JP6259433B2 - Method for producing negative electrode active material for secondary battery - Google Patents
Method for producing negative electrode active material for secondary battery Download PDFInfo
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- JP6259433B2 JP6259433B2 JP2015180468A JP2015180468A JP6259433B2 JP 6259433 B2 JP6259433 B2 JP 6259433B2 JP 2015180468 A JP2015180468 A JP 2015180468A JP 2015180468 A JP2015180468 A JP 2015180468A JP 6259433 B2 JP6259433 B2 JP 6259433B2
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- negative electrode
- titanium
- electrode active
- active material
- niobium oxide
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- 239000007773 negative electrode material Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 22
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 239000010955 niobium Substances 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
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- 238000010304 firing Methods 0.000 claims description 17
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- 238000001035 drying Methods 0.000 claims description 10
- 150000002822 niobium compounds Chemical class 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012071 phase Substances 0.000 description 18
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
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- GIMXAEZBXRIECN-UHFFFAOYSA-J 2-hydroxyacetate;titanium(4+) Chemical compound [Ti+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O GIMXAEZBXRIECN-UHFFFAOYSA-J 0.000 description 1
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 0.000 description 1
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- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、チタンニオブ酸化物を得る工程を含む、固相法による二次電池用負極活物質の製造方法に関する。 The present invention relates to a method for producing a negative electrode active material for a secondary battery by a solid phase method including a step of obtaining a titanium niobium oxide.
従来より、リチウムイオン電池の負極としてグラファイトの使用が普及している。かかるグラファイトは、リチウム基準で０．１〜０．３Ｖ近傍に作動電位を有しており、リチウムイオン電池の高電圧化及び高エネルギー密度化を実現する上で大きな役割を果たしている。 Conventionally, the use of graphite as a negative electrode for lithium ion batteries has been widespread. Such graphite has an operating potential in the vicinity of 0.1 to 0.3 V on the basis of lithium, and plays a large role in realizing higher voltage and higher energy density of the lithium ion battery.
一方、かかるグラファイトの作動電位は金属リチウムの析出電位近傍でもあるために、電池が過充電状態となると、グラファイト表面の不動状皮膜から漏出した金属リチウムが対極に向かって結晶化してデンドライトが生成されてしまう。また、放電過程では、デンドライトの根元部が溶出して先端部がグラファイト表面から離脱し、電池の中に残留してしまう。こうした電解液中に残留して浮遊する金属リチウムは、デッドリチウムとも称され、非常に活性の高い微小金属リチウムとなって、充放電効率を低下させるだけでなく、電池内での内部短絡や発熱等を引き起こすおそれもある。 On the other hand, since the working potential of such graphite is also close to the deposition potential of metallic lithium, when the battery is overcharged, metallic lithium leaking from the immobile film on the graphite surface crystallizes toward the counter electrode and dendrites are generated. End up. Further, in the discharge process, the dendrite root part elutes and the tip part separates from the graphite surface and remains in the battery. The metallic lithium that remains in the electrolyte and floats is also called dead lithium, and it becomes very active micro metallic lithium, which not only lowers the charge / discharge efficiency but also causes internal short circuits and heat generation in the battery. There is also a risk of causing this.
デンドライトの生成やデッドリチウムの発生を回避するには、負極の作動電位がリチウム基準で１Ｖ以上となる材料が求められるところ、例えば非特許文献１では、チタンニオブ酸化物（ＴｉＮｂ2Ｏ7）であれば、リチウム基準で１Ｖ以上の電位範囲において、２５０〜２８０ｍＡｈ／ｇの高容量を示すことが報告されている。このようなチタンニオブ酸化物の製造方法としては、水熱法によるもの、固相法によるもの、及び錯体重合法によるものに大別されるが、なかでも特殊な設備が不要であることや操作が簡便であることから、固相法による製造方法が広く採用されている。
In order to avoid the generation of dendrite and the generation of dead lithium, a material whose operating potential of the negative electrode is 1 V or more with respect to lithium is required. For example, in
例えば、特許文献１には、固相法により得られた単斜晶のＴｉＮｂ2Ｏ7やＴｉ2Ｎｂ10Ｏ29を大気雰囲気下１０００〜１４００℃で２４時間熱処理した後、粉砕を経て、再度同温度で２４時間熱処理をする方法が開示されている。また特許文献２には、大気雰囲気下１０００℃で１２時間熱処理した後、粉砕を経て、１１００℃で１２時間熱処理を施すＴｉＮｂ2Ｏ7の製造方法が開示されている。
For example, in
しかしながら、いずれの文献に記載の製造方法であっても、長時間の熱処理を余儀なくされるため、二次電池用負極活物質としての良好な性能を確保しつつ、固相法による製造方法でありながら熱処理の短縮化を図ることは、依然として困難な状況であった。 However, in any of the production methods described in the literature, since a long-time heat treatment is required, the production method is a solid-phase method while ensuring good performance as a negative electrode active material for a secondary battery. However, it was still difficult to shorten the heat treatment.
したがって、本発明の課題は、固相法による製造方法であっても、有効に熱処理時間の短縮を図ることのできる、二次電池用負極活物質の製造方法を提供することにある。 Therefore, the subject of this invention is providing the manufacturing method of the negative electrode active material for secondary batteries which can aim at shortening of heat processing time effectively even if it is the manufacturing method by a solid-phase method.
そこで本発明者らは、種々検討したところ、特定の原料を含有する懸濁液を調製し、次いで湿式混合、乾燥及び焼成を介する製造方法であれば、固相法によるものであっても熱処理時間を短縮することができ、従来の製造方法で得られる負極活物質と比べても、同等或いはそれ以上の性能を発現し得る二次電池用負極活物質が得られることを見出し、本発明を完成させるに至った。 Therefore, the present inventors have made various studies and prepared a suspension containing a specific raw material, and then a heat treatment, even if it is a solid phase method, as long as it is a production method through wet mixing, drying and firing. It was found that a negative electrode active material for a secondary battery capable of shortening the time and capable of expressing the performance equal to or higher than that of the negative electrode active material obtained by a conventional manufacturing method was obtained. It came to complete.
すなわち、本発明は、ニオブ化合物、チタン化合物、過酸化水素、及び水を含有する懸濁液を調製する工程（Ｉ）、
得られた懸濁液を湿式混合して混合物を得る工程（II）、並びに
得られた混合物を、乾燥及び焼成してチタンニオブ酸化物を得る工程（III）
を備える、固相法による二次電池用負極活物質の製造方法を提供するものである。
That is, the present invention provides a step (I) of preparing a suspension containing a niobium compound, a titanium compound, hydrogen peroxide, and water.
Step (II) for obtaining a mixture by wet-mixing the obtained suspension, and Step (III) for obtaining titanium niobium oxide by drying and firing the obtained mixture.
The manufacturing method of the negative electrode active material for secondary batteries by a solid-phase method is provided.
本発明の製造方法によれば、チタンニオブ酸化物を得る工程を含む、固相法による二次電池用負極活物質の製造方法であっても熱処理を効果的に短縮することができ、操作や設備等の簡略化を実現しつつ、得られる電池において良好な性能を確保することができる。 According to the production method of the present invention, heat treatment can be effectively shortened even in the production method of a negative electrode active material for a secondary battery by a solid phase method including a step of obtaining a titanium niobium oxide. In the obtained battery, good performance can be ensured while realizing simplification of the above.
以下、本発明について詳細に説明する。
本発明の固相法による二次電池用負極活物質の製造方法は、ニオブ化合物、チタン化合物、過酸化水素、及び水を含有する懸濁液を調製する工程（Ｉ）、
得られた懸濁液を湿式混合して混合物を得る工程（II）、並びに
得られた混合物を、乾燥及び焼成してチタンニオブ酸化物を得る工程（III）
を備える。
Hereinafter, the present invention will be described in detail.
The method for producing a negative electrode active material for a secondary battery according to the solid phase method of the present invention comprises a step (I) of preparing a suspension containing a niobium compound, a titanium compound, hydrogen peroxide, and water,
Step (II) for obtaining a mixture by wet-mixing the obtained suspension, and Step (III) for obtaining titanium niobium oxide by drying and firing the obtained mixture.
Is provided.
工程（Ｉ）において用いるニオブ化合物は、後の工程でチタンニオブ酸化物を得るにあたり、ニオブ源として用いる化合物である。かかるニオブ化合物としては、例えば水酸化ニオブ（Ｎｂ(ＯＨ)５、Ｎｂ(ＯＨ)２、Ｎｂ(ＯＨ)４）、酸化ニオブ（Ｎｂ２Ｏ５、ＮｂＯ２、Ｎｂ２Ｏ３、ＮｂＯ等）、五塩化ニオブ、シュウ酸ニオブアンモニウム、オキシ塩化ニオブ、臭化ニオブ、フッ化ニオブ、及び酸化ニオブゾルから選ばれる１種又は２種が挙げられる。なかでも、反応性や操作性、及び熱処理を効果的に短縮化する観点から、水酸化ニオブ(Ｖ)（Ｎｂ(ＯＨ)５）が好ましい。
かかるニオブ化合物の含有量は、ニオブ化合物の種類によっても変動し得るが、工程（Ｉ）において得られる懸濁液中に、好ましくは２０〜６０質量％であり、より好ましくは２５〜５５質量％であり、さらに好ましくは３０〜５０質量％である。
The niobium compound used in the step (I) is a compound used as a niobium source in obtaining a titanium niobium oxide in a later step. Examples of such niobium compounds include niobium hydroxide (Nb (OH) 5 , Nb (OH) 2 , Nb (OH) 4 ), niobium oxide (Nb 2 O 5 , NbO 2 , Nb 2 O 3 , NbO, etc.), Examples thereof include one or two selected from niobium pentachloride, ammonium niobium oxalate, niobium oxychloride, niobium bromide, niobium fluoride, and niobium oxide sol. Of these, niobium hydroxide (V) (Nb (OH) 5 ) is preferable from the viewpoint of effectively shortening the reactivity, operability, and heat treatment.
The content of the niobium compound may vary depending on the type of niobium compound, but is preferably 20 to 60% by mass, more preferably 25 to 55% by mass in the suspension obtained in the step (I). More preferably, it is 30-50 mass%.
工程（Ｉ）において用いるチタン化合物は、後の工程でチタンニオブ酸化物を得るにあたり、チタン源として用いる化合物である。かかるチタン化合物としては、例えば酸化チタン（アナターゼ型、ルチル型等）、チタン錯体（グリコール酸チタン錯体、クエン酸チタン錯体等）、チタンアルコキシド（チタンイソプロポキシド等）、チタン塩（硫酸チタン、硝酸チタン等）、及びチタン塩化物（四塩化チタン等）から選ばれる１種又は２種以上が挙げられ、金属チタンを用いることもできる。なかでも、反応性や操作性、及び熱処理を効果的に短縮化する観点から、酸化チタン（アナターゼ型）が好ましい。 The titanium compound used in step (I) is a compound used as a titanium source in obtaining titanium niobium oxide in a later step. Examples of the titanium compound include titanium oxide (anatase type, rutile type, etc.), titanium complex (titanium glycolate complex, titanium citrate complex, etc.), titanium alkoxide (titanium isopropoxide, etc.), titanium salt (titanium sulfate, nitric acid, etc.). And one or more selected from titanium chloride (titanium tetrachloride, etc.), and titanium metal can also be used. Among these, titanium oxide (anatase type) is preferable from the viewpoint of effectively shortening the reactivity, operability, and heat treatment.
また、かかるチタン化合物は、不可避的に混入する場合も含め、その一部にチタン及びニオブ以外の異種金属Ｍ（ＭはＺｒ、Ｈｆ、Ｖ、Ｔａ、Ｆｅ、Ｂｉ、Ｓｂ、Ａｓ、Ｐ、Ｃｒ、Ｍｏ、Ｗ、Ｂ、Ｎａ、Ｍｇ、Ａｌ及びＳｉからなる群より選ばれる少なくとも一種を示す。）を含んでいてもよい。異種金属（Ｍ）の含有量は、より良好な電池物性を確保する観点から、チタン化合物中に、好ましくは３３質量％以下であり、より好ましくは１５質量％以下であり、さらに好ましくは７質量％以下である。 In addition, such a titanium compound is inevitably mixed, and a part thereof is a different metal M other than titanium and niobium (M is Zr, Hf, V, Ta, Fe, Bi, Sb, As, P, Cr). And at least one selected from the group consisting of Mo, W, B, Na, Mg, Al, and Si. The content of the foreign metal (M) is preferably 33% by mass or less, more preferably 15% by mass or less, and further preferably 7% by mass in the titanium compound from the viewpoint of securing better battery physical properties. % Or less.
かかるチタン化合物の含有量は、工程（Ｉ）において得られる懸濁液中におけるニオブとのモル比（Ｎｂ／Ｔｉ）で、好ましくは１．８〜５．４であり、より好ましくは１．８５〜５．３であり、さらに好ましくは１．９〜５．２である。より具体的には、本発明で得られるチタンニオブ酸化物が後述する式（１）で表される場合、チタン化合物の含有量は、工程（Ｉ）において得られる懸濁液中におけるニオブとのモル比（Ｎｂ／Ｔｉ）で、好ましくは１．８〜２．４であり、より好ましくは１．８５〜２．３であり、さらに好ましくは１．９〜２．１である。また、本発明で得られるチタンニオブ酸化物が後述する式（２）で表される場合、チタン化合物の含有量は、工程（Ｉ）において得られる懸濁液中におけるニオブとのモル比（Ｎｂ／Ｔｉ）で、４．６〜５．４であり、より好ましくは４．７〜５．３であり、さらに好ましくは４．８〜５．２である。 The content of such a titanium compound is preferably 1.8 to 5.4, more preferably 1.85 in terms of a molar ratio (Nb / Ti) with niobium in the suspension obtained in the step (I). It is -5.3, More preferably, it is 1.9-5.2. More specifically, when the titanium niobium oxide obtained in the present invention is represented by the formula (1) described later, the content of the titanium compound is the mole of niobium in the suspension obtained in step (I). The ratio (Nb / Ti) is preferably 1.8 to 2.4, more preferably 1.85 to 2.3, and still more preferably 1.9 to 2.1. Moreover, when the titanium niobium oxide obtained by this invention is represented by Formula (2) mentioned later, content of a titanium compound is molar ratio (Nb / N) with the niobium in the suspension obtained in process (I). Ti) is 4.6 to 5.4, more preferably 4.7 to 5.3, and even more preferably 4.8 to 5.2.
工程（Ｉ）において用いる過酸化水素は、水溶液として用いてもよく、工程（Ｉ）において得られる懸濁液中の各成分の分散性や反応性を高め、熱処理の短縮化を効果的に促進することができる。かかる過酸化水素の含有量は、工程（Ｉ）において得られる懸濁液中に、ニオブに対する過酸化水素のモル比（過酸化水素／Ｎｂ）で、好ましくは１〜１０であり、より好ましくは１．５〜８であり、さらに好ましくは２〜６である。 The hydrogen peroxide used in the step (I) may be used as an aqueous solution, and enhances the dispersibility and reactivity of each component in the suspension obtained in the step (I) and effectively promotes shortening of the heat treatment. can do. The hydrogen peroxide content is preferably 1 to 10 in terms of the molar ratio of hydrogen peroxide to niobium (hydrogen peroxide / Nb) in the suspension obtained in step (I), more preferably It is 1.5-8, More preferably, it is 2-6.
工程（Ｉ）では、上記ニオブ化合物、チタン化合物、及び過酸化水素のほか、水を用いて懸濁液を調製する。かかる水としては、上記過酸化水素を水溶液として用いるのみでもよく、別途水を添加してもよい。
懸濁液における水の含有量は、過酸化水素溶液等、その他の成分に含まれる水分量をも含む、懸濁液中に含まれる全水分量を意味し、懸濁液中の各成分の分散性や反応性を確保する観点から、工程（Ｉ）において得られる懸濁液中に、好ましくは１０〜９０質量％であり、より好ましくは２０〜８０質量％である。
In step (I), a suspension is prepared using water in addition to the niobium compound, titanium compound, and hydrogen peroxide. As such water, hydrogen peroxide may be used as an aqueous solution, or water may be added separately.
The content of water in the suspension means the total amount of water contained in the suspension, including the amount of water contained in other components such as hydrogen peroxide solution. From the viewpoint of ensuring dispersibility and reactivity, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass in the suspension obtained in step (I).
工程（Ｉ）における懸濁液のｐＨは、後述する工程（II）及び（III）を経ることにより、目的物であるチタンニオブ酸化物を良好に得る観点から、好ましくは７〜１２であり、より好ましくは８〜１１である。なお、適宜ｐＨ調整剤を用いてもよい。 The pH of the suspension in the step (I) is preferably 7 to 12 from the viewpoint of favorably obtaining the target titanium niobium oxide through the steps (II) and (III) described later. Preferably it is 8-11. In addition, you may use a pH adjuster suitably.
工程（Ｉ）において、これらニオブ化合物、チタン化合物、過酸化水素、及び水の添加順序は特に制限されないが、工程（Ｉ）において得られる懸濁液中の各成分の分散性や反応性を高め、適度な結晶子径を有するチタンニオブ酸化物を生成させる観点、及び熱処理の短縮化を促進する観点から、予めニオブ化合物、チタン化合物、及び水を混合し、これに過酸化水素（又は過酸化水素水溶液）、及び必要に応じてｐＨ調整剤を添加するのが好ましい。また、工程（II）に移行する前に、得られる懸濁液中において各成分をより均一に分散させる観点、及び発生する過酸化水素ガスを除去する観点から、さらに混合して脱ガス処理を施すのが好ましい。 In step (I), the order of addition of these niobium compound, titanium compound, hydrogen peroxide, and water is not particularly limited, but the dispersibility and reactivity of each component in the suspension obtained in step (I) are increased. From the viewpoint of producing a titanium niobium oxide having an appropriate crystallite diameter and promoting the shortening of the heat treatment, a niobium compound, a titanium compound, and water are mixed in advance, and hydrogen peroxide (or hydrogen peroxide) Aqueous solution) and, if necessary, a pH adjuster is preferably added. Further, before proceeding to step (II), from the viewpoint of more uniformly dispersing each component in the obtained suspension and from the viewpoint of removing the generated hydrogen peroxide gas, further mixing and degassing treatment are performed. It is preferable to apply.
この際、混合時間は、充分に脱ガス処理を行う観点から、好ましくは０．２〜５時間であり、より好ましくは０．３〜１時間である。また、混合時の温度は、過酸化水素の添加によって発熱を伴うこともあり、好ましくは５０〜１００℃であり、より好ましくは７０〜９０℃である。脱ガス処理を良好に行う観点から、混合処理は開放系で行うことが望ましい。混合装置としては、例えばマグネチックスターラーや回転翼を備えた装置等、懸濁液の混合を行うことができる通常の装置が使用できる。 At this time, the mixing time is preferably 0.2 to 5 hours, more preferably 0.3 to 1 hour, from the viewpoint of sufficiently performing the degassing treatment. Moreover, the temperature at the time of mixing may generate heat | fever by addition of hydrogen peroxide, Preferably it is 50-100 degreeC, More preferably, it is 70-90 degreeC. From the viewpoint of favoring degassing treatment, it is desirable to perform the mixing treatment in an open system. As the mixing device, for example, a normal device capable of mixing the suspension, such as a device equipped with a magnetic stirrer or a rotating blade, can be used.
工程（II）は、工程（Ｉ）で得られた懸濁液を湿式混合して混合物を得る工程である。湿式混合の手段としては、特に制限されず、常法により行うことができるが、ボールミルを用いた湿式混合であるのが好ましい。 Step (II) is a step in which the suspension obtained in step (I) is wet-mixed to obtain a mixture. The means for wet mixing is not particularly limited and can be carried out by a conventional method, but is preferably wet mixing using a ball mill.
ボールミルで用いる装置の容器としては、鋼、ステンレス、ナイロン製が挙げられ、内壁はアルミナ煉瓦、磁気質、天然ケイ石、ゴム、ウレタン等が挙げられる。ボールとしては、アルミナ球石、天然ケイ石、鉄球、ジルコニアボール等が用いられる。ボール径は、０．１ｍｍから２０ｍｍが好ましく、０．５〜５ｍｍがより好ましい。ボールの充填量は、使用するミルの内容積に対し、ボールの充填体積が５〜５０％を占める割合とするのが好ましい。また、ボールミルにて湿式混合を行う場合、例えば公転５０〜８００ｒｐｍ、自転１００〜１，６００ｒｐｍの条件とするのが好ましい。 Examples of the container of the apparatus used in the ball mill include steel, stainless steel, and nylon, and the inner wall includes alumina brick, magnetic material, natural silica, rubber, urethane, and the like. As the ball, alumina sphere, natural silica, iron ball, zirconia ball or the like is used. The ball diameter is preferably 0.1 mm to 20 mm, and more preferably 0.5 to 5 mm. It is preferable that the filling amount of the ball is a ratio in which the filling volume of the ball occupies 5 to 50% with respect to the internal volume of the mill to be used. Moreover, when performing wet mixing with a ball mill, it is preferable to set it as conditions, for example, 50 to 800 rpm of revolution and 100 to 1,600 rpm of rotation.
工程（II）における湿式混合時の温度は、好ましくは５〜５０℃であり、より好ましくは１０〜３０℃である。また、湿式混合する時間は、好ましくは０．５〜２４時間であり、より好ましくは１〜１２時間であり、さらに好ましくは２〜６時間である。 The temperature at the time of wet mixing in the step (II) is preferably 5 to 50 ° C, more preferably 10 to 30 ° C. The wet mixing time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours, and further preferably 2 to 6 hours.
工程（III）は、工程（II）で得られた混合物を、乾燥及び焼成してチタンニオブ酸化物を得る工程である。すなわち、かかる工程では、焼成の前に乾燥を行う。乾燥手段としては、噴霧乾燥、真空乾燥、凍結乾燥等が挙げられる。なかでも、粉砕することなく均一に微細化されたチタンニオブ酸化物を得る観点から、噴霧乾燥が好ましい。かかる噴霧乾燥を行う場合、通常採用し得る諸条件を適宜選択すればよいが、チタンニオブ酸化物の結晶子径の粗大化を有効に抑制して焼成時間の短縮化を効果的に図る観点から、例えば入口温度は、好ましくは１６０〜２１０℃であり、出口温度は、好ましくは７５〜９５℃であり、噴霧圧力は、好ましくは０．５〜０．９ｋｇ／ｃｍ2である。さらに、噴霧乾燥により造粒化されるチタンニオブ酸化物の粒径は、好ましくは０．５〜２０μｍであり、より好ましくは１〜１０μｍである。かかる粒径となるよう、用いるノズルを適宜選定すればよい。
なお、乾燥手段として、真空乾燥や凍結乾燥を選択する場合、予め乾燥に付する前に、フィルタープレス機、遠心濾過機等を用いて固液分離し、液相含有量を極力低減しておくのがよい。
Step (III) is a step of obtaining a titanium niobium oxide by drying and firing the mixture obtained in step (II). That is, in this step, drying is performed before firing. Examples of the drying means include spray drying, vacuum drying, freeze drying and the like. Of these, spray drying is preferred from the viewpoint of obtaining a uniformly refined titanium niobium oxide without pulverization. When performing such spray drying, various conditions that can be usually employed may be selected as appropriate, but from the viewpoint of effectively reducing the firing time by effectively suppressing the coarsening of the crystallite diameter of the titanium niobium oxide, For example, the inlet temperature is preferably 160 to 210 ° C., the outlet temperature is preferably 75 to 95 ° C., and the spray pressure is preferably 0.5 to 0.9 kg / cm 2 . Furthermore, the particle size of the titanium niobium oxide granulated by spray drying is preferably 0.5 to 20 μm, more preferably 1 to 10 μm. What is necessary is just to select the nozzle to be used suitably so that it may become this particle size.
When vacuum drying or freeze-drying is selected as the drying means, the liquid phase content is reduced as much as possible by subjecting it to solid-liquid separation using a filter press, a centrifugal filter or the like prior to drying. It is good.
工程（III）における焼成は、チタンの価数を+４価とするために酸化雰囲気下で焼成する必要があり、簡便性、経済性の観点から大気雰囲気で行うのが好ましい。焼成温度は、チタンニオブ酸化物の結晶子径の粗大化を有効に抑制する観点、短時間で固相反応を完了させる観点、及び焼成時間の短縮化を効果的に図る観点から、好ましくは７００〜１４００℃であり、より好ましくは１０００〜１４００℃であり、さらに好ましくは１１００〜１４００℃である。焼成に用いる装置としては、焼成雰囲気及び温度の調整が可能な物であれば特に限定されず、バッチ式、連続式、加熱方式（間接又は直接）のいずれの方式のものも使用することができる。かかる装置としては、例えば、外熱キルンやローラーハース等の焼成炉が挙げられる。 Firing in step (III) needs to be performed in an oxidizing atmosphere in order to make the valence of titanium +4, and is preferably performed in an air atmosphere from the viewpoint of simplicity and economy. From the viewpoint of effectively suppressing the coarsening of the crystallite diameter of the titanium niobium oxide, from the viewpoint of completing the solid phase reaction in a short time, and from the viewpoint of effectively shortening the firing time, the firing temperature is preferably 700 to It is 1400 degreeC, More preferably, it is 1000-1400 degreeC, More preferably, it is 1100-1400 degreeC. The apparatus used for firing is not particularly limited as long as the firing atmosphere and temperature can be adjusted, and any of batch, continuous, and heating (indirect or direct) systems can be used. . Examples of such an apparatus include firing furnaces such as an external heat kiln and a roller hearth.
本発明の製造方法であれば、効果的に熱処理の短縮化を図ることができるため、工程（III）における焼成時間は、好ましくは０．２〜２時間であり、より好ましくは０．３〜１時間であり、さらに０．３〜０．８時間とすることも可能である。 If it is the manufacturing method of this invention, since shortening of heat processing can be aimed at effectively, the baking time in process (III) becomes like this. Preferably it is 0.2 to 2 hours, More preferably, it is 0.3 to 1 hour, and further 0.3 to 0.8 hours is possible.
本発明により得られるチタンニオブ酸化物は、具体的には、例えば、下記式（１）又は（２）で表され、単斜晶構造を有する化合物である。
Ｔｉ1-xＭxＮｂ2Ｏ7 ・・・（１）
（式（１）中、ＭはＺｒ、Ｈｆ、Ｖ、Ｔａ、Ｆｅ、Ｂｉ、Ｓｂ、Ａｓ、Ｐ、Ｃｒ、Ｍｏ、Ｗ、Ｂ、Ｎａ、Ｍｇ、Ａｌ及びＳｉからなる群より選ばれる少なくとも一種を示す。ｘは、０≦ｘ＜０．１を満たす数を示す。）
Ｔｉ2-ｙＭｙＮｂ10Ｏ29 ・・・（２）
（式（２）中、ＭはＺｒ、Ｈｆ、Ｖ、Ｔａ、Ｆｅ、Ｂｉ、Ｓｂ、Ａｓ、Ｐ、Ｃｒ、Ｍｏ、Ｗ、Ｂ、Ｎａ、Ｍｇ、Ａｌ及びＳｉからなる群より選ばれる少なくとも一種を示す。ｙは、０≦ｙ＜０．２を満たす数を示す。）
上記チタンニオブ酸化物は、本発明の効果を阻害しない範囲内で、式（１）で表される場合は、Ｔｉ2Ｎｂ10Ｏ29及び／又はＴｉＯ2の夾雑相を含んでいてもよく、式（２）で表される場合は、ＴｉＮｂ2Ｏ7及び／又はＴｉＯ2の夾雑相を含んでいてもよい。これら夾雑相の含有率は、優れた充放電特性を発揮する観点から、チタンニオブ酸化物中に、好ましくは５質量％以下であり、より好ましくは４質量％以下であり、さらに好ましくは３質量％以下である。なお、かかる夾雑相の含有率とは、得られたチタンニオブ酸化物について、Ｘ線回折−リートベルト法を適用して求めた定量値を意味する。
The titanium niobium oxide obtained by the present invention is specifically a compound represented by the following formula (1) or (2) and having a monoclinic structure.
Ti 1-x M x Nb 2 O 7 (1)
(In formula (1), M is at least one selected from the group consisting of Zr, Hf, V, Ta, Fe, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Al, and Si. X represents a number satisfying 0 ≦ x <0.1.)
Ti 2-y M y Nb 10 O 29 ··· (2)
(In the formula (2), M is at least one selected from the group consisting of Zr, Hf, V, Ta, Fe, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Al and Si. Y represents a number satisfying 0 ≦ y <0.2.)
The titanium niobium oxide may contain a mixed phase of Ti 2 Nb 10 O 29 and / or TiO 2 when represented by the formula (1) within a range that does not impair the effects of the present invention. When represented by (2), a mixed phase of TiNb 2 O 7 and / or TiO 2 may be included. The content of these contaminated phases is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass in the titanium niobium oxide from the viewpoint of exhibiting excellent charge / discharge characteristics. It is as follows. In addition, the content rate of this contaminating phase means the quantitative value calculated | required about the obtained titanium niobium oxide by applying the X-ray diffraction-Riet belt method.
本発明により得られるチタンニオブ酸化物は、充放電効率及び電池容量が高い電池を得る観点から、そのＢＥＴ比表面積が、好ましくは１．０ｍ2／ｇ以上であり、より好ましくは１．２ｍ2／ｇ以上であり、さらに好ましくは１．５ｍ2／ｇ以上である。ＢＥＴ比表面積の上限は特に制限されないが、通常１０ｍ2／ｇ以下であり、好ましくは７ｍ2／ｇ以下であり、より好ましくは５ｍ2／ｇ以下である。 Chitan'niobu oxide obtained by the present invention, from the viewpoint of charge and discharge efficiency and the battery capacity to obtain a high battery, the BET specific surface area, is preferably 1.0 m 2 / g or more, more preferably 1.2 m 2 / g or more, more preferably 1.5 m 2 / g or more. The upper limit of the BET specific surface area is not particularly limited, but is usually 10 m 2 / g or less, preferably 7 m 2 / g or less, more preferably 5 m 2 / g or less.
本発明により得られるチタンニオブ酸化物は、その結晶子径が、好ましくは２５〜２５０ｎｍであり、より好ましくは２５〜２２０ｎｍであり、その結晶性も高いものである。また、チタンニオブ酸化物の平均粒子径は、５０〜９００ｎｍであり、より好ましくは５０〜８００ｎｍである。なお、チタンニオブ酸化物の結晶子径は、Ｃｕ−ｋα線による回折角２θの範囲が１０°〜８０°のＸ線回折プロファイルについて、シェラーの式を適用して求めた値を意味する。ここで、得られたチタンニオブ酸化物が、例えば上記式（１）で表され、ＴｉＯ2等の夾雑相を含有する場合は、結晶構造パラメーター（ＩＣＤＤデータベース）に基づいて計算されたそれら夾雑相のＸ線回折プロファイルを、得られたチタンニオブ酸化物混合体のＸ線回折プロファイルから差し引いて求めたＴｉＮｂ2Ｏ7のＸ線回折プロファイルについて、シェラーの式を適用して求めた値を意味する。 The titanium niobium oxide obtained by the present invention has a crystallite diameter of preferably 25 to 250 nm, more preferably 25 to 220 nm, and high crystallinity. Moreover, the average particle diameter of a titanium niobium oxide is 50-900 nm, More preferably, it is 50-800 nm. The crystallite diameter of the titanium niobium oxide means a value obtained by applying Scherrer's equation for an X-ray diffraction profile having a diffraction angle 2θ range of 10 ° to 80 ° by Cu-kα rays. Here, when the obtained titanium niobium oxide is expressed by, for example, the above formula (1) and contains a contaminating phase such as TiO 2 , those contaminating phases calculated based on the crystal structure parameter (ICDD database) The value obtained by applying Scherrer's equation to the X-ray diffraction profile of TiNb 2 O 7 obtained by subtracting the X-ray diffraction profile from the X-ray diffraction profile of the obtained titanium niobium oxide mixture is meant.
上記チタンニオブ酸化物は、そのままでも二次電池用負極材活物質として用いることができるが、チタンニオブ酸化物の表面に炭素を担持させて、より十分な電子伝導性を確保して優れた電池特性を発現させる観点から、グルコース、サッカロース、フルクトース、デキストリン、デンプン、ポリエチレングリコール、ポリビニルアルコール、カルボキシメチルセルロース、カーボンブラック、繊維状炭素等の炭素源を添加して混合し、焼成するのが好ましい。この際、炭素源の添加量は、炭素原子換算量で、二次電池用負極材活物質中に、好ましくは１〜１０質量％であり、より好ましくは３〜８質量％である。
焼成条件は、不活性ガス雰囲気下又は還元条件下にて行うのが好ましく、また焼成温度は、好ましくは５００〜８００℃であり、より好ましくは５５０〜７５０℃であり、さらに好ましくは６００〜７５０℃である。また、焼成時間は、好ましくは１０分〜５時間、より好ましくは３０分〜４時間とするのがよい。
The titanium niobium oxide can be used as a negative electrode active material for a secondary battery as it is, but carbon is supported on the surface of the titanium niobium oxide to ensure more sufficient electron conductivity and excellent battery characteristics. From the viewpoint of expression, it is preferable to add a carbon source such as glucose, saccharose, fructose, dextrin, starch, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, carbon black, fibrous carbon, and the like, and calcinate. Under the present circumstances, the addition amount of a carbon source is a carbon atom conversion amount, Preferably it is 1-10 mass% in the negative electrode active material for secondary batteries, More preferably, it is 3-8 mass%.
The firing conditions are preferably performed under an inert gas atmosphere or under reducing conditions, and the firing temperature is preferably 500 to 800 ° C, more preferably 550 to 750 ° C, and further preferably 600 to 750. ° C. The firing time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 4 hours.
得られたチタンニオブ酸化物を負極活物質として用いて二次電池を製造する方法は特に限定されず、公知の方法をいずれも使用できる。例えば、かかる負極活物質を結着剤や溶剤等の添加剤とともに混合して塗工液を得る。この際、必要に応じて、さらに導電助剤を添加して混合してもよい。かかる結着剤としては、特に限定されず、公知の剤をいずれも使用できる。具体的には、ポリテトラフルオロエチレン、ポリビニリデンフルオライド、ポリビニルクロライド、エチレンプロピレンジエンポリマー等が挙げられる。また、かかる導電助剤としては、特に限定されず、黒鉛以外の公知の剤をいずれも使用できる。具体的には、アセチレンブラック、ケッチェンブラック、繊維状炭素等が挙げられる。次いで、かかる塗工液を銅箔等の負極集電体上に塗布し、乾燥させて負極とする。 A method for producing a secondary battery using the obtained titanium niobium oxide as a negative electrode active material is not particularly limited, and any known method can be used. For example, the negative electrode active material is mixed with additives such as a binder and a solvent to obtain a coating liquid. At this time, if necessary, a conductive additive may be further added and mixed. The binder is not particularly limited, and any known agent can be used. Specific examples include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, and ethylene propylene diene polymer. Moreover, it does not specifically limit as this conductive support agent, Any well-known agents other than graphite can be used. Specific examples include acetylene black, ketjen black, and fibrous carbon. Subsequently, this coating liquid is apply | coated on negative electrode collectors, such as copper foil, and it is made to dry and is set as a negative electrode.
得られる二次電池用負極活物質は、リチウムイオン電池やナトリウムイオン電池等の二次電池の負極として非常に優れた放電容量及びサイクル特定を発揮する点で有用である。かかる負極を適用できる二次電池としては、正極と負極と電解液とセパレータを必須構成とするものであれば特に限定されない。 The obtained negative electrode active material for a secondary battery is useful in that it exhibits a very excellent discharge capacity and cycle specification as a negative electrode for a secondary battery such as a lithium ion battery or a sodium ion battery. A secondary battery to which such a negative electrode can be applied is not particularly limited as long as it has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components.
ここで、正極については、リチウムイオン又はナトリウムイオン等、所定の金属イオンを充電時には放出し、かつ放電時には吸蔵することができれば、その材料構成で特に限定されるものではなく、公知の材料構成のものを用いることができる。例えば、原料を水熱反応させることにより得られる各種オリビン型化合物を好適に用いることが好ましい。 Here, the positive electrode is not particularly limited in its material configuration as long as it can release a predetermined metal ion such as lithium ion or sodium ion at the time of charging and can be occluded at the time of discharging. Things can be used. For example, it is preferable to suitably use various olivine compounds obtained by hydrothermal reaction of the raw materials.
電解液は、有機溶媒に支持塩を溶解させたものである。有機溶媒は、通常リチウムイオン電池やナトリウムイオン電池等の二次電池の電解液に用いられる有機溶媒であれば特に限定されるものではなく、例えば、カーボネート類、ハロゲン化炭化水素、エーテル類、ケトン類、ニトリル類、ラクトン類、オキソラン化合物等を用いることができる。 The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte of a secondary battery such as a lithium ion battery or a sodium ion battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones , Nitriles, lactones, oxolane compounds and the like can be used.
支持塩は、その種類が特に限定されるものではないが、例えばリチウムイオン二次電池の場合、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ３ＣＦ３、ＬｉＣ（ＳＯ３ＣＦ３）２、ＬｉＮ（ＳＯ３ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２及びＬｉＮ（ＳＯ２ＣＦ３）（ＳＯ２Ｃ４Ｆ９）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。また、例えばナトリウムイオン二次電池の場合、ＮａＰＦ６、ＮａＢＦ４、ＮａＣｌＯ４及びＮａＡｓＦ６から選ばれる無機塩、該無機塩の誘導体、ＮａＳＯ３ＣＦ３、ＮａＣ（ＳＯ３ＣＦ３）２及びＮａＮ（ＳＯ３ＣＦ３）２、ＮａＮ（ＳＯ２Ｃ２Ｆ５）２及びＮａＮ（ＳＯ２ＣＦ３）（ＳＯ２Ｃ４Ｆ９）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。 The type of the supporting salt is not particularly limited. For example, in the case of a lithium ion secondary battery, an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , LiC (SO 3 CF 3 ) 2 , LiN (SO 3 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ) It is preferably at least one of an organic salt and a derivative of the organic salt. In the case of a sodium ion secondary battery, for example, an inorganic salt selected from NaPF 6 , NaBF 4 , NaClO 4 and NaAsF 6 , a derivative of the inorganic salt, NaSO 3 CF 3 , NaC (SO 3 CF 3 ) 2 and NaN ( At least one organic salt selected from SO 3 CF 3 ) 2 , NaN (SO 2 C 2 F 5 ) 2 and NaN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and a derivative of the organic salt Preferably there is.
セパレータは、正極及び負極を電気的に絶縁し、電解液を保持する役割を果たすものである。たとえば、多孔性合成樹脂膜、特にポリオレフィン系高分子（ポリエチレン、ポリプロピレン）の多孔膜を用いればよい。 The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［実施例１］
ＴｉＯ2（粉末、関東化学（株）製 試薬鹿一級、純度９８．５％）２４．３２４ｇ、Ｎｂ（ＯＨ）5（粉末、H.C. Starck製、純度９２．４％）１１５．５５２ｇ、及び水１００ｇをビーカーに投入後、マグネチックスターラーにて３０分間混合して混合液を得た。得られた混合液に、過酸化水素水（キシダ化学（株）製 試薬特級、純度３５％）を５８．３２ｇ添加し、マグネチックスターラーにてさらに３０分間混合して脱酸素処理を行い、懸濁液を得た。
次いで、得られた懸濁液をボールミル（回転数１２０ｒｐｍ、内径７．６ｃｍ、媒体φ１ｍｍＺｒＯ２ボール、媒体充填率７０％）にて、２５℃で１８時間湿式混合を行い、混合物を得た。
得られた混合物をスプレードライ法（スプレードライヤー：藤崎電機(株)製ＭＤＬ−０５０Ｍ）により噴霧乾燥し、得られた粉末を大気雰囲気下、１２００℃で２０分間焼成して、上記式（１）で表されるチタンニオブ酸化物（ＴｉＮｂ2Ｏ7）を得た。
そして、得られたチタンニオブ酸化物 ３ｇに、グルコース ０．４７４ｇ、水２ｇ、及びエタノール ８ｍｌ添加してボールミル（遊星型、フリッチュジャパン（株）製Ｐ−５）で６０分間混合した後、窒素雰囲気下、７５０℃で１時間焼成して、二次電池用負極活物質を得た。
[Example 1]
24.324 g of TiO 2 (powder, manufactured by Kanto Chemical Co., Inc., grade 18.5% purity), Nb (OH) 5 (powder, HC Starck, purity 92.4%) 115.552 g, and 100 g of water Was put into a beaker and mixed with a magnetic stirrer for 30 minutes to obtain a mixed solution. 58.32 g of hydrogen peroxide solution (special grade reagent manufactured by Kishida Chemical Co., Ltd., purity 35%) was added to the obtained mixed solution, and the mixture was further mixed for 30 minutes with a magnetic stirrer for deoxygenation treatment. A turbid liquid was obtained.
Next, the obtained suspension was wet-mixed at 25 ° C. for 18 hours in a ball mill (rotation speed 120 rpm, inner diameter 7.6 cm, medium φ1 mm ZrO 2 ball,
The obtained mixture was spray-dried by a spray-drying method (spray dryer: MDL-050M manufactured by Fujisaki Electric Co., Ltd.), and the obtained powder was fired at 1200 ° C. for 20 minutes in the air atmosphere to obtain the above formula (1) in yield represented Chitan'niobu oxides of (TiNb 2 O 7).
Then, 0.474 g of glucose, 2 g of water and 8 ml of ethanol were added to 3 g of the obtained titanium niobium oxide and mixed for 60 minutes with a ball mill (planet type, P-5 manufactured by Fritsch Japan Co., Ltd.). And calcining at 750 ° C. for 1 hour to obtain a negative electrode active material for a secondary battery.
［実施例２］
Ｎｂ源を、Ｎｂ2Ｏ5（粉末、関東化学（株）製 高純度試薬、純度９９．９％）７９．７４３ｇとした以外、実施例１と同様にして湿式混合を行い、得られた懸濁液をスプレードライ法により噴霧乾燥した。次いで、得られた粉末を大気雰囲気下、１１５０℃で５０分間焼成して、上記式（１）で表されるチタンニオブ酸化物（ＴｉＮｂ2Ｏ7）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Example 2]
The suspension obtained by wet-mixing was performed in the same manner as in Example 1 except that the Nb source was 79.743 g of Nb 2 O 5 (powder, high-purity reagent manufactured by Kanto Chemical Co., Inc., purity 99.9%). The turbid liquid was spray-dried by a spray drying method. Next, the obtained powder was baked at 1150 ° C. for 50 minutes in an air atmosphere to obtain titanium niobium oxide (TiNb 2 O 7 ) represented by the above formula (1).
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
［比較例１］
実施例１と同様にして混合液を得た後、過酸化水素水を添加することなく、実施例１と同様にして湿式混合を行い、得られた懸濁液をスプレードライ法により噴霧乾燥した。次いで、得られた粉末を大気雰囲気下、１１００℃で１２時間焼成して、上記式（１）で表されるチタンニオブ酸化物（ＴｉＮｂ2Ｏ7）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Comparative Example 1]
After obtaining a mixed solution in the same manner as in Example 1, wet mixing was performed in the same manner as in Example 1 without adding aqueous hydrogen peroxide, and the resulting suspension was spray-dried by a spray drying method. . Next, the obtained powder was baked at 1100 ° C. for 12 hours in an air atmosphere to obtain titanium niobium oxide (TiNb 2 O 7 ) represented by the above formula (1).
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
［比較例２］
ＴｉＯ2 １．６２２ｇｇ、及びＮｂ2Ｏ5１１５．５５２ｇに、エタノールを５ｍＬｇ添加し、乳鉢にて１０分間湿式混合を行った後、大気雰囲気下、１０００℃で１２時間仮焼成した。
得られた仮焼成後の混合物を乳鉢にて１０分間粉砕した後、大気雰囲気下、１１００℃で１２時間焼成して、上記式（１）で表されるチタンニオブ酸化物（ＴｉＮｂ2Ｏ7）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Comparative Example 2]
Ethanol ( 5 mLg) was added to TiO 2 ( 1.622 gg) and Nb 2 O 5 ( 115.552 g), and after wet mixing in a mortar for 10 minutes, the mixture was calcined at 1000 ° C. for 12 hours in an air atmosphere.
The obtained mixture after calcination was pulverized in a mortar for 10 minutes and then baked at 1100 ° C. for 12 hours in an air atmosphere to obtain titanium niobium oxide (TiNb 2 O 7 ) represented by the above formula (1). Obtained.
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
［比較例３］
比較例２と同様にして仮焼成後の混合物を得た後、かかる混合物を大気雰囲気下、１１００℃で１２時間の焼成と乳鉢での１０分間の粉砕を、３回繰り返して、上記式（１）で表されるチタンニオブ酸化物（ＴｉＮｂ2Ｏ7）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Comparative Example 3]
After obtaining a mixture after pre-baking in the same manner as in Comparative Example 2, the mixture was fired at 1100 ° C. for 12 hours and pulverized in a mortar for 10 minutes three times in the air atmosphere, and the above formula (1 It was obtained Chitan'niobu oxide represented (TiNb 2 O 7) in).
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
［実施例３］
ＴｉＯ2を８．１０８ｇ、Ｎｂ（ＯＨ）5を９６．２９３ｇ、及び水を１００ｇとし、過酸化水素水を４８．６ｇ添加した以外、実施例１と同様にして懸濁液を得た。次いで、得られた懸濁液を実施例１と同様にして噴霧乾燥し、得られた粉末を大気雰囲気下、１２００℃で３０分間焼成して、上記式（２）で表されるチタンニオブ酸化物（Ｔｉ2Ｎｂ10Ｏ29）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Example 3]
A suspension was obtained in the same manner as in Example 1 except that 8.108 g of TiO 2 , 96.293 g of Nb (OH) 5 and 100 g of water were added, and 48.6 g of hydrogen peroxide was added. Subsequently, the obtained suspension was spray-dried in the same manner as in Example 1, and the obtained powder was calcined at 1200 ° C. for 30 minutes in the air atmosphere to obtain a titanium niobium oxide represented by the above formula (2). (Ti 2 Nb 10 O 29 ) was obtained.
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
［比較例４］
実施例３と同様にして混合液を得た後、過酸化水素水を添加することなく、実施例３と同様にして湿式混合を行い、得られた懸濁液をスプレードライ法により噴霧乾燥した。次いで、得られた粉末を大気雰囲気下、１１００℃で１２時間焼成して、上記式（２）で表されるチタンニオブ酸化物（Ｔｉ2Ｎｂ10Ｏ29）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Comparative Example 4]
After obtaining a mixed solution in the same manner as in Example 3, wet mixing was performed in the same manner as in Example 3 without adding hydrogen peroxide, and the resulting suspension was spray-dried by a spray-drying method. . Subsequently, the obtained powder was baked at 1100 ° C. for 12 hours in an air atmosphere to obtain a titanium niobium oxide (Ti 2 Nb 10 O 29 ) represented by the above formula (2).
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
［比較例５］
ＴｉＯ2 １．６２２ｇｇ、及びＮｂ2Ｏ5 １３．２９０ｇに、エタノールを５ｍＬｇ添加し、乳鉢にて１０分間湿式混合を行った後、大気雰囲気下、１１００℃で１２時間仮焼成した。
得られた仮焼成後の混合物を乳鉢にて１０分間粉砕した後、大気雰囲気下、１１００℃で１２時間焼成して、上記式（２）で表されるチタンニオブ酸化物（Ｔｉ2Ｎｂ10Ｏ29）を得た。
そして、得られたチタンニオブ酸化物を用い、実施例１と同様にして、二次電池用負極活物質を得た。
[Comparative Example 5]
Ethanol ( 5 mLg) was added to TiO 2 ( 1.622 g) and Nb 2 O 5 ( 13.290 g), and after wet mixing in a mortar for 10 minutes, the mixture was temporarily fired at 1100 ° C. for 12 hours in an air atmosphere.
The obtained mixture after calcination was pulverized in a mortar for 10 minutes and then baked at 1100 ° C. for 12 hours in an air atmosphere to obtain titanium niobium oxide (Ti 2 Nb 10 O 29 ) represented by the above formula (2). )
And the negative electrode active material for secondary batteries was obtained like Example 1 using the obtained titanium niobium oxide.
《チタンニオブ酸化物の構成相、夾雑相含有率、及び結晶子径の評価》
実施例及び比較例で得られたチタンニオブ酸化物の構成相をＸ線回折分析により判別し、各構成相の含有率をＸ線回折−リートベルト法を適用して求めた。次いで、各々ＴｉＮｂ2Ｏ7又はＴｉ2Ｎｂ10Ｏ29の結晶子径を、Ｘ線回折プロファイル（全角）にシェラーの式を適用（ＪＩＳ Ｋ ０１３１「Ｘ線回折分析通則」に準拠）することにより求めた。
結晶子径の評価において、チタンニオブ酸化物の構成相が複数の場合には、得られたチタンニオブ酸化物のＸ線回折プロファイルから主相以外の夾雑相のＸ線回折プロファイルを差し引いて得られたＴｉＮｂ2Ｏ7単相又はＴｉ2Ｎｂ10Ｏ29単相のＸ線回折プロファイルを使用した。なお、含有率及び結晶子径の計算に用いた夾雑相のＸ線回折プロファイルは、ＩＣＤＤデータベースの結晶構造パラメーターを使用して計算で求めた。
結果を表１に示すとともに、実施例１及び比較例２のＸＲＤ回折パターン図を図１に示す。
<< Evaluation of constituent phase, contamination phase content, and crystallite size of titanium niobium oxide >>
The constituent phases of the titanium niobium oxide obtained in the examples and comparative examples were determined by X-ray diffraction analysis, and the content of each constituent phase was determined by applying the X-ray diffraction-Riet belt method. Next, by applying the Scherrer formula to the crystallite diameter of TiNb 2 O 7 or Ti 2 Nb 10 O 29 , respectively, to the X-ray diffraction profile (full angle) (based on JIS K 0131 “X-ray diffraction analysis general rules”) Asked.
In the evaluation of the crystallite diameter, when there are a plurality of constituent phases of the titanium niobium oxide, TiNb obtained by subtracting the X-ray diffraction profile of the impurity phase other than the main phase from the X-ray diffraction profile of the obtained titanium niobium oxide. X-ray diffraction profiles of 2 O 7 single phase or Ti 2 Nb 10 O 29 single phase were used. Note that the X-ray diffraction profile of the contaminating phase used for the calculation of the content ratio and the crystallite size was obtained by calculation using the crystal structure parameters of the ICDD database.
The results are shown in Table 1, and XRD diffraction pattern diagrams of Example 1 and Comparative Example 2 are shown in FIG.
〈Ｘ線回折測定条件〉
試料調整：粉末試料成形機（東京科学(株)製ＴＫ−７５０）にて、７０ｋｇの圧力
でプレス
装置：Ｘ線回折装置：ブルカー・エイエックスエス(株)製 Ｄ８Ａｄｖａｎｃｅ
Ｘ線：Cu-kα（管電圧−電流＝３５ｋＶ−３５０ｍＡ）
測定条件：ステップスキャン（ステップサイズ０．０２３°、０．１３秒／ステ
ップ）、２θ： １０°〜８０°
解析ソフトウェア：ブルカー・エイエックスエス(株)製 ＤＩＦＦＲＡＣｐｌｕｓ
ＴＯＰＡＳ（ｖｅｒ．３）
<X-ray diffraction measurement conditions>
Sample preparation: 70 kg of pressure using a powder sample molding machine (TK-750, manufactured by Tokyo Science Co., Ltd.)
Press machine: X-ray diffractometer: Bruker AXS Co., Ltd. D8 Advance
X-ray: Cu-kα (tube voltage-current = 35 kV-350 mA)
Measurement conditions: Step scan (step size 0.023 °, 0.13 sec / step
2θ: 10 ° -80 °
Analysis software: DIFFRACplus manufactured by Bruker AXS Co., Ltd.
TOPAS (ver. 3)
《チタンニオブ酸化物のＢＥＴ比表面積の測定》
測定装置（(株)島津製作所製ＦｌｏｗＳｏｒｂIII ２３０５）を用いて、実施例及び比較例で得られたチタンニオブ酸化物の窒素吸着法によるＢＥＴ比表面積を測定した。
結果を表１に示す。
<< Measurement of BET specific surface area of titanium niobium oxide >>
Using a measuring apparatus (FlowSorbIII 2305 manufactured by Shimadzu Corporation), the BET specific surface area of the titanium niobium oxide obtained in Examples and Comparative Examples was measured by a nitrogen adsorption method.
The results are shown in Table 1.
《充放電特性の評価》
実施例及び比較例で得られた二次電池用負極活物質、ケッチェンブラック（導電剤）、ポリフッ化ビニリデン(粘結剤)を質量比９０：３：７の配合割合で混合し、これにＮ−メチル−２−ピロリドンを加えて充分混練し、負極スラリーを調製した。
得られた負極スラリーを厚さ２０μｍのアルミニウム箔からなる集電体に塗工機を用いて塗布し、８０ ℃で１２時間の真空乾燥を行った。その後、φ１４ｍｍの円盤状に打ち抜いてハンドプレスを用いて１６ＭＰａで２分間プレスし、負極とした。
次いで、φ１５ｍｍに打ち抜いたＬｉ箔を正極とし、電解液としてエチレンカーボネート及びエチルメチルカーボネートを体積比１：１の割合で混合した混合溶媒にＬｉＰＦ6を１ ｍｏl/Ｌの濃度で溶解したものを用い、セパレータに高分子多孔フィルム（ポリプロピレン製）を用いて、露点が−５０℃以下の雰囲気で常法により組み込み収容し、コイン型リチウム二次電池（ＣＲ−２０３２）を製造した。
作成した各リチウム二次電池について、気温３０℃環境下、充電条件を電流１ＣＡ（３８７ｍＡ／ｇ）、電圧３Ｖの定電流充電とし、放電条件を１ＣＡ（３８７ｍＡ／ｇ）、終止電圧１Ｖの定電流定電圧放電として、０．２ＣＡおよび３ＣＡにおける放電容量を測定（測定装置：北斗電工(株)製 ＨＪ−１００１ＳＤ８）した。
結果を表２に示す。
<Evaluation of charge / discharge characteristics>
The negative electrode active materials for secondary batteries, ketjen black (conductive agent), and polyvinylidene fluoride (binder) obtained in Examples and Comparative Examples were mixed at a mass ratio of 90: 3: 7, and this was mixed therewith. N-methyl-2-pyrrolidone was added and sufficiently kneaded to prepare a negative electrode slurry.
The obtained negative electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a negative electrode.
Next, Li foil punched out to φ15 mm was used as the positive electrode, and an electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1. Using a polymer porous film (made of polypropylene) as a separator, the separator was incorporated and housed in an ordinary manner in an atmosphere having a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).
For each lithium secondary battery created, the charging condition was a constant current charge of 1 CA (387 mA / g) and a voltage of 3 V under a temperature of 30 ° C., the discharge condition was a constant current of 1 CA (387 mA / g) and a final voltage of 1 V. As constant voltage discharge, discharge capacities at 0.2 CA and 3 CA were measured (measuring device: HJ-1001SD8 manufactured by Hokuto Denko Co., Ltd.).
The results are shown in Table 2.
図１の結果より、比較例２では、ＴｉＮｂ2Ｏ7にＴｉ2Ｎｂ10Ｏ29とＴｉＯ2の夾雑相が混在するのに対し、実施例１では、これらの夾雑相が存在しないことが確認できる。
また、表１〜２の結果より、実施例１〜３で得られた二次電池用負極活物質は、効果的に熱処理時間の短縮を図ることができ、得られる電池においても、比較例と同等若しくはそれ以上の放電容量を確保することができる。
From the result of FIG. 1, in Comparative Example 2, it is confirmed that TiNb 2 O 7 contains a mixed phase of Ti 2 Nb 10 O 29 and TiO 2 , whereas in Example 1, these mixed phases do not exist. it can.
Moreover, from the results of Tables 1 and 2, the negative electrode active materials for secondary batteries obtained in Examples 1 to 3 can effectively shorten the heat treatment time. An equivalent or higher discharge capacity can be ensured.
Claims (5)
得られた懸濁液を湿式混合して混合物を得る工程（II）、並びに
得られた混合物を、乾燥及び焼成してチタンニオブ酸化物を得る工程（III）
を備える、固相法による二次電池用負極活物質の製造方法。 A step (I) of preparing a suspension containing a niobium compound, a titanium compound, hydrogen peroxide, and water;
Step (II) for obtaining a mixture by wet-mixing the obtained suspension, and Step (III) for obtaining titanium niobium oxide by drying and firing the obtained mixture.
A method for producing a negative electrode active material for a secondary battery by a solid phase method.
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