JP5343528B2 - Negative electrode for lithium ion secondary battery and lithium ion secondary battery - Google Patents
Negative electrode for lithium ion secondary battery and lithium ion secondary battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
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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、リチウムイオン二次電池用負極及びリチウムイオン二次電池に関する。 The present invention relates to a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery.
従来、リチウムイオン二次電池としては、ＬｉＣｏＯ2の一次粒子を凝集させ、球状とすることにより電極上に塗布・プレスさせたときのＸ線回折の（１１０）／（００３）のピーク強度を０．１以上とする、即ち配向性を低減させることにより内部抵抗を低減し、大電流放電時の容量を向上させるものが提案されている（例えば、特許文献１参照）。また、リチウム金属酸化物を活物質とする正極とＬｉ2Ｔｉ3Ｏ7で表されるリチウムチタン酸化物を活物質とする負極とを備え、リチウム金属酸化物の実容量に対するリチウムチタン酸化物の実容量の比を０．８以下とすることにより、充放電の繰り返しによる正極活物質の結晶構造の破壊を抑制し充放電サイクルの寿命特性を高めたものが提案されている（例えば、特許文献２参照）。更に、ラムスデライト構造を有するリチウムチタン酸化物を用い、正極と負極との容量比を負極／正極＝１〜７にした電気化学キャパシタが提案されている（例えば、特許文献３参照）。この電気化学キャパシタは、電気化学キャパシタと電池とを並列につなぐことにより、高容量且つ長寿命なハイブリッド電源になるとされている。
このように、特許文献１〜３に記載されたリチウムイオン二次電池などでは、負極活物質の配向性の検討や、負極活物質としてのリチウムチタン酸化物の検討などにより、高容量化を図り、繰返充放電におけるサイクル特性を向上させていた。しかしながら、まだ十分でなく、サイクル特性及び負荷特性をより高めることが望まれていた。
As described above, in the lithium ion secondary batteries described in
本発明は、このような課題に鑑みなされたものであり、サイクル特性及び負荷特性をより高めることができるリチウムイオン二次電池用負極及びリチウムイオン二次電池を提供することを主目的とする。 This invention is made | formed in view of such a subject, and it aims at providing the negative electrode for lithium ion secondary batteries and lithium ion secondary battery which can improve cycling characteristics and load characteristics more.
上述した目的を達成するために鋭意研究したところ、本発明者らは、ラムスデライト構造を有するチタン化合物を含む負極活物質において、電極のＸ線回折測定を行ったときの各回折面のピーク面積を用いて求めた値Ｒintが所定の好適な範囲にあると、サイクル特性及び負荷特性をより高めることができることを見いだし、本発明を完成するに至った。 As a result of diligent research to achieve the above-described object, the present inventors have found that in a negative electrode active material containing a titanium compound having a ramsdellite structure, the peak area of each diffraction surface when X-ray diffraction measurement of the electrode is performed. It has been found that the cycle characteristic and the load characteristic can be further improved when the value R int obtained by using is within a predetermined preferable range, and the present invention has been completed.
即ち、本発明のリチウムイオン二次電池用負極は、
ラムスデライト型構造を有するチタン化合物を含む負極活物質を備え、電極のＸ線回折測定を行ったときの（１０１）面の回折ピークの面積をＩ（１０１）、（２００）面の回折ピークの面積をＩ（２００）、（２０１）面の回折ピークの面積をＩ（２０１）、（３０１）面の回折ピークの面積をＩ（３０１）とし回折ピークの面積強度比をＲint＝Ｉ（１０１）／［Ｉ（２００）＋Ｉ（２０１）＋Ｉ（３０１）］としたときに、Ｒint≧３．０を満たすものである。
That is, the negative electrode for a lithium ion secondary battery of the present invention is
A negative electrode active material containing a titanium compound having a ramsdellite structure is provided, and the area of the diffraction peak of the (101) plane when the X-ray diffraction measurement of the electrode is performed is the diffraction peak of the I (101) and (200) planes. The area of the diffraction peak of the (201) plane is I (201), the area of the diffraction peak of the (301) plane is I (301), and the area intensity ratio of the diffraction peaks is R int = I (101 ) / [I (200) + I (201) + I (301)], R int ≧ 3.0 is satisfied.
また、本発明のリチウムイオン二次電池は、
リチウムを吸蔵・放出可能な正極活物質を有する正極と、
上述のリチウムイオン二次電池用負極と、
前記正極と前記リチウムイオン二次電池用負極との間に介在しリチウムイオンを伝導するイオン伝導媒体と、
を備えたものである。
The lithium ion secondary battery of the present invention is
A positive electrode having a positive electrode active material capable of inserting and extracting lithium;
A negative electrode for a lithium ion secondary battery as described above;
An ion conduction medium that is interposed between the positive electrode and the negative electrode for a lithium ion secondary battery and conducts lithium ions;
It is equipped with.
このリチウムイオン二次電池用負極及びリチウムイオン二次電池では、サイクル特性及び負荷特性をより高めることができる。ここで、従来では電極内での活物質の配向は、例えばリチウムイオンのアクセスする方向が限定されるため望ましくないものとされているのに対し、本発明では電極内で活物質が（１０１）で配向することによりサイクル特性及び負荷特性を向上させることができる。このような効果が得られる理由は明らかではないが、以下のように推測される。例えば、ラムスデライト構造内では、リチウムイオンの通り道が一次元のトンネルとなっており、配向することにより電極内でこのトンネルがリチウムイオンの輸送に効果的に配列し、負荷特性が向上したものと考えられる。また、電極内で活物質が配向することにより充放電時の結晶構造の膨張・収縮が効果的に抑制されたため、サイクル特性が向上したものと推察される。なお、サイクル特性としては、繰り返し充放電を行ったときの放電容量の維持率としてもよい。また、負荷特性としては、低電流（例えば０．１Ｃ）による放電容量に対する高電流（例えば２Ｃ）による放電容量の比による評価としてもよい。 In the negative electrode for lithium ion secondary battery and the lithium ion secondary battery, cycle characteristics and load characteristics can be further improved. Here, the orientation of the active material in the electrode is conventionally undesirable because, for example, the access direction of lithium ions is limited, whereas in the present invention, the active material is (101) in the electrode. Cycle characteristics and load characteristics can be improved by orienting at. The reason why such an effect is obtained is not clear, but is presumed as follows. For example, in the ramsdellite structure, the path of lithium ions is a one-dimensional tunnel, and by aligning this tunnel, the tunnel is effectively arranged for transport of lithium ions in the electrode, and the load characteristics are improved. Conceivable. In addition, it is presumed that the cycle characteristics were improved because the expansion and contraction of the crystal structure during charge / discharge was effectively suppressed by the orientation of the active material in the electrode. The cycle characteristics may be the discharge capacity maintenance rate when repeated charge / discharge is performed. Further, the load characteristics may be evaluated by a ratio of a discharge capacity by a high current (for example, 2C) to a discharge capacity by a low current (for example, 0.1C).
本発明のリチウムイオン二次電池は、リチウムを吸蔵・放出可能な正極活物質を有する正極と、リチウムを吸蔵・放出可能な負極活物質を有する負極と、正極と負極との間に介在しリチウムイオンを伝導するイオン伝導媒体と、を備えている。 The lithium ion secondary battery of the present invention includes a positive electrode having a positive electrode active material capable of occluding and releasing lithium, a negative electrode having a negative electrode active material capable of occluding and releasing lithium, and a lithium ion interposed between the positive electrode and the negative electrode. An ion conduction medium that conducts ions.
本発明のリチウムイオン二次電池の正極は、例えば正極活物質に導電材及びバインダーを混合し、適当な溶剤を加えてペースト状の正極合材としたものを、正極集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成することができる。正極活物質としては、リチウムと遷移金属元素とを含む酸化物、又はポリアニオン系化合物を用いることができる。具体的には、例えばリチウムコバルト複合酸化物（Ｌｉ(1-n)ＣｏＯ2など（０＜ｎ＜１、以下同じ））、リチウムニッケル複合酸化物（Ｌｉ(1-n)ＮｉＯ2など）、リチウムマンガン複合酸化物（Ｌｉ(1-n)ＭｎＯ2、Ｌｉ(1-n)Ｍｎ2Ｏ4など）、リチウム鉄複合リン酸化物（ＬｉＦｅＰＯ4など）、リチウムバナジウム複合酸化物（ＬｉＶ2Ｏ3など）などが挙げられる。正極集電体としては、導電性材料で形成されたものであれば特に限定されないが、例えば、アルミニウムや銅、ステンレス鋼、ニッケルメッキ鋼などの金属で形成されている箔やメッシュを用いることができる。バインダーは、活物質粒子及び導電材粒子を繋ぎ止める役割を果たすものであり、例えばポリテトラフルオロエチレン、ポリフッ化ビニリデン、フッ素ゴムなどの含フッ素樹脂、或いはポリプロピレン、ポリエチレンなどの熱可塑性樹脂などを用いることができる。導電材は、正極の電気伝導性を確保するためのものであり、例えばカーボンブラック、アセチレンブラック、天然黒鉛、人造黒鉛、コークス類などの炭素物質粉末状体の１種又は２種以上を混合したものを用いることができる。正極活物質、導電材、バインダーを分散させる溶剤としては、例えばＮ−メチル−２−ピロリドンなどの有機溶剤を用いることができる。 The positive electrode of the lithium ion secondary battery of the present invention is, for example, obtained by mixing a positive electrode active material with a conductive material and a binder and adding a suitable solvent to form a paste-like positive electrode mixture on the surface of the positive electrode current collector. It can be dried and compressed to increase the electrode density as needed. As the positive electrode active material, an oxide containing lithium and a transition metal element or a polyanionic compound can be used. Specifically, for example, lithium cobalt composite oxide (Li (1-n) CoO 2 etc. (0 <n <1, the same applies hereinafter)), lithium nickel composite oxide (Li (1-n) NiO 2 etc.), Lithium manganese composite oxide (Li (1-n) MnO 2 , Li (1-n) Mn 2 O 4 etc.), lithium iron composite phosphorous oxide (LiFePO 4 etc.), lithium vanadium composite oxide (LiV 2 O 3) Etc.). The positive electrode current collector is not particularly limited as long as it is formed of a conductive material. For example, a foil or mesh formed of a metal such as aluminum, copper, stainless steel, or nickel-plated steel may be used. it can. The binder plays a role of connecting the active material particles and the conductive material particles. For example, a fluorine-containing resin such as polytetrafluoroethylene, polyvinylidene fluoride, or fluororubber, or a thermoplastic resin such as polypropylene or polyethylene is used. be able to. The conductive material is for ensuring the electrical conductivity of the positive electrode. For example, one or more of carbon powder materials such as carbon black, acetylene black, natural graphite, artificial graphite, and cokes are mixed. Things can be used. As the solvent for dispersing the positive electrode active material, the conductive material, and the binder, for example, an organic solvent such as N-methyl-2-pyrrolidone can be used.
本発明のリチウムイオン二次電池の負極は、例えば負極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の負極材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよい。本発明の負極は、ラムスデライト型構造を有するチタン化合物を含む負極活物質を備えている。このラムスデライト型構造を有するチタン化合物は、ＴｉＯ2、ＬｉＴｉ2Ｏ4及びＬｉ2Ｔｉ3Ｏ7（Ｌｉ1.14Ｔｉ1.71Ｏ4）のうち１以上の基本組成を有するものとしてもよい。なお、「基本組成」とは、負極活物質に他の元素などを含むものとしてもよい趣旨である。例えば、ラムスデライト型構造を有するチタン化合物は、ＴｉＯ2や一般式ＬｉxＡyＴｉzＯ4で表されるものとしてもよい。ここで、Ａは、遷移金属、周期律表の１族、２族及び３族元素のうち少なくとも１以上であり、０≦ｘ≦２、０≦ｙ≦１、１≦ｚ≦２を満たすものとする。このラムスデライト型構造を有するチタン化合物としては、例えば、ＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、Ｌｉ3Ｃｒ3Ｔｉ4Ｏ14などが挙げられる。この負極は、電極のＸ線回折測定を行ったときの（１０１）面の回折ピークの面積をＩ（１０１）、（２００）面の回折ピークの面積をＩ（２００）、（２０１）面の回折ピークの面積をＩ（２０１）、（３０１）面の回折ピークの面積をＩ（３０１）とし、回折ピークの面積強度比をＲint＝Ｉ（１０１）／［Ｉ（２００）＋Ｉ（２０１）＋Ｉ（３０１）］としたときに、Ｒint≧３．０を満たしている。ここで、電極のＲintが３．０以上というのは、ラムスデライト型構造を有するチタン化合物が、（１０１）面で配向していることを意味する。こうすれば、電極内で活物質が効果的に配向することにより、サイクル特性及び負荷特性をより高めることができる。これは、ラムスデライト構造による１次元トンネルがリチウム輸送に効果的に配列したり、充放電時の膨張・収縮が効果的に抑制されたりするためであると推察される。このＲint比は、４．０以上を満たしていることがより好ましい。また、Ｒint比は、１０以下であることが配向特性の限界からみて好ましい。また、この負極活物質は、その密度が２．０ｇ／ｃｍ3以上２．３ｇ／ｃｍ3以下であることが好ましい。活物質密度が２．０ｇ／ｃｍ3以上では活物質同士の接触がより高まり電池性能が向上し、２．３ｇ／ｃｍ3以下では、電極に空隙が十分あり電極内に電解液が行き渡りやすく、電池性能が向上しやすい。この範囲では、リチウムイオン二次電池のサイクル特性及び負荷特性をより高めることができる。
The negative electrode of the lithium ion secondary battery of the present invention is prepared by mixing a negative electrode active material, a conductive material, and a binder, and adding a suitable solvent to form a paste-like negative electrode material on the surface of the current collector. It may be formed by coating and drying, and compressing to increase the electrode density as necessary. The negative electrode of the present invention includes a negative electrode active material containing a titanium compound having a ramsdellite structure. The titanium compound having the ramsdellite structure may have one or more basic compositions of TiO 2 , LiTi 2 O 4 and Li 2 Ti 3 O 7 (Li 1.14 Ti 1.71 O 4 ). The “basic composition” means that the negative electrode active material may contain other elements. For example, the titanium compound having a ramsdellite type structure may be represented by TiO 2 or a general formula Li x A y Ti z O 4 . Here, A is at least one of transition metal,
また、負極に用いられる導電材、結着材、溶剤などは、それぞれ正極で例示したものを用いることができる。負極の集電体には、銅、ニッケル、ステンレス鋼、チタン、アルミニウム、焼成炭素、導電性高分子、導電性ガラス、Ａｌ−Ｃｄ合金などのほか、接着性、導電性及び耐還元性向上の目的で、例えば銅などの表面をカーボン、ニッケル、チタンや銀などで処理したものも用いることができる。これらについては、表面を酸化処理することも可能である。集電体の形状は、正極と同様のものを用いることができる。 In addition, as the conductive material, binder, solvent, and the like used for the negative electrode, those exemplified for the positive electrode can be used. The negative electrode current collector includes copper, nickel, stainless steel, titanium, aluminum, calcined carbon, conductive polymer, conductive glass, Al-Cd alloy, etc., as well as improved adhesion, conductivity and reduction resistance. For the purpose, for example, a copper surface treated with carbon, nickel, titanium, silver or the like can be used. For these, the surface can be oxidized. The shape of the current collector can be the same as that of the positive electrode.
本発明のリチウムイオン二次電池において、イオン伝導媒体は、支持塩を有機溶媒に溶かした非水電解液やイオン性液体、ゲル電解質、固体電解質などを用いることができる。このうち、非水電解液であることが好ましい。支持塩としては、例えば、ＬｉＰＦ6，ＬｉＣｌＯ4，ＬｉＡｓＦ6，ＬｉＢＦ4，Ｌｉ（ＣＦ3ＳＯ2）2Ｎ，Ｌｉ（ＣＦ3ＳＯ3），ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2などの公知の支持塩を用いることができる。支持塩の濃度としては、０．１〜２．０Ｍであることが好ましく、０．８〜１．２Ｍであることがより好ましい。有機溶媒としては、例えば、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、γ−ブチロラクトン（γ−ＢＬ）、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネート（ＤＭＣ）など従来の二次電池やキャパシタに使われる有機溶媒が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。また、イオン性液体としては、特に限定されるものではないが、１−メチル−３−プロピルイミダゾリウムビス（トリフルオロスルホニル）イミドや１−エチル−３−ブチルイミダゾリウムテトラフルオロボレートなどを用いることができる。ゲル電解質としては、特に限定されるものではないが、例えば、ポリフッ化ビニリデンやポリエチレングリコール、ポリアクリロニトリルなどの高分子類またはアミノ酸誘導体やソルビトール誘導体などの糖類に、支持塩を含む電解液を含ませてなるゲル電解質が挙げられる。固体電解質としては、無機固体電解質や有機固体電解質などが挙げられる。無機固体電解質としては、例えば、Ｌｉの窒化物、ハロゲン化物、酸素酸塩などがよく知られている。なかでも、Ｌｉ4ＳｉＯ4、Ｌｉ4ＳｉＯ4−ＬｉＩ−ＬｉＯＨ、ｘＬｉ3ＰＯ4−（１−ｘ)Ｌｉ4ＳｉＯ4、Ｌｉ2ＳｉＳ3、Ｌｉ3ＰＯ4−Ｌｉ2Ｓ−ＳｉＳ2、硫化リン化合物などが挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。有機固体電解質としては、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリビニルアルコール、ポリフッ化ビニリデン、ポリホスファゼン、ポリエチレンスルフィド、ポリヘキサフルオロプロピレンなどやこれらの誘導体が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。
In the lithium ion secondary battery of the present invention, the ion conduction medium may be a non-aqueous electrolyte solution, an ionic liquid, a gel electrolyte, a solid electrolyte, or the like in which a supporting salt is dissolved in an organic solvent. Of these, a non-aqueous electrolyte is preferable. Examples of the supporting salt include LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 3 ), and LiN (C 2 F 5 SO 2 ) 2. The supporting salt can be used. The concentration of the supporting salt is preferably 0.1 to 2.0M, and more preferably 0.8 to 1.2M. As an organic solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (γ-BL), diethyl carbonate (DEC), dimethyl carbonate (DMC) and the like are used for conventional secondary batteries and capacitors. An organic solvent is mentioned. These may be used alone or in combination. Further, the ionic liquid is not particularly limited, but 1-methyl-3-propylimidazolium bis (trifluorosulfonyl) imide, 1-ethyl-3-butylimidazolium tetrafluoroborate, or the like is used. Can do. The gel electrolyte is not particularly limited. For example, a polymer such as polyvinylidene fluoride, polyethylene glycol, or polyacrylonitrile, or a saccharide such as an amino acid derivative or sorbitol derivative is added with an electrolyte containing a supporting salt. And a gel electrolyte. Examples of the solid electrolyte include inorganic solid electrolytes and organic solid electrolytes. Well-known inorganic solid electrolytes include, for example, Li nitrides, halides, oxyacid salts, and the like. Among them, Li 4 SiO 4, Li 4 SiO 4 -LiI-LiOH,
本発明のリチウムイオン二次電池は、負極と正極との間にセパレータを備えていてもよい。セパレータとしては、リチウムイオン二次電池の使用範囲に耐えうる組成であれば特に限定されないが、例えば、ポリプロピレン製不織布やポリフェニレンスルフィド製不織布などの高分子不織布、ポリエチレンやポリプロピレンなどのオレフィン系樹脂の薄い微多孔膜が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。 The lithium ion secondary battery of the present invention may include a separator between the negative electrode and the positive electrode. The separator is not particularly limited as long as the composition can withstand the use range of the lithium ion secondary battery. For example, a polymer nonwoven fabric such as a polypropylene nonwoven fabric or a polyphenylene sulfide nonwoven fabric, or a thin olefin resin such as polyethylene or polypropylene is used. A microporous membrane is mentioned. These may be used alone or in combination.
本発明のリチウムイオン二次電池の形状は、特に限定されないが、例えばコイン型、ボタン型、シート型、積層型、円筒型、偏平型、角型などが挙げられる。また、電気自動車等に用いる大型のものなどに適用してもよい。このリチウムイオン二次電池の一例を図１に示す。図１は、コイン型電池２０の構成の概略を表す断面図である。このコイン型電池２０は、カップ形状の電池ケース２１と、正極活物質を有しこの電池ケース２１の下部に設けられた正極２２と、負極活物質を有し正極２２に対してセパレータ２４を介して対向する位置に設けられた負極２３と、絶縁材により形成されたガスケット２５と、電池ケース２１の開口部に配設されガスケット２５を介して電池ケース２１を密封する封口板２６と、を備えている。ここでは、負極２３は、ラムスデライト型構造を有するチタン化合物を負極活物質として備え、電極のＸ線回折によるＲint比が３．０以上を満たしている。
The shape of the lithium ion secondary battery of the present invention is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type. Moreover, you may apply to the large sized thing used for an electric vehicle etc. An example of this lithium ion secondary battery is shown in FIG. FIG. 1 is a cross-sectional view schematically showing the configuration of the coin-
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
以下には、リチウム電池を具体的に作製した例を、実施例として説明する。 Below, the example which produced the lithium battery concretely is demonstrated as an Example.
［ラムスデライト型チタン酸化物：ＴｉＯ2，ＬｉＴｉ2Ｏ4，Ｌｉ2Ｔｉ3Ｏ7］
ラムスデライト型ＬｉＴｉ2Ｏ4の合成では、出発原料として、Ｌｉ［Ｌｉ1/3Ｔｉ5/3］Ｏ4、ＴｉＯ2（和光純薬工業製、ルチル型）、Ｔｉ金属粉末（高純度化学研究所製）を用いた。このＬｉ［Ｌｉ1/3Ｔｉ5/3］Ｏ4は、ＬｉＯＨ・Ｈ2Ｏ（和光純薬工業製）とＴｉＯ2（和光純薬工業製、アナターゼ型）を所定のモル比で秤量、混合後、直径２ｃｍ、厚さ５ｍｍのペレットに３０ＭＰａで加圧成型し、窒素雰囲気下８００℃、１２時間焼成することにより合成した。次に、ＬｉＴｉ2Ｏ4，１ｍｏｌあたりＬｉ［Ｌｉ1/3Ｔｉ5/3］Ｏ4を０．７５ｍｏｌ、ＴｉＯ2を０．５ｍｏｌ、Ｔｉ金属粉末を０．２５ｍｏｌとなるように秤量し、これらを乳鉢で混合した。混合粉末を直径２ｃｍ、厚さ５ｍｍ程度のペレットに３０ＭＰａで加圧成型し、焼成時にこの成型体が空気酸化されるのを避けるよう作製したペレットを銅箔に包んだ。これをアルゴン雰囲気下１０００℃で１６時間焼成することによりラムスデライト型ＬｉＴｉ2Ｏ4を得た。また、ラムスデライト型ＴｉＯ2の合成では、この合成したＬｉＴｉ2Ｏ4を１Ｍ塩酸水溶液中に投入し３日間攪拌後、濾過し、８０℃で１２時間乾燥させることによりラムスデライト型ＴｉＯ2を得た。また、Ｌｉ2Ｔｉ3Ｏ7の合成では、出発原料としてＬｉ［Ｌｉ1/3Ｔｉ5/3］Ｏ4、ＴｉＯ2（ルチル型）、Ｔｉ金属粉末を用い、Ｌｉ2Ｔｉ3Ｏ7］１ｍｏｌあたりＬｉ［Ｌｉ1/3Ｔｉ5/3］Ｏ4を１．５ｍｏｌ、ＴｉＯ2を０．５ｍｏｌとなるように秤量し、ＬｉＴｉ2Ｏ4と同様の合成工程により混合・焼成することにより、ラムスデライト型Ｌｉ2Ｔｉ3Ｏ7を得た。
[Ramsdellite type titanium oxide: TiO 2, LiTi 2 O 4 ,
In the synthesis of ramsdellite type LiTi 2 O 4 , Li [Li 1/3 Ti 5/3 ] O 4 , TiO 2 (made by Wako Pure Chemical Industries, Rutile type), Ti metal powder (high purity chemical research) Used). This Li [Li 1/3 Ti 5/3 ] O 4 is prepared by weighing and mixing LiOH.H 2 O (manufactured by Wako Pure Chemical Industries) and TiO 2 (manufactured by Wako Pure Chemical Industries, anatase type) at a predetermined molar ratio. Then, it pressure-molded at 30 MPa to the pellet of diameter 2cm and thickness 5mm, and synthesize | combined by baking at 800 degreeC and 12 hours in nitrogen atmosphere. Next, Li [Li 1/3 Ti 5/3 ] O 4 per liter of LiTi 2 O 4 , 0.75 mol of TiO 2 , 0.5 mol of TiO 2 , and 0.25 mol of Ti metal powder were weighed, and these Were mixed in a mortar. The mixed powder was press-molded into a pellet having a diameter of about 2 cm and a thickness of about 5 mm at 30 MPa, and the pellet prepared so as to avoid air oxidation of the molded body during firing was wrapped in copper foil. This was calcined at 1000 ° C. for 16 hours in an argon atmosphere to obtain ramsdellite-type LiTi 2 O 4 . In the synthesis of ramsdellite TiO 2, the synthesized LiTi 2 O 4 was put into a 1M hydrochloric acid aqueous solution, stirred for 3 days, filtered, and dried at 80 ° C. for 12 hours to obtain ramsdellite TiO 2 . It was. In the synthesis of Li 2 Ti 3 O 7 , Li [Li 1/3 Ti 5/3 ] O 4 , TiO 2 (rutile type), Ti metal powder is used as a starting material, and Li 2 Ti 3 O 7 ] 1 mol By weighing Li [Li 1/3 Ti 5/3 ] O 4 at 1.5 mol and TiO 2 at 0.5 mol per unit, and mixing and firing by the same synthesis process as LiTi 2 O 4 , Delite type Li 2 Ti 3 O 7 was obtained.
［実施例１］
（塗工電極の作製）
ラムスデライト型ＴｉＯ2を８５重量％、導電材としてカーボンブラックを５重量％、結着材としてポリフッ化ビニリデンを１０重量％混合し、分散剤としてＮ−メチル−２−ピロリドンを適量添加し、スラリー状の合材とした。この合材スラリーを２０μｍ厚のアルミニウム箔集電体に均一に塗布し、加熱乾燥して塗布シートを作製した。シート中に含まれる活物質の密度が２．１ｇ／ｃｍ3となるように電極をプレス処理し、２．０５ｃｍ2の面積に打ち抜いて円盤状の電極を作製した。活物質密度の測定は、以下の手法により行った。まず、作成した円盤状の電極の重量から同面積のアルミニウム箔集電体の重量を差し引き、それに電極内での活物質の割合（８５重量％）を積算したものを活物質重量とした。次に、円盤状電極の厚さを測定し、そこからアルミニウム箔集電体の厚さ（２０μｍ）を差し引いたものを電極の厚さとした。この電極の厚さ及び面積から求めた体積で上記活物質重量を除算した値を活物質密度（ｇ／ｃｍ3）とした。
[Example 1]
(Preparation of coated electrode)
85% by weight of ramsdellite type TiO 2 , 5% by weight of carbon black as a conductive material, 10% by weight of polyvinylidene fluoride as a binder, and an appropriate amount of N-methyl-2-pyrrolidone as a dispersing agent is added to the slurry. In the form of a composite material. This mixed material slurry was uniformly applied to an aluminum foil current collector having a thickness of 20 μm and dried by heating to prepare a coated sheet. The electrode was pressed so that the density of the active material contained in the sheet was 2.1 g / cm 3, and punched out to an area of 2.05 cm 2 to produce a disk-shaped electrode. The active material density was measured by the following method. First, the weight of the aluminum foil current collector of the same area was subtracted from the weight of the prepared disc-shaped electrode, and the weight of the active material in the electrode (85% by weight) was integrated to obtain the active material weight. Next, the thickness of the disk-shaped electrode was measured, and the thickness obtained by subtracting the thickness of the aluminum foil current collector (20 μm) was taken as the electrode thickness. A value obtained by dividing the weight of the active material by the volume determined from the thickness and area of the electrode was defined as the active material density (g / cm 3 ).
（Ｘ線回折測定によるＲint比の算出）
この実施例１の電極をＸ線回折装置（リガク社製ＲＩＮＴ−２２００）を用いて測定した。測定条件は、Ｃｕ−Ｋα線により４０ｋＶ−３０ｍＡで１５°〜３０°までスキャンするものとした。実施例１のＸ線回折の測定結果を図２に示す。この測定結果を用いて、（１０１）面の回折ピークの面積をＩ（１０１）、（２００）面の回折ピークの面積をＩ（２００）、（２０１）面の回折ピークの面積をＩ（２０１）、（３０１）面の回折ピークの面積をＩ（３０１）とし、回折ピークの面積強度比をＲint＝Ｉ（１０１）／［Ｉ（２００）＋Ｉ（２０１）＋Ｉ（３０１）］として求めた。この結果、実施例１のＲintは、４．５であった。なお、このＸ線回折測定及びＲint比の算出は、後述する実施例２〜１０、比較例１〜１０の電極についても同様に行った。
(Calculation of R int ratio by X-ray diffraction measurement)
The electrode of Example 1 was measured using an X-ray diffractometer (RINT-2200 manufactured by Rigaku Corporation). Measurement conditions were set to scan from 15 ° to 30 ° at 40 kV-30 mA with Cu-Kα rays. The measurement result of the X-ray diffraction of Example 1 is shown in FIG. Using this measurement result, the area of the diffraction peak of the (101) plane is I (101), the area of the diffraction peak of the (200) plane is I (200), and the area of the diffraction peak of the (201) plane is I (201). ), The area of the diffraction peak of the (301) plane was defined as I (301), and the area intensity ratio of the diffraction peak was determined as R int = I (101) / [I (200) + I (201) + I (301)]. . As a result, R int of Example 1 was 4.5. The X-ray diffraction measurement and the calculation of the R int ratio were similarly performed for the electrodes of Examples 2 to 10 and Comparative Examples 1 to 10 described later.
（二極式評価セルの作製）
エチレンカーボネートとジエチルカーボネートとを体積比で３：７となるように混合した混合溶媒に、ＬｉＰＦ6を１ｍｏｌ／Ｌの濃度で溶解した非水電解液（イオン伝導媒体）を作製した。上記実施例１の電極を作用極とし、リチウム金属箔（厚さ３００μｍ）を対極として、両電極の間に、上記非水電解液を含浸させたセパレータ（東燃タピルス）を挟んで作製した二極式評価セルを実施例１の評価セルとした。
(Preparation of bipolar evaluation cell)
A non-aqueous electrolyte solution (ion conductive medium) was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 3: 7. A bipolar electrode prepared using the electrode of Example 1 as a working electrode, a lithium metal foil (thickness: 300 μm) as a counter electrode, and sandwiching a separator (Tonen Tapils) impregnated with the non-aqueous electrolyte between both electrodes. The formula evaluation cell was used as the evaluation cell of Example 1.
（充放電試験）
作製した実施例１の二極式評価セルを用い、０．１Ｃ（０．３ｍＡ）で１．０Ｖまで還元（充電）したのち、０．１Ｃ（０．３ｍＡ）で３．０Ｖまで酸化（放電）させた。この充放電操作を３回繰り返して放電状態にしたものを初期状態とした。次に、２０℃の温度環境下で、初期状態の二極式評価セルを０．１Ｃ（０．３ｍＡ）で充電させ、０．１Ｃ（０．３ｍＡ）で放電させたときの放電容量Ｑ(0.1C)に対する２Ｃ（６．０ｍＡ）での放電容量Ｑ(2C)の割合Ｒrate（％）＝［（Ｑ(2C)／Ｑ(0.1C)）×１００］を負荷特性の指標とした。その後、０．２Ｃ（０．６ｍＡ）で５０サイクル充放電を行い、初期状態の放電容量Ｑ1(0.1C)に対する５０サイクル後の０．１Ｃ（０．３ｍＡ）での放電容量Ｑ50(0.1c)の割合Ｒcyc（％）＝［（Ｑ50(0.1c)／Ｑ1(0.1C)）×１００］を用いてサイクル特性を評価した。
(Charge / discharge test)
Using the prepared bipolar evaluation cell of Example 1, after reducing (charging) to 0.1 V at 0.1 C (0.3 mA), oxidation (discharging) to 3.0 V at 0.1 C (0.3 mA) ) This charging / discharging operation was repeated three times to obtain a discharged state as an initial state. Next, under a temperature environment of 20 ° C., the discharge capacity Q (2 ) when the bipolar evaluation cell in the initial state is charged at 0.1 C (0.3 mA) and discharged at 0.1 C (0.3 mA). 2C for 0.1 C) and (ratio R rate of discharge capacity at 6.0mA) Q (2C) (% ) = [(Q (2C) / Q (0.1C)) × 100] was used as an index of the load characteristics. Thereafter, 50 cycles of charge and discharge are performed at 0.2 C (0.6 mA), and the discharge capacity Q 50 (0.1 mA) at 0.1 C (0.3 mA) after 50 cycles with respect to the discharge capacity Q 1 (0.1 C) in the initial state. The cycle characteristics were evaluated using the ratio R cyc (%) = [(Q 50 (0.1c) / Q 1 ( 0.1C ) ) × 100] of c) .
［実施例２］
実施例１で作製した塗工電極の代わりに以下に示す方法で作製した圧粉電極を用いた以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例２とした。圧粉電極の作製は、ラムスデライト型ＴｉＯ2を７５重量％、導電材としてカーボンブラックを１５重量％、結着材としてポリフッ化ビニリデンを１０重量％混合し、分散剤としてＮ−メチル−２−ピロリドンを適量添加し、スラリー状の合材とした。この合材スラリーをガラス板上に滴下させ、１２０℃で減圧乾燥して混合粉末を作製し、それを加圧成型して面積２．０５ｃｍ2の圧粉電極を作製した。このとき、Ｒint比が３．１、成型体内に含まれる活物質の密度が２．１ｇ／ｃｍ3となるように圧粉電極の成型圧力を調整した。
[Example 2]
Example 2 shows an electrode and a bipolar evaluation cell obtained through the same steps as in Example 1 except that a dust electrode produced by the method shown below was used instead of the coated electrode produced in Example 1. It was. Preparation of the powder electrode a
［比較例１，２］
実施例２で作製した圧粉電極のＲint比が２．９、活物質の密度が２．１ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例２と同様の工程を経て得られた電極及び二極式評価セルを比較例１とした。また、圧粉電極のＲint比が２．１、活物質の密度が２．０ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例２と同様の工程を経て得られた電極及び二極式評価セルを比較例２とした。
[Comparative Examples 1 and 2]
Obtained through the same steps except that R int ratio of the produced powder electrodes 2.9, density of the active material was adjusted molding pressure so that 2.1 g / cm 3 and Example 2 in Example 2 The obtained electrode and bipolar evaluation cell were designated as Comparative Example 1. Also, R int ratio of the powder electrode 2.1, density of 2.0 g / cm 3 and so as to except that the molding pressure was adjusted electrodes obtained through the same process as in Example 2 and the active material The bipolar evaluation cell was designated as Comparative Example 2.
ラムスデライト型ＴｉＯ2を用い、Ｒint比を検討した実施例１，２及び比較例１，２の電極形成方法、Ｒint比、活物質密度、負荷特性Ｒrate、サイクル特性Ｒcycをまとめて表１に示す。図３は、Ｒint比に対する負荷特性Ｒrate及びサイクル特性Ｒcycの関係を表す図である。表１及び図３に示すように、ラムスデライト型ＴｉＯ2電極は、Ｒint比が３を境に負荷特性、サイクル特性が屈曲的に変化することが明らかとなった。このＲint比が３以上であるラムスデライト型ＴｉＯ2電極は、負荷特性、サイクル特性共に優れていることがわかった。なお、活物質密度が２．１ｇ／ｃｍ3以外であっても、この傾向を示すものと類推される。最もＲint比が大きい４．５を示す実施例１の場合、特にその特性が高かった。圧粉電極ではＲint比を調整するために導電材を１５重量％としているのに対し、塗工電極では５重量％である。通常であれば導電材が少ないと導電性が低く、電池性能も低くなるが、この塗工電極では、導電材を減らしているにもかかわらず導電性の高い圧粉電極よりも負荷特性、サイクル特性が優れており、ラムスデライト型ＴｉＯ2の配向の効果が顕著に表れていることがわかった。 The electrode formation method, R int ratio, active material density, load characteristic R rate , and cycle characteristic R cyc of Examples 1 and 2 and Comparative Examples 1 and 2 in which R int ratio was examined using rams delite type TiO 2 were summarized. Table 1 shows. FIG. 3 is a diagram illustrating the relationship between the load characteristic R rate and the cycle characteristic R cyc with respect to the R int ratio. As shown in Table 1 and FIG. 3, it became clear that the load characteristics and the cycle characteristics of the ramsdellite type TiO 2 electrode change flexibly with an R int ratio of 3. It was found that the Ramsdelite type TiO 2 electrode having an R int ratio of 3 or more is excellent in both load characteristics and cycle characteristics. It is assumed that even if the active material density is other than 2.1 g / cm 3 , this tendency is shown. In the case of Example 1 showing 4.5 with the largest R int ratio, the characteristics were particularly high. In the dust electrode, the conductive material is 15% by weight in order to adjust the R int ratio, whereas in the coated electrode, it is 5% by weight. Usually, if there is little conductive material, the conductivity will be low and the battery performance will be low, but with this coated electrode, even though the conductive material is reduced, the load characteristics and cycle are higher than the highly conductive powder electrode It was found that the characteristics were excellent and the effect of orientation of the ramsdellite type TiO 2 appeared remarkably.
［実施例３，４］
塗工電極の活物質の密度が２．０ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例３とした。なお、実施例３のＲint比は４．３であった。また、塗工電極の活物質の密度が２．３ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例４とした。なお、実施例４のＲint比は４．６であった。
[Examples 3 and 4]
An electrode and a bipolar evaluation cell obtained through the same steps as in Example 1 except that the molding pressure was adjusted so that the density of the active material of the coated electrode was 2.0 g / cm 3 were the same as in Example 3. did. The R int ratio of Example 3 was 4.3. Further, an electrode and a bipolar evaluation cell obtained through the same steps as in Example 1 except that the molding pressure was adjusted so that the density of the active material of the coated electrode was 2.3 g / cm 3 It was set to 4. The R int ratio of Example 4 was 4.6.
［比較例３，４］
塗工電極の活物質の密度が１．９ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを比較例３とした。なお、比較例３のＲint比は４．３であった。また、塗工電極の活物質の密度が２．４ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを比較例４とした。なお、比較例４のＲint比は４．６であった。
[Comparative Examples 3 and 4]
The electrode and bipolar evaluation cell obtained through the same steps as in Example 1 except that the molding pressure was adjusted so that the density of the active material of the coated electrode was 1.9 g / cm 3 were compared with those in Comparative Example 3. did. The R int ratio of Comparative Example 3 was 4.3. Moreover, the electrode and bipolar evaluation cell which were obtained through the process similar to Example 1 except having adjusted the shaping | molding pressure so that the density of the active material of a coating electrode might be 2.4 g / cm < 3 > are comparative examples. It was set to 4. The R int ratio of Comparative Example 4 was 4.6.
ラムスデライト型ＴｉＯ2を用い、活物質密度を検討した実施例１，３，４及び比較例３，４の電極形成方法、Ｒint比、活物質密度、負荷特性Ｒrate、サイクル特性Ｒcycをまとめて表２に示す。ここでは、Ｒint比が３を大きく上回る塗工電極において活物質密度を種々変化させたときの負荷特性及びサイクル特性を示した。電極内の活物質密度が２．０ｇ／ｃｍ3以上２．３ｇ／ｃｍ3以下の範囲に含まれるときに特に負荷特性、サイクル特性が優れていることがわかった。 The electrode forming method, R int ratio, active material density, load characteristic R rate , and cycle characteristic R cyc in Examples 1, 3, and 4 and Comparative Examples 3 and 4 in which the active material density was examined using rams delite type TiO 2 These are summarized in Table 2. Here, the load characteristic and the cycle characteristic when the active material density is variously changed in the coated electrode having a R int ratio greatly exceeding 3 are shown. It was found that when the active material density in the electrode is in the range of 2.0 g / cm 3 or more and 2.3 g / cm 3 or less, the load characteristics and the cycle characteristics are particularly excellent.
［実施例５〜７］
実施例２で作製した圧粉電極の負極活物質をラムスデライト型ＬｉＴｉ2Ｏ4とし、Ｒint比を３．１とし、活物質密度を２．１ｇ／ｃｍ3とした以外は実施例２と同様の工程を経て得られた電極及び二極式評価セルを実施例５とした。また、実施例１で作製した塗工電極の活物質をラムスデライト型ＬｉＴｉ2Ｏ4とし、活物質密度が２．０ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例６とした。なお、実施例６のＲint比は４．４であった。また、塗工電極の活物質をラムスデライト型ＬｉＴｉ2Ｏ4とし、活物質密度が２．３ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例７とした。なお、実施例７のＲint比は４．５であった。
[Examples 5 to 7]
Example 2 except that the negative electrode active material of the compacted electrode prepared in Example 2 was Ramsdelite type LiTi 2 O 4 , the R int ratio was 3.1, and the active material density was 2.1 g / cm 3. An electrode and a bipolar evaluation cell obtained through the same steps were taken as Example 5. Further, except that the active material of the coating electrode prepared in Example 1 and ramsdellite LiTi 2 O 4, the active material density was adjusted molded pressure so that 2.0 g / cm 3 as in Example 1 An electrode and a bipolar evaluation cell obtained through the steps were designated as Example 6. The R int ratio of Example 6 was 4.4. Moreover, it obtained through the process similar to Example 1 except having made the active material of the coating electrode into ramsdellite type LiTi 2 O 4 and adjusting the molding pressure so that the active material density was 2.3 g / cm 3. The electrode and the bipolar evaluation cell were designated as Example 7. The R int ratio of Example 7 was 4.5.
［比較例５〜７］
実施例５で作製した圧粉電極のＲint比を２．９とし、活物質密度を２．１ｇ／ｃｍ3とした以外は実施例５と同様の工程を経て得られた電極及び二極式評価セルを比較例５とした。また、実施例６で作製した塗工電極の活物質の密度が１．９ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例６と同様の工程を経て得られた電極及び二極式評価セルを比較例６とした。なお、比較例６のＲint比は４．４であった。また、塗工電極の活物質密度が２．４ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例７と同様の工程を経て得られた電極及び二極式評価セルを比較例７とした。なお、比較例７のＲint比は４．５であった。
[Comparative Examples 5 to 7]
The R int ratio of the powder electrode prepared in Example 5 and 2.9, the active material density 2.1 g / cm 3 and with other than the can obtained by the same process as in Example 5 electrodes and bipolar The evaluation cell was designated as Comparative Example 5. Further, an electrode and a bipolar electrode obtained through the same steps as in Example 6 except that the molding pressure was adjusted so that the density of the active material of the coated electrode produced in Example 6 was 1.9 g / cm 3. The formula evaluation cell was designated as Comparative Example 6. The R int ratio of Comparative Example 6 was 4.4. Moreover, the electrode and bipolar evaluation cell which were obtained through the process similar to Example 7 except having adjusted the shaping | molding pressure so that the active material density of a coating electrode might be 2.4 g / cm < 3 > were compared with Comparative Example 7. It was. The R int ratio of Comparative Example 7 was 4.5.
ラムスデライト型ＬｉＴｉ2Ｏ4を用いた評価結果を表３に示す。表３の実施例５及び比較例５に示すように、Ｒint比が３以上で、負荷特性及びサイクル特性が優れていることがわかった。また、実施例６，７及び比較例６，７に示すように、電極内の活物質密度が２．０ｇ／ｃｍ3以上２．３ｇ／ｃｍ3以下の範囲に含まれるときに特に負荷特性、サイクル特性が優れていることがわかった。 Table 3 shows the evaluation results using ramsdellite type LiTi 2 O 4 . As shown in Example 5 and Comparative Example 5 in Table 3, it was found that the Rint ratio was 3 or more and the load characteristics and cycle characteristics were excellent. Further, as shown in Examples 6 and 7 and Comparative Examples 6 and 7, particularly when the active material density in the electrode is included in a range of 2.0 g / cm 3 or more and 2.3 g / cm 3 or less, load characteristics, It was found that the cycle characteristics were excellent.
［実施例８〜１０］
実施例２で作製した圧粉電極の負極活物質をラムスデライト型Ｌｉ2Ｔｉ3Ｏ7とし、Ｒint比を３．１とし、活物質密度を２．１ｇ／ｃｍ3とした以外は実施例２と同様の工程を経て得られた電極及び二極式評価セルを実施例８とした。また、実施例１で作製した塗工電極の活物質をラムスデライト型Ｌｉ2Ｔｉ3Ｏ7とし、活物質密度が２．０ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例９とした。なお、実施例９のＲint比は４．６であった。また、塗工電極の活物質をラムスデライト型Ｌｉ2Ｔｉ3Ｏ7とし、活物質密度が２．３ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１と同様の工程を経て得られた電極及び二極式評価セルを実施例１０とした。なお、実施例１０のＲint比は４．７であった。
[Examples 8 to 10]
Example except that the negative electrode active material of the dust electrode produced in Example 2 was Ramsdelite type Li 2 Ti 3 O 7 , the R int ratio was 3.1, and the active material density was 2.1 g / cm 3. An electrode and a bipolar evaluation cell obtained through the same steps as in Example 2 were referred to as Example 8. Example 1 except that the active material of the coated electrode produced in Example 1 was Ramsdelite type Li 2 Ti 3 O 7 and the molding pressure was adjusted so that the active material density was 2.0 g / cm 3. An electrode and a bipolar evaluation cell obtained through the same steps as in Example 9 were designated as Example 9. The R int ratio of Example 9 was 4.6. Further, the same process as in Example 1 was performed except that the active material of the coating electrode was ramsdellite-type Li 2 Ti 3 O 7 and the molding pressure was adjusted so that the active material density was 2.3 g / cm 3. The obtained electrode and bipolar evaluation cell were determined as Example 10. The R int ratio of Example 10 was 4.7.
［比較例８〜１０］
実施例８で作製した圧粉電極のＲint比を２．９とし、活物質密度を２．１ｇ／ｃｍ3とした以外は実施例８と同様の工程を経て得られた電極及び二極式評価セルを比較例８とした。また、実施例９で作製した塗工電極の活物質の密度が１．９ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例９と同様の工程を経て得られた電極及び二極式評価セルを比較例９とした。なお、比較例９のＲint比は４．６であった。また、塗工電極の活物質密度が２．４ｇ／ｃｍ3となるように成型圧力を調整した以外は実施例１０と同様の工程を経て得られた電極及び二極式評価セルを比較例１０とした。なお、比較例１０のＲint比は４．７であった。
[Comparative Examples 8 to 10]
The R int ratio of the powder electrode prepared in Example 8 and 2.9, the active material density 2.1 g / cm 3 and with other than the can obtained by the same process as in Example 8 electrodes and bipolar The evaluation cell was Comparative Example 8. Further, an electrode and a bipolar electrode obtained through the same steps as in Example 9 except that the molding pressure was adjusted so that the density of the active material of the coated electrode produced in Example 9 was 1.9 g / cm 3. The formula evaluation cell was designated as Comparative Example 9. The R int ratio of Comparative Example 9 was 4.6. Moreover, the electrode and bipolar evaluation cell which were obtained through the process similar to Example 10 except having adjusted the shaping | molding pressure so that the active material density of a coating electrode might be 2.4 g / cm < 3 > were compared with Comparative Example 10. It was. The R int ratio of Comparative Example 10 was 4.7.
ラムスデライト型Ｌｉ2Ｔｉ3Ｏ7を用いた評価結果を表４に示す。表４の実施例８及び比較例８に示すように、Ｒint比が３を上回ると、負荷特性及びサイクル特性が優れていることがわかった。また、実施例９，１０及び比較例９，１０に示すように、電極内の活物質密度が２．０ｇ／ｃｍ3以上２．３ｇ／ｃｍ3以下の範囲に含まれるときに特に負荷特性、サイクル特性が優れていることがわかった。 Table 4 shows the results of evaluation using ramsdellite type Li 2 Ti 3 O 7 . As shown in Example 8 and Comparative Example 8 in Table 4, it was found that when the R int ratio exceeded 3, load characteristics and cycle characteristics were excellent. Further, as shown in Examples 9 and 10 and Comparative Examples 9 and 10, particularly when the active material density in the electrode is included in the range of 2.0 g / cm 3 or more and 2.3 g / cm 3 or less, It was found that the cycle characteristics were excellent.
２０ コイン型電池、２１ 電池ケース、２２ 正極、２３ 負極、２４ セパレータ、２５ ガスケット、２６ 封口板。 20 coin-type battery, 21 battery case, 22 positive electrode, 23 negative electrode, 24 separator, 25 gasket, 26 sealing plate.
Claims (2)
１０１）／［Ｉ（２００）＋Ｉ（２０１）＋Ｉ（３０１）］としたときに、Ｒint≧３．
０を満たし、
前記負極活物質は、ＴｉＯ2及びＬｉＴｉ2Ｏ4のうち１以上の基本組成を有する前記チ
タン化合物を含んでおり、
電極に含まれる前記負極活物質の密度が２．１ｇ／ｃｍ3以上２．３ｇ／ｃｍ 3 以下である、
リチウムイオン二次電池用負極。 A negative electrode active material containing a titanium compound having a ramsdellite structure is provided, and the area of the diffraction peak of the (101) plane when the X-ray diffraction measurement of the electrode is performed is the diffraction peak of the I (101) and (200) planes. The area of the diffraction peak on the (201) plane is I (201), the area of the diffraction peak on the (301) plane is I (301), and the area intensity ratio of the diffraction peaks is R int = I (
101) / [I (200) + I (201) + I (301)], R int ≧ 3.
Meets 0,
The negative electrode active material includes the titanium compound having one or more basic compositions of TiO 2 and LiTi 2 O 4 ,
The density of the negative electrode active material contained in the electrode is 2.1 g / cm 3 or more and 2.3 g / cm 3 or less .
Negative electrode for lithium ion secondary battery.
請求項１に記載のリチウムイオン二次電池用負極と、
前記正極と前記リチウムイオン二次電池用負極との間に介在しリチウムイオンを伝導するイオン伝導媒体と、
を備えたリチウムイオン二次電池。 A positive electrode having a positive electrode active material capable of inserting and extracting lithium;
A negative electrode for a lithium ion secondary battery according to claim 1 ;
An ion conduction medium that is interposed between the positive electrode and the negative electrode for a lithium ion secondary battery and conducts lithium ions;
Lithium ion secondary battery equipped with.
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