JP3985104B2 - Lithium battery and its active material - Google Patents
Lithium battery and its active material Download PDFInfo
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- JP3985104B2 JP3985104B2 JP10653897A JP10653897A JP3985104B2 JP 3985104 B2 JP3985104 B2 JP 3985104B2 JP 10653897 A JP10653897 A JP 10653897A JP 10653897 A JP10653897 A JP 10653897A JP 3985104 B2 JP3985104 B2 JP 3985104B2
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- active material
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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
Description
【発明の属する技術分野】
本発明は、リチウム電池用活物質およびリチウム電池に関する。
【従来の技術】
これまでのところ、酸化チタンのスピネル相だけが電気化学的に活性を示すことが判っている。「Ｊ．Ｅｌｅｃｔｏｃｈｅｍ．Ｓｏｃ．１４２，１４３１（１９９５年）」。式Ｌｉ（Ｌｉ1/3Ｔｉ5/3）Ｏ4で表されるこの物質は、空間群Ｆｄ３ｍに属する欠陥スピネル型骨格構造を呈し、単位格子パラメータはａ＝８．３５Åである。この物質は、歪みのない挿入反応によってＬｉ2（Ｌｉ1/3Ｔｉ5/3）０4へ変化し、その結果、より良好な繰り返し可逆性を示すようになることが判っている。
【発明が解決しようとする課題】
本発明は、リチウムを吸蔵できる新規な活物質およびそれを使用したリチウム二次電池を提供することである。
【課題を解決するための手段】
本発明は、ラムスデライト型構造を有する式Ｌｉ1+XＴｉ2-2XＯ4（０≦Ｘ≦０．５）で示されることを特徴とするリチウム二次電池用活物質であり、正極または負極のいずれか一方あるいは両方の活物質に用いたことを特徴としたリチウム電池とすることである。
【発明の実施の形態】
本発明によれば、Ｌｉ1+XＴｉ2-2XＯ4（０≦Ｘ≦０．５）で示される物質はラムスデライト型構造を呈し、ＴｉＯ6型八面体構造を含むとともに、該八面体構造は稜を共有することにより互いに結合して無限二重鎖を形成する。これらの二重鎖は、隣接する鎖とそれらの頂点で連結して三次元骨格を形成することによって、隣接する二重鎖間にリチウムイオンを吸蔵出来る空の（２×１）トンネルを構築する。
【実施例】
次に、本発明を実施例及び図面を参照して説明するが本発明はこれらの例によって制限をうけるものではない。
本発明のＬｉ1+XＴｉ2-2XＯ4（０≦Ｘ≦０．５）をＬｉ4Ｔｉ5Ｏ12、ＴｉＯ2、および金属Ｔｉが関与する２段階反応によって調整した。第一段階では、最初にＬｉ2ＣＯ3とＴｉＯ2とを混合し、その混合物を７００℃の温度で焼成してＣＯ2除去することによってＬｉ4Ｔｉ5Ｏ12を調整した。次に、得られた混合物を２〜３トンでペレット化し、９２０℃において４日間再度焼成してスピネル型のＬｉ4Ｔｉ5Ｏ12を形成させた。続いて、Ｌｉ4Ｔｉ5Ｏ12、、ＴｉＯ2および金属Ｔｉを使用してスピネル型のＬｉＴｉＯ2を調整した。この混合物をペレット化し、８４０℃において５％水素含有アルゴン下で焼成した。得られたスピネル相のＬｉＴｉ2Ｏ4を真空下かつ温度範囲８００〜１０００℃において加熱し、ラムスデライト相のＬｉＴｉ2Ｏ4を得た。
図１は、本発明に従って得られた物質のＸ線回折パターンを示している。本発明のＬｉＴｉ2Ｏ4のＸ線回折は、単位胞パラメータａ＝５．０３±０．２Å、ｂ＝９．６２±０．２Å、およびｃ＝２．９５±０．２Å、ならびに空間群の斜方晶系ラムスデライト型構造に帰属することを示していると言える。この場合、この構造をγＭｎＯ2で報告された構造と類似の図２に示すトンネル型構造とみなすことができる。
この構造はＴｉＯ6型八面体構造を含むとともに、該八面体構造は稜を共有することにより互いに結合して無限二重鎖を形成する。これらの二重鎖は、隣接する鎖とそれらのの頂点で連結して三次元骨格を形成することによって、隣接する二重鎖間にリチウムイオンを可逆的に吸蔵できる空の（２×１）トンネルを構築する。
図３は、本発明の物質の最初のサイクルの充放電を示している。この試験は、電解液としてＬｉＣｌＯ4＋（２ＥＣ＋２ＤＭＣ＋ＤＥＣ）を使用するタイプのガラス電池で電流密度０．２５ｍＡ／ｃ〓において実施した。この電池は、負極（８７％の本発明の活物質、５％カーボンブラック、８％ＰＶＤＦ）と、リチウム対電極と、リチウム照合電極とを備えている。最初に、この電池を充電して本発明の物質のトンネルからリチウムを放出させ、次に放電させてリチウムイオンをトンネル内へ吸蔵させた。
この電池は２Ｖと１Ｖとの間で単調な電位の変化を呈することから、充放電中、均一１相反応を起こすことが示唆される。中間電位は約１．３Ｖで、容量は１８０ｍＡｈ／ｇを超える。この物質は、図４サイクリックボルタンモグラム曲線に示されるように、１．５Ｖを超える電位においても酸化−還元ピークを呈する。
【発明の効果】
本発明は、１８０ｍＡｈ／ｇにも上る大容量を有するリチウムイオン電池の正極または負極活物質として使用可能な新しい酸化チタンを基材とする活物質を提供する。この物質は可逆的にリチウムを吸蔵しうる大きな２×１チャンネルを呈するラムスデライト型構造を有するために、繰り返し可逆性が良く、しかも放電率が高いリチウム二次電池の活物質としての有用性が極めて高いものである。
【図面の簡単な説明】
【図１】本発明のリチウム電池用活物質のＸ線回折パターンを示す図である。
【図２】本発明のリチウム電池用活物質のトンネル型ラムスデライト構造を表す図である。
【図３】リチウム対電極と、リチウム照合電極と、本発明の活物質から作られる電極とから成る電池の最初のサイクルの充放電曲線を示す図である。この場合には、活物質を負極として使用し、最初に充電してリチウムイオンを吸蔵させ、次に放電させてリチウムを放出させた。
【図４】本発明のリチウム電池用活物質のサイクリックボルタンモグラムを示す図である。（走査速度は３ｍＶ／分であった。）BACKGROUND OF THE INVENTION
The present invention relates to an active material for a lithium battery and a lithium battery.
[Prior art]
So far, it has been found that only the spinel phase of titanium oxide is electrochemically active. “J. Electrochem. Soc. 142, 1431 (1995)”. This material represented by the formula Li (Li 1/3 Ti 5/3 ) O 4 exhibits a defect spinel skeleton structure belonging to the space group Fd3m, and the unit cell parameter is a = 8.35Å. This material has been found to change to Li 2 (Li 1/3 Ti 5/3 ) 0 4 by an unstrained insertion reaction, resulting in better repeatable reversibility.
[Problems to be solved by the invention]
The present invention is to provide a novel active material capable of occluding lithium and a lithium secondary battery using the same.
[Means for Solving the Problems]
The present invention is an active material for a lithium secondary battery characterized by being represented by the formula Li 1 + X Ti 2-2X O 4 (0 ≦ X ≦ 0.5) having a ramsdellite structure, The lithium battery is characterized in that it is used for either or both of the negative electrode active materials.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, the substance represented by Li 1 + X Ti 2-2X O 4 (0 ≦ X ≦ 0.5) exhibits a ramsdellite type structure, includes a TiO 6 type octahedral structure, and the octahedron The structures are joined together by sharing an edge to form an infinite duplex. These duplexes connect to adjacent chains at their vertices to form a three-dimensional skeleton, thereby constructing an empty (2 × 1) tunnel that can occlude lithium ions between adjacent duplexes. .
【Example】
Next, the present invention will be described with reference to examples and drawings, but the present invention is not limited by these examples.
Li 1 + X Ti 2-2X O 4 (0 ≦ X ≦ 0.5) of the present invention was prepared by a two-stage reaction involving Li 4 Ti 5 O 12 , TiO 2 , and metal Ti. In the first stage, Li 4 Ti 5 O 12 was prepared by first mixing Li 2 CO 3 and TiO 2 and firing the mixture at a temperature of 700 ° C. to remove CO 2 . Next, the obtained mixture was pelletized at 2 to 3 tons and fired again at 920 ° C. for 4 days to form spinel type Li 4 Ti 5 O 12 . Subsequently, spinel-type LiTiO 2 was prepared using Li 4 Ti 5 O 12, TiO 2 and metal Ti. The mixture was pelletized and fired at 840 ° C. under 5% hydrogen containing argon. The obtained spinel phase LiTi 2 O 4 was heated in a vacuum at a temperature range of 800 to 1000 ° C. to obtain a ramsdellite phase LiTi 2 O 4 .
FIG. 1 shows the X-ray diffraction pattern of the material obtained according to the invention. The X-ray diffraction of the LiTi 2 O 4 of the present invention shows that the unit cell parameters a = 5.03 ± 0.2Å, b = 9.62 ± 0.2Å, and c = 2.95 ± 0.2Å, and the space group It can be said that it belongs to the orthorhombic ramsdellite type structure. In this case, this structure can be regarded as the tunnel type structure shown in FIG. 2 similar to the structure reported for γMnO 2 .
This structure includes a TiO 6 type octahedral structure, and the octahedral structure is bonded to each other by sharing an edge to form an infinite double chain. These duplexes are empty (2 × 1) that can reversibly occlude lithium ions between adjacent duplexes by linking adjacent strands at their vertices to form a three-dimensional skeleton. Build a tunnel.
FIG. 3 shows the charge and discharge of the first cycle of the material of the invention. This test was carried out at a current density of 0.25 mA / c〓 with a glass battery of the type using LiClO 4 + (2EC + 2DMC + DEC) as the electrolyte. This battery includes a negative electrode (87% of the active material of the present invention, 5% carbon black, 8% PVDF), a lithium counter electrode, and a lithium reference electrode. First, the battery was charged to release lithium from the tunnel of the material of the invention and then discharged to occlude lithium ions into the tunnel.
This battery exhibits a monotonous change in potential between 2 V and 1 V, suggesting that it causes a uniform one-phase reaction during charge and discharge. The intermediate potential is about 1.3 V, and the capacity exceeds 180 mAh / g. This material exhibits an oxidation-reduction peak even at potentials above 1.5 V, as shown in the cyclic voltammogram curve of FIG.
【The invention's effect】
The present invention provides a new titanium oxide-based active material that can be used as a positive electrode or negative electrode active material of a lithium ion battery having a large capacity up to 180 mAh / g. Since this material has a ramsdellite structure exhibiting a large 2 × 1 channel capable of reversibly occluding lithium, it is useful as an active material for a lithium secondary battery having good repetitive reversibility and high discharge rate. It is extremely expensive.
[Brief description of the drawings]
FIG. 1 is a diagram showing an X-ray diffraction pattern of an active material for a lithium battery according to the present invention.
FIG. 2 is a diagram showing a tunnel-type ramsdellite structure of an active material for a lithium battery according to the present invention.
FIG. 3 shows a charge / discharge curve for the first cycle of a battery comprising a lithium counter electrode, a lithium reference electrode, and an electrode made from the active material of the present invention. In this case, the active material was used as the negative electrode, charged first to occlude lithium ions, and then discharged to release lithium.
FIG. 4 is a view showing a cyclic voltammogram of an active material for a lithium battery according to the present invention. (The scanning speed was 3 mV / min.)
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10653897A JP3985104B2 (en) | 1997-03-04 | 1997-03-04 | Lithium battery and its active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10653897A JP3985104B2 (en) | 1997-03-04 | 1997-03-04 | Lithium battery and its active material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10247496A JPH10247496A (en) | 1998-09-14 |
| JP3985104B2 true JP3985104B2 (en) | 2007-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP10653897A Expired - Fee Related JP3985104B2 (en) | 1997-03-04 | 1997-03-04 | Lithium battery and its active material |
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4642959B2 (en) * | 2000-01-26 | 2011-03-02 | 東邦チタニウム株式会社 | Method for producing lithium titanate |
| JP4642960B2 (en) * | 2000-01-26 | 2011-03-02 | 東邦チタニウム株式会社 | Method for producing lithium titanate |
| JP4644895B2 (en) * | 2000-01-24 | 2011-03-09 | 株式会社豊田中央研究所 | Lithium secondary battery |
| JP3931228B2 (en) * | 2002-06-21 | 2007-06-13 | 独立行政法人物質・材料研究機構 | Lithium chromium titanium composite oxide having ramsdellite type crystal structure and method for producing the same |
| US7828879B2 (en) | 2005-09-16 | 2010-11-09 | Chuo University | Carbon dioxide absorbing material, method for producing carbon dioxide absorbing material, method for absorbing carbon dioxide, and apparatus for absorbing carbon dioxide |
| JP5095179B2 (en) * | 2006-11-10 | 2012-12-12 | 株式会社東芝 | Nonaqueous electrolyte battery, lithium titanium composite oxide and battery pack |
| JP5438891B2 (en) * | 2007-08-23 | 2014-03-12 | 株式会社東芝 | Non-aqueous electrolyte secondary battery negative electrode material, non-aqueous electrolyte secondary battery negative electrode material manufacturing method, non-aqueous electrolyte secondary battery, and battery pack |
| JP5178111B2 (en) | 2007-09-26 | 2013-04-10 | 株式会社東芝 | Non-aqueous electrolyte battery and pack battery |
| JP5300502B2 (en) | 2008-03-13 | 2013-09-25 | 株式会社東芝 | Battery active material, non-aqueous electrolyte battery and battery pack |
| JP5121614B2 (en) | 2008-07-18 | 2013-01-16 | 株式会社東芝 | Battery active material, non-aqueous electrolyte battery and battery pack |
| JP5474695B2 (en) * | 2010-07-27 | 2014-04-16 | 日本電信電話株式会社 | Negative electrode material for lithium secondary battery and lithium secondary battery |
| JP2012084358A (en) * | 2010-10-08 | 2012-04-26 | Nippon Telegr & Teleph Corp <Ntt> | Lithium secondary battery anode material and manufacturing method thereof and lithium secondary battery using the same |
| JP5671969B2 (en) * | 2010-11-24 | 2015-02-18 | 日立化成株式会社 | Lithium titanium compound particles and method for producing the same, electrode material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| KR101296592B1 (en) * | 2011-01-12 | 2013-08-14 | 주식회사 엘지화학 | Novel Cathode Active Material, Method for Preparation the Same, and Lithium Secondary Battery Comprising the Same |
| JP5662261B2 (en) * | 2011-06-20 | 2015-01-28 | 日本電信電話株式会社 | Method for producing negative electrode material for lithium secondary battery and lithium secondary battery |
| JP5706364B2 (en) * | 2012-03-29 | 2015-04-22 | 株式会社東芝 | Nonaqueous electrolyte battery, lithium titanium composite oxide and battery pack |
| WO2013157873A1 (en) | 2012-04-18 | 2013-10-24 | 주식회사 엘지화학 | Electrode for secondary battery, and secondary battery comprising same |
| JP2014001110A (en) * | 2012-06-20 | 2014-01-09 | Taiyo Yuden Co Ltd | Lithium titanium complex oxide, production method thereof and electrode for battery |
| JP6257222B2 (en) * | 2013-08-28 | 2018-01-10 | テイカ株式会社 | Ramsdelite type lithium titanate, lithium ion secondary battery and lithium ion capacitor using this ramsdelite type lithium titanate |
| JP6555987B2 (en) * | 2015-09-01 | 2019-08-07 | テイカ株式会社 | Lithium titanium composite oxide, method for producing lithium titanium composite oxide, lithium ion secondary battery and lithium ion capacitor using the lithium titanium composite oxide |
| JP7025620B2 (en) * | 2017-01-30 | 2022-02-25 | セントラル硝子株式会社 | Method for manufacturing electrode laminate for all-solid-state lithium battery, electrode composite for all-solid-state lithium battery and method for manufacturing the same |
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| JPH10247496A (en) | 1998-09-14 |
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