径が適正であり、結晶性が低く、かつＬｉイオン伝導性を有するガラスセラミックス粒子を、適正な量で含有する負極を有する実施例１〜４のテストセルは、ガラスセラミックス粒子を含有しない負極を有する比較例１のテストセルに比べて、２Ｃといった比較的高負荷でも充放電サイクル特性が優れている。また、実施例１〜４のテストセルは、比較例１のテストセルに比べると、初回充放電効率はやや低いものの、その大きな低下は抑えられており、不可逆容量の増大が抑制できている。 As is clear from Tables 1 to 3, Examples having negative electrodes containing glass ceramic particles having an appropriate amount of glass ceramic particles having an appropriate primary particle average particle size, low crystallinity, and Li ion conductivity. The test cells 1 to 4 are excellent in charge / discharge cycle characteristics even at a relatively high load of 2C, compared to the test cell of Comparative Example 1 having a negative electrode that does not contain glass ceramic particles. Moreover, although the first charge / discharge efficiency of the test cells of Examples 1 to 4 is slightly lower than that of the test cell of Comparative Example 1, the large decrease is suppressed, and the increase in irreversible capacity can be suppressed.
一方、結晶性が高く、かつ一次粒子の平均粒子径が大きすぎるガラスセラミックス粒子を含有する負極を有する比較例２のテストセル、およびガラスセラミックス粒子の量が多すぎる負極を有する比較例３のテストセルは、初回充放電効率が低く、初回充電でのガラスセラミックス粒子のＬｉ吸蔵量が多いために、不可逆容量が増大したと考えられる。 On the other hand, the test cell of Comparative Example 2 having a negative electrode containing glass ceramic particles having high crystallinity and the average particle diameter of primary particles being too large, and the test of Comparative Example 3 having a negative electrode having an excessive amount of glass ceramic particles It is considered that the irreversible capacity increased because the cell had low initial charge / discharge efficiency and a large amount of Li occlusion in the glass ceramic particles in the initial charge.
実施例５
鱗片状黒鉛（日立化成工業社製、一次粒子径の平均粒子径：約４５０μｍ）：９４．１質量部、表面を炭素（ＣＶＤ法で形成した炭素）で被覆したＳｉＯ（ＳｉＯと表面の炭素との質量比が８５：１５、平均粒子径：約５μｍ）：３．７質量部、ＣＭＣ：１．２質量部およびＳＢＲ：１質量部を、水：１００質量部に分散させて分散体を調製した。この分散体：１００質量部に、実施例４で調製したものと同じガラスセラミックス粒子の水分散体：５．０質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を１．０質量％の量で含有する負極合剤含有組成物を調製した。そして、この負極合剤含有組成物を用い、実施例１と同様にして、厚みが７９μｍの負極合剤層を集電体の片面に有する負極を作製した。
Example 5
Scale-like graphite (manufactured by Hitachi Chemical Co., Ltd., average particle diameter of primary particle diameter: about 450 μm): 94.1 parts by mass, SiO coated with carbon (carbon formed by CVD method) (SiO and surface carbon The mass ratio is 85:15, the average particle size is about 5 μm): 3.7 parts by mass, CMC: 1.2 parts by mass, and SBR: 1 part by mass are dispersed in water: 100 parts by mass to prepare a dispersion. did. To this dispersion: 100 parts by weight, add the same glass ceramic particle aqueous dispersion as prepared in Example 4: 5.0 parts by weight, and mix for about 15 minutes with a paint shaker without using beads for dispersion. A negative electrode mixture-containing composition containing glass ceramic particles in an amount of 1.0% by mass in a total of 100% by mass of flake graphite and glass ceramic particles was prepared. Then, using this negative electrode mixture-containing composition, a negative electrode having a negative electrode mixture layer having a thickness of 79 μm on one side of the current collector was produced in the same manner as in Example 1.
また、正極合剤含有組成物の集電体への塗布量を、正極活物質が３１ｍｇ／ｃｍ２となるように変更した以外は実施例１と同様にして、厚みが１１２μｍの正極合剤層を集電体の片面に有する正極を作製した。 Further, a positive electrode mixture layer having a thickness of 112 μm was obtained in the same manner as in Example 1 except that the amount of the positive electrode mixture-containing composition applied to the current collector was changed so that the positive electrode active material was 31 mg / cm 2. Was produced on one side of the current collector.
そして、前記の負極と前記の正極とを用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。得られたテストセルの設計容量は４０ｍＡｈである（後記の比較例４のテストセルも同様である）。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said negative electrode and the said positive electrode. The design capacity of the obtained test cell is 40 mAh (the same applies to the test cell of Comparative Example 4 described later).
比較例４
実施例５で負極合剤含有組成物の調製に用いた鱗片状黒鉛および表面を炭素で被覆したＳｉＯなどを含む分散体を、負極合剤含有組成物に用いた以外は、実施例５と同様にして、厚みが７９μｍの負極合剤層を集電体の片面に有する負極を作製した。
Comparative Example 4
The same as Example 5 except that the dispersion containing the scaly graphite used for the preparation of the negative electrode mixture-containing composition in Example 5 and SiO having a surface coated with carbon was used for the negative electrode mixture-containing composition. Thus, a negative electrode having a negative electrode mixture layer having a thickness of 79 μm on one side of the current collector was produced.
そして、前記の負極を用いた以外は、実施例５と同様にしてテストセル（リチウムイオン二次電池）を作製した。 And the test cell (lithium ion secondary battery) was produced like Example 5 except having used the said negative electrode.
実施例５および比較例４のテストセルについて、実施例１のテストセルなどと同様にして初回充放電効率および充放電サイクル特性を評価した。これらのテストセルの負極の構成を表４および表５に、評価結果を表６に、それぞれ示す。 For the test cells of Example 5 and Comparative Example 4, the initial charge / discharge efficiency and the charge / discharge cycle characteristics were evaluated in the same manner as the test cell of Example 1. Tables 4 and 5 show the configurations of the negative electrodes of these test cells, and Table 6 shows the evaluation results.
表４〜表６から明らかなように、一次粒子の平均粒子径が適正であり、結晶性が低く、かつＬｉイオン伝導性を有するガラスセラミックス粒子を、適正な量で含有する負極を有する実施例５のテストセルは、ガラスセラミックス粒子を含有しない負極を有する比較例４のテストセルに比べて、２Ｃといった比較的高負荷でも充放電サイクル特性が優れている。また、実施例５のテストセルは、比較例４のテストセルに比べると、初回充放電効率はやや低いものの、その大きな低下は抑えられており、不可逆容量の増大は抑制できている。 As is apparent from Tables 4 to 6, examples having negative electrodes containing glass ceramic particles having an appropriate amount of glass ceramic particles having an appropriate primary particle average particle size, low crystallinity, and Li ion conductivity. The test cell No. 5 has excellent charge / discharge cycle characteristics even at a relatively high load such as 2C, as compared with the test cell of Comparative Example 4 having a negative electrode containing no glass ceramic particles. In addition, the test cell of Example 5 has a slightly lower initial charge / discharge efficiency than the test cell of Comparative Example 4, but its large decrease is suppressed, and an increase in irreversible capacity can be suppressed.
実施例５のテストセルは、負極活物質に、鱗片状黒鉛よりも高容量のＳｉＯを鱗片状黒鉛と併用することで、更なる高容量化を図った例であるが、このような電池の場合にも、前記の通り、比較的負荷での充放電サイクル特性の向上効果と、不可逆容量増大の抑制効果とが認められる。 The test cell of Example 5 is an example in which a higher capacity is achieved by using SiO having a capacity higher than that of flaky graphite in combination with flaky graphite as the negative electrode active material. Even in this case, as described above, the effect of improving the charge / discharge cycle characteristics under a relatively load and the effect of suppressing the increase in irreversible capacity are recognized.
実施例６
正極活物質であるＬｉ１．０２Ｎｉ０．５Ｍｎ０．２Ｃｏ０．３Ｏ３（一次粒子の平均粒子径：１５μｍ）：９３．７質量部、アセチレンブラック：４質量部、ＰＶＤＦ：２質量部およびポリビニルピロリドン：０．３質量部を、ＮＭＰ：４０質量部に分散させて分散体を調製した。この分散体：１００質量部に、実施例４で調製したものと同じガラスセラミックス粒子の水分散体：６．７質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、正極活物質粒子とガラスセラミックス粒子との合計１００質量％中、ガラスセラミックス粒子を１．０質量％の量で含有する正極合剤含有組成物を調製した。そして、この正極合剤含有組成物を用いた以外は、実施例５と同様に、集電体への正極合剤含有組成物の塗布量を、正極活物質が３１ｍｇ／ｃｍ２となるようにして、厚みが１１２μｍの正極合剤層を集電体の片面に有する正極を作製した。
Example 6
Li 1.02 Ni 0.5 Mn 0.2 Co 0.3 O 3 (average particle size of primary particles: 15 μm): 93.7 parts by mass, acetylene black: 4 parts by mass, PVDF: 2 A dispersion was prepared by dispersing 0.3 part by mass of polyvinyl pyrrolidone and 0.3 part by mass of NMP: 40 parts by mass. To this dispersion: 100 parts by mass, add 6.7 parts by mass of an aqueous dispersion of glass ceramic particles same as that prepared in Example 4, and mix for about 15 minutes with a paint shaker without using beads for dispersion. A positive electrode mixture-containing composition containing 1.0% by mass of glass ceramic particles in a total of 100% by mass of positive electrode active material particles and glass ceramic particles was prepared. Then, except that this positive electrode mixture-containing composition was used, the amount of the positive electrode mixture-containing composition applied to the current collector was adjusted so that the positive electrode active material was 31 mg / cm 2 , as in Example 5. Thus, a positive electrode having a positive electrode mixture layer with a thickness of 112 μm on one side of the current collector was produced.
また、比較例１と同様にして調製した負極合剤含有組成物を用い、集電体への負極合剤含有組成物の塗布量を変更した以外は、実施例１と同様にして、厚みが１３７μｍの負極合剤層（ガラスセラミックス粒子を含有しない負極合剤層）を集電体の片面に有する負極を作製した。 Further, the thickness was reduced in the same manner as in Example 1 except that the negative electrode mixture-containing composition prepared in the same manner as in Comparative Example 1 was used and the amount of the negative electrode mixture-containing composition applied to the current collector was changed. A negative electrode having a 137 μm negative electrode mixture layer (a negative electrode mixture layer not containing glass ceramic particles) on one side of the current collector was produced.
そして、前記の正極と前記の負極とを用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。得られたテストセルの設計容量は４０ｍＡｈである（後記の比較例５のテストセルも同様である）。 And the test cell (lithium ion secondary battery) was produced like Example 1 except having used the said positive electrode and the said negative electrode. The design capacity of the obtained test cell is 40 mAh (the same applies to the test cell of Comparative Example 5 described later).
比較例５
実施例５で作製したものと同じ正極（ガラスセラミックス粒子を含有しない正極合剤層を有する正極）と、実施例６で作製したものと同じ負極（ガラスセラミックス粒子を含有しない負極合剤層を有する負極）とを用いた以外は、実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。
Comparative Example 5
The same positive electrode (positive electrode having a positive electrode mixture layer not containing glass ceramic particles) as that produced in Example 5 and the same negative electrode (negative electrode mixture layer not containing glass ceramic particles) produced in Example 6 A test cell (lithium ion secondary battery) was produced in the same manner as in Example 1 except that the negative electrode was used.
実施例６および比較例５のテストセルについて、実施例１のテストセルなどと同様にして初回充放電効率および充放電サイクル特性を評価した。これらのテストセルの負極の構成を表７および表８に、評価結果を表９に、それぞれ示す。 For the test cells of Example 6 and Comparative Example 5, the initial charge / discharge efficiency and the charge / discharge cycle characteristics were evaluated in the same manner as the test cell of Example 1. Tables 7 and 8 show the configurations of the negative electrodes of these test cells, and Table 9 shows the evaluation results.
表７〜表９から明らかなように、一次粒子の平均粒子径が適正であり、結晶性が低く、かつＬｉイオン伝導性を有するガラスセラミックス粒子を、適正な量で含有する負極を有する実施例６のテストセルは、ガラスセラミックス粒子を含有しない負極を有する比較例５のテストセルに比べて、２Ｃといった比較的高負荷でも充放電サイクル特性が優れている。また、実施例６のテストセルは、比較例５のテストセルに比べると、初回充放電効率はやや低いものの、その大きな低下は抑えられており、不可逆容量の増大は抑制できている。 As is apparent from Tables 7 to 9, Examples having negative electrodes containing glass ceramic particles having an appropriate amount of primary ceramic particles having an appropriate average particle diameter, low crystallinity, and Li ion conductivity. The test cell No. 6 has excellent charge / discharge cycle characteristics even at a relatively high load of 2C, compared with the test cell of Comparative Example 5 having a negative electrode containing no glass ceramic particles. In addition, the test cell of Example 6 has a slightly lower initial charge / discharge efficiency than the test cell of Comparative Example 5, but its major decrease is suppressed, and an increase in irreversible capacity can be suppressed.
実施例６のテストセルは、正極合剤層および負極合剤層を厚くすることで高容量化を図り、また、正極合剤層に前記ガラスセラミックス粒子を含有させた例であるが、このような電池の場合にも、前記の通り、比較的高負荷でも充放電サイクル特性の向上効果と、不可逆容量増大の抑制効果とが認められる。 The test cell of Example 6 is an example in which the positive electrode mixture layer and the negative electrode mixture layer are thickened to increase the capacity, and the positive electrode mixture layer contains the glass ceramic particles. Even in the case of a simple battery, as described above, the effect of improving the charge / discharge cycle characteristics and the effect of suppressing the increase in irreversible capacity are recognized even at a relatively high load.
Claims (11)
ガラスセラミックス粒子、Ｌｉを吸蔵放出可能な活物質粒子および樹脂製バインダを含む電極合剤層を有しており、
前記ガラスセラミックス粒子は、Ｌｉイオン伝導性を有していて、一次粒子の平均粒子径が５〜５０ｎｍであり、粉末Ｘ線回折スペクトルにおける２θ＝２０〜７０°の範囲内において、ピークを有していないか、または最も強度の大きなピークの半値幅が１．０°以上であり、
前記ガラスセラミックス粒子と前記活物質粒子との合計を１００質量％としたとき、前記ガラスセラミックス粒子の割合が０．１〜１０質量％であることを特徴とするリチウムイオン二次電池用電極。 A lithium ion secondary battery electrode used for the positive electrode and / or the negative electrode of a lithium ion secondary battery having a positive electrode, a negative electrode, a non-aqueous electrolyte and a separator,
Glass ceramic particles, which have a electrode mixture layer containing an active material capable of intercalating and deintercalating particles and a resin binder and Li,
The glass ceramic particles have Li ion conductivity, the average particle diameter of primary particles is 5 to 50 nm, and have a peak in the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum. Or the full width at half maximum of the strongest peak is 1.0 ° or more,
An electrode for a lithium ion secondary battery, wherein a ratio of the glass ceramic particles is 0.1 to 10% by mass when a total of the glass ceramic particles and the active material particles is 100% by mass.
前記正極および／または前記負極が、請求項１〜９のいずれかに記載のリチウムイオン二次電池用電極であることを特徴とするリチウムイオン二次電池。 A lithium ion secondary battery having a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator,
The said positive electrode and / or the said negative electrode are the electrodes for lithium ion secondary batteries in any one of Claims 1-9, The lithium ion secondary battery characterized by the above-mentioned.
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