JP2018131370A - Lower-order titanium oxide and method for producing the same - Google Patents
Lower-order titanium oxide and method for producing the same Download PDFInfo
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 24
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- 238000004438 BET method Methods 0.000 claims abstract description 8
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Classifications
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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
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
本発明は、低次酸化チタン及びその製造方法に関し、特にＢＥＴ法による比表面積が１０〜１０００ｍ２／ｇであり、そして粉体抵抗率が１０．０Ω・ｃｍ以下である高い比表面積と優れた導電性を有する低次酸化チタン及びその製造方法に関する。 The present invention relates to a low-order titanium oxide and a method for producing the same, and in particular, has a high specific surface area and an excellent specific surface area of 10 to 1000 m 2 / g by a BET method and a powder resistivity of 10.0 Ω · cm or less. The present invention relates to conductive low-order titanium oxide and a method for producing the same.
特開２０１６−８１５８４号公報（特許文献１）、特開２０１２−１４８９２０号公報（特許文献２）及び特開２０１６−１９３８１６号公報（特許文献３）などに記載されているように、Ｔｉ４Ｏ７やＴｉ５Ｏ９など一般式：ＴｉｎＯ２ｎ−１（２≦ｎ≦１０）で表されるマグネリ相を有する低次酸化チタンは優れた導電性を有することが知られている。 As described in JP-A-2016-81584 (Patent Document 1), JP-A-2012-148920 (Patent Document 2), JP-A-2006-193816 (Patent Document 3), and the like, Ti 4 O It is known that low-order titanium oxide having a magnetic phase represented by a general formula: Ti n O 2n-1 (2 ≦ n ≦ 10) such as 7 and Ti 5 O 9 has excellent conductivity.
また、低次酸化チタンを工業的に製造するための代表的な方法としては、（ａ）二酸化チタン粉体（ＴｉＯ２粉体）を水素気流中で高温焼成する水素還元法、（ｂ）二酸化チタン粉体をアンモニア（＋水素）気流中で高温焼成するアンモニア還元法、（ｃ）金属チタン粉体と二酸化チタン粉体を均一に混合した後、還元雰囲気で高温焼成する金属チタン粉体との均一化反応法、（ｄ）二酸化チタンを水素化ホウ素ナトリウムなどの水素化物と共に還元焼成する方法などの製造方法が知られている。 In addition, representative methods for industrially producing low-order titanium oxide include (a) a hydrogen reduction method in which titanium dioxide powder (TiO 2 powder) is calcined at high temperature in a hydrogen stream, and (b) dioxide dioxide. Ammonia reduction method in which titanium powder is calcined at high temperature in an ammonia (+ hydrogen) stream, and (c) metal titanium powder and titanium dioxide powder are uniformly mixed and then calcined at high temperature in a reducing atmosphere. Production methods such as a homogenization reaction method and (d) a method of reducing and firing titanium dioxide together with a hydride such as sodium borohydride are known.
一方、低次酸化チタンを燃料電池やキャパシタなどの電極として用いる場合、高い反応効率を得るためには低次酸化チタンが高い比表面積を有していることが好ましい。ところが、特許文献１〜３に記載されている製造方法や上記（ａ）〜（ｄ）の一般的な製造方法を用いて高い比表面積を有する低次酸化チタンを得ようとすると、粒子同士の接点が増加してその接触抵抗が増大してしまい、その結果低次酸化チタンを利用した電極の導電性が低下し、期待した特性を得ることができないという問題があった。 On the other hand, when low-order titanium oxide is used as an electrode for a fuel cell or a capacitor, it is preferable that the low-order titanium oxide has a high specific surface area in order to obtain high reaction efficiency. However, when trying to obtain low-order titanium oxide having a high specific surface area using the production methods described in Patent Documents 1 to 3 and the general production methods (a) to (d) above, There is a problem that the contact resistance increases and the contact resistance increases, and as a result, the conductivity of the electrode using low-order titanium oxide is lowered, and the expected characteristics cannot be obtained.
そこで、本発明は、導電性を低下させることなく高い比表面積を有する低次酸化チタン及びその製造方法を提供することを目的とする。 Then, an object of this invention is to provide the low order titanium oxide which has a high specific surface area, and its manufacturing method, without reducing electroconductivity.
本発明者らは、二酸化チタン（ＴｉＯ２）を出発原料として低次酸化チタンを得るための製造方法について鋭意研究を重ねた結果、二酸化チタンを特定の有機化合物と混合し不活性ガス雰囲気下で焼成すれば、得られる低次酸化チタンのモルフォロジー制御（形状制御）を行うことができることを見出し、本発明を完成するに至った。 As a result of intensive research on a production method for obtaining low-order titanium oxide using titanium dioxide (TiO 2 ) as a starting material, the present inventors have mixed titanium dioxide with a specific organic compound and in an inert gas atmosphere. It has been found that the morphology control (shape control) of the obtained low-order titanium oxide can be performed by firing, and the present invention has been completed.
具体的には、本発明によれば、二酸化チタン（ＴｉＯ２）と有機化合物との混合物を窒素やアルゴン等の不活性ガス雰囲気下にて焼成することにより、高い比表面積と優れた導電性を有する低次酸化チタンを製造する方法が提供される。本発明の製造方法では、不活性ガス以外に水素等の還元ガス、または不活性ガスと還元ガスとの混合ガスなどの使用も可能であるが、必ずしも水素等の還元ガスや触媒を使用する必要はなく、経済性や安全面を考慮すれば窒素ガスを使用することが好ましい。 Specifically, according to the present invention, by firing a mixture of titanium dioxide (TiO 2 ) and an organic compound in an inert gas atmosphere such as nitrogen or argon, a high specific surface area and excellent conductivity are obtained. A method for producing low order titanium oxide is provided. In the production method of the present invention, it is possible to use a reducing gas such as hydrogen or a mixed gas of an inert gas and a reducing gas in addition to the inert gas, but it is necessary to use a reducing gas such as hydrogen or a catalyst. However, it is preferable to use nitrogen gas in consideration of economy and safety.
本発明の製造方法により得られる低次酸化チタンは、ＢＥＴ法による比表面積が１０〜１０００ｍ２／ｇであり、そして粉体抵抗率が１０．０Ω・ｃｍ以下であり、より好ましくはＢＥＴ法による比表面積が１０〜５００ｍ２／ｇであり、そして粉体抵抗率が１．０Ω・ｃｍ以下であるという特徴を有している。また、その形態は、平均の一次粒子径が約１００ｎｍ以下であり球形に近い形状を有している。 The low-order titanium oxide obtained by the production method of the present invention has a specific surface area by the BET method of 10 to 1000 m 2 / g and a powder resistivity of 10.0 Ω · cm or less, more preferably by the BET method. The specific surface area is 10 to 500 m 2 / g, and the powder resistivity is 1.0 Ω · cm or less. Moreover, the form has a shape close | similar to a spherical shape with an average primary particle diameter of about 100 nm or less.
得られた低次酸化チタンは、一般式：ＴｉｎＯ２ｎ−１（２≦ｎ≦１０）で表されるものであり、高い比表面積と優れた導電性を得るためには、低次酸化チタン中にＴｉ４Ｏ７が７０重量％以上、より好ましくは９０重量％以上含まれていることが望ましい。 The obtained low-order titanium oxide is represented by the general formula: Ti n O 2n-1 (2 ≦ n ≦ 10). In order to obtain a high specific surface area and excellent conductivity, low-order oxidation is performed. It is desirable that Ti 4 O 7 is contained in titanium in an amount of 70% by weight or more, more preferably 90% by weight or more.
本発明の製造方法において、上述したような高い比表面積と優れた導電性を有する低次酸化チタンを得るためには、出発原料である二酸化チタンの還元、および焼成時の粒子成長抑制の両効果を発現させる添加剤が必要である。 In the production method of the present invention, in order to obtain low-order titanium oxide having a high specific surface area and excellent conductivity as described above, both effects of reduction of titanium dioxide as a starting material and suppression of particle growth during firing are obtained. It is necessary to have an additive that causes
低次酸化チタンの製造で使用される二酸化チタンは、アナタース型、ルチル型、ブルッカイト型、無定形などがあり、低温焼成による粒子成長抑制効果を考慮すると無定形であることが好ましい。 Titanium dioxide used in the production of low-order titanium oxide includes anatase type, rutile type, brookite type, and amorphous, and is preferably amorphous in consideration of the effect of suppressing particle growth by low-temperature firing.
添加剤としては、カーボン粉体や水素化カルシウムのような材料の適用例があるが、粒子成長抑制の観点では二酸化チタン表面に均一に添加剤が混合されていることが好ましく、その添加剤として水溶性あるいは焼成時にガス化するような有機化合物が挙げられる。 As additives, there are application examples of materials such as carbon powder and calcium hydride, but from the viewpoint of suppressing particle growth, it is preferable that the additive is uniformly mixed on the surface of titanium dioxide. Organic compounds that are water-soluble or gasify upon firing can be mentioned.
二酸化チタンと混合する有機化合物としては、水溶性高分子や単糖類、少糖類、多糖類を用いることができ、例えば、単糖類としてはグルコース、フルクトース、ガラクトース、少糖類としてはスクロース、マルトース、ラクトースなど、多糖類としてはデンプン、水溶性高分子としてはポリビニルアルコール、ポリアクリル酸、カルボキシメチルセルロースなどを使用することができる。 As an organic compound mixed with titanium dioxide, water-soluble polymers, monosaccharides, oligosaccharides, and polysaccharides can be used. For example, monosaccharides include glucose, fructose, galactose, and oligosaccharides include sucrose, maltose, and lactose. For example, starch can be used as the polysaccharide, and polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, and the like can be used as the water-soluble polymer.
また、本発明の製造方法では、得られる低次酸化チタンの焼結を抑制しモルフォロジー制御（形状制御）を向上させる必要があることから、９００〜１２００℃の温度で焼成することが好ましい。 Moreover, in the manufacturing method of this invention, since it is necessary to suppress sintering of the low order titanium oxide obtained and to improve morphology control (shape control), it is preferable to bake at the temperature of 900-1200 degreeC.
上述のように、本発明の製造方法で得られる低次酸化チタンは高い比表面積と優れた導電性を有しているため、燃料電池やキャパシタなどの蓄電デバイス用の電極として使用するのに適している。 As described above, since the low-order titanium oxide obtained by the production method of the present invention has a high specific surface area and excellent conductivity, it is suitable for use as an electrode for power storage devices such as fuel cells and capacitors. ing.
本発明の低次酸化チタンは、ＢＥＴ法による比表面積が１０〜１０００ｍ２／ｇであり、そして粉体抵抗率が１０．０Ω・ｃｍ以下であり、より好ましくはＢＥＴ法による比表面積が１０〜５００ｍ２／ｇであり、そして粉体抵抗率が１．０Ω・ｃｍ以下であるという極めて高い比表面積と優れた導電性を有している。 The low-order titanium oxide of the present invention has a specific surface area by the BET method of 10 to 1000 m 2 / g and a powder resistivity of 10.0 Ω · cm or less, more preferably a specific surface area by the BET method of 10 to 10 It has an extremely high specific surface area and excellent electrical conductivity of 500 m 2 / g and a powder resistivity of 1.0 Ω · cm or less.
また、本発明の低次酸化チタンは、二酸化チタン（ＴｉＯ２）とカーボン源としての有機化合物との混合物を不活性ガス雰囲気下にて焼成するというモルフォロジー制御性（形状制御性）に極めて優れた製造方法により提供され、また安全で経済的でもある。 Moreover, the low-order titanium oxide of the present invention is extremely excellent in morphology controllability (shape controllability) in which a mixture of titanium dioxide (TiO 2 ) and an organic compound as a carbon source is fired in an inert gas atmosphere. It is provided by the manufacturing method and is also safe and economical.
以下、高い比表面積と優れた導電性を有する本発明の低次酸化チタン、低次酸化チタンを用いた電極及び蓄電デバイス、低次酸化チタンの製造方法について、具体例を交えながら詳細に説明する。なお、本発明は以下に示される実施形態に限定されるものではなく、本発明の技術的思想を逸脱しない範囲内で各種の変更が可能である。 Hereinafter, the low-order titanium oxide of the present invention having a high specific surface area and excellent conductivity, an electrode and an electricity storage device using the low-order titanium oxide, and a method for producing the low-order titanium oxide will be described in detail with specific examples. . The present invention is not limited to the embodiments shown below, and various modifications can be made without departing from the technical idea of the present invention.
Ａ．低次酸化チタンの製造方法：
実施例１
水４５００ｇが入った容器中に無定形の二酸化チタン（ＴｉＯ２）５００ｇを撹拌しながら投入し、１０ｗｔ％二酸化チタンスラリーを調整した。水２３５０ｇが入った容器の中にポリビニルアルコール（ＰＶＡ）１５０ｇを撹拌させながら投入後、９０℃の温度で１時間保持後、冷却することで６ｗｔ％ポリビニルアルコール水溶液を調整した。１０ｗｔ％二酸化チタンスラリー５００ｇに６ｗｔ％ポリビニルアルコール水溶液２５０ｇを撹拌しながら混合し、二酸化チタン−ＰＶＡ混合スラリーを調整した。その混合スラリーを噴霧式乾燥機（ＭＤＬ−５０Ｂ，藤崎電機社製）で乾燥し、低次酸化チタンの前駆体を得た。得られた前駆体２０ｇをアルミナ製ルツボへ投入後、前駆体が入ったアルミナルツボをタンマン管式雰囲気焼成炉（ＮＬＴ−２０３５Ｄ−ＳＰ モトヤマ製）の中へ入れ、窒素雰囲気下、焼成条件１０００℃×３時間の条件で焼成することにより実施例１の低次酸化チタンを得た。
A. Production method of low-order titanium oxide:
Example 1
Into a container containing 4500 g of water, 500 g of amorphous titanium dioxide (TiO 2 ) was added while stirring to prepare a 10 wt% titanium dioxide slurry. Into a container containing 2350 g of water, 150 g of polyvinyl alcohol (PVA) was added while stirring, then held at 90 ° C. for 1 hour, and then cooled to prepare a 6 wt% polyvinyl alcohol aqueous solution. 250 g of a 6 wt% polyvinyl alcohol aqueous solution was mixed with 500 g of 10 wt% titanium dioxide slurry while stirring to prepare a titanium dioxide-PVA mixed slurry. The mixed slurry was dried with a spray dryer (MDL-50B, manufactured by Fujisaki Electric Co., Ltd.) to obtain a precursor of low-order titanium oxide. After 20 g of the obtained precursor was put into an alumina crucible, the alumina crucible containing the precursor was placed in a Tamman tube atmosphere firing furnace (NLT-2035D-SP made by Motoyama), and the firing condition was 1000 ° C. in a nitrogen atmosphere. The low-order titanium oxide of Example 1 was obtained by baking under conditions of × 3 hours.
実施例２
１０ｗｔ％二酸化チタンスラリーと混合する６ｗｔ％ポリビニルアルコール水溶液の添加量を２５０ｇから３４０ｇに変更した以外は実施例１と同様の操作を行い、実施例２の低次酸化チタンを得た。
Example 2
The same operation as in Example 1 was performed except that the addition amount of the 6 wt% polyvinyl alcohol aqueous solution mixed with the 10 wt% titanium dioxide slurry was changed from 250 g to 340 g, and the low-order titanium oxide of Example 2 was obtained.
実施例３
１０ｗｔ％二酸化チタンスラリーと混合する６ｗｔ％ポリビニルアルコール水溶液の添加量を２５０ｇから４２０ｇに変更した以外は実施例１と同様の操作を行い、実施例３の低次酸化チタンを得た。
Example 3
The same operation as in Example 1 was performed except that the addition amount of the 6 wt% polyvinyl alcohol aqueous solution mixed with the 10 wt% titanium dioxide slurry was changed from 250 g to 420 g, and the low-order titanium oxide of Example 3 was obtained.
実施例４
１０ｗｔ％二酸化チタンスラリーと混合する６ｗｔ％ポリビニルアルコール水溶液の添加量を２５０ｇから７００ｇに変更した以外は実施例１と同様の操作を行い、実施例４の低次酸化チタンを得た。
Example 4
The same operation as in Example 1 was performed except that the addition amount of the 6 wt% polyvinyl alcohol aqueous solution mixed with the 10 wt% titanium dioxide slurry was changed from 250 g to 700 g, and the low-order titanium oxide of Example 4 was obtained.
実施例５
１０ｗｔ％二酸化チタンスラリーと混合する６ｗｔ％ポリビニルアルコール水溶液の添加量を２５０ｇから１００ｇに変更した以外は実施例１と同様の操作を行い、実施例５の低次酸化チタンを得た。
Example 5
The same operation as in Example 1 was performed except that the addition amount of the 6 wt% polyvinyl alcohol aqueous solution mixed with the 10 wt% titanium dioxide slurry was changed from 250 g to 100 g, and the low-order titanium oxide of Example 5 was obtained.
実施例６
焼成温度を９５０℃に変更した以外は実施例１と同様の操作を行い、実施例６の低次酸化チタンを得た。
Example 6
Except having changed the calcination temperature to 950 degreeC, operation similar to Example 1 was performed and the low order titanium oxide of Example 6 was obtained.
実施例７
焼成温度を１１５０℃に変更した以外は実施例１と同様の操作を行い、実施例７の低次酸化チタンを得た。
Example 7
Except having changed the calcination temperature to 1150 degreeC, operation similar to Example 1 was performed and the low order titanium oxide of Example 7 was obtained.
実施例８
１０ｗｔ％二酸化チタンスラリーと混合する６ｗｔ％ポリビニルアルコール水溶液の添加量を２５０ｇから２００ｇに変更した以外は実施例１と同様の操作を行い、実施例８の低次酸化チタンを得た。
Example 8
The same operation as in Example 1 was performed except that the addition amount of the 6 wt% polyvinyl alcohol aqueous solution mixed with the 10 wt% titanium dioxide slurry was changed from 250 g to 200 g, and the low-order titanium oxide of Example 8 was obtained.
比較例１
二酸化チタン５gをアルミナ製ルツボに入れ、焼成条件１１７０℃×２時間、窒素９０％−水素１０％混合雰囲気下で焼成し、比較例１の低次酸化チタンを得た。
Comparative Example 1
5 g of titanium dioxide was placed in an alumina crucible and baked under a firing condition of 1170 ° C. for 2 hours under a mixed atmosphere of 90% nitrogen and 10% hydrogen to obtain low-order titanium oxide of Comparative Example 1.
比較例２
二酸化チタン５ｇと金属チタン１ｇ混合した粉末をキャリアガスであるアルゴンガスでプラズマトーチへ搬送し、アルゴン雰囲気下約４ＭＨｚ、約８０ｋＶＡの高周波電圧を印加した条件で高周波熱プラズマ処理し、比較例２の低次酸化チタンを得た。
Comparative Example 2
A powder obtained by mixing 5 g of titanium dioxide and 1 g of metal titanium is conveyed to a plasma torch with an argon gas as a carrier gas, and subjected to a high-frequency thermal plasma treatment in a condition where a high-frequency voltage of about 4 MHz and about 80 kVA is applied in an argon atmosphere. Low-order titanium oxide was obtained.
比較例３
比較例２の低次酸化チタン２ｇと導電性カーボンであるアセチレンブラック０．０８ｇを自転・公転ミキサー（あわとり練太郎（登録商標）ＡＲ−１００，シンキー社製）で２０分混合し、比較例３の低次酸化チタンとアセチレンブラック混合粉末を得た。
Comparative Example 3
Comparative Example 2 2 g of low-order titanium oxide and 0.08 g of acetylene black, which is a conductive carbon, were mixed for 20 minutes with a rotating / revolving mixer (Awatori Nerita (registered trademark) AR-100, manufactured by Sinky Corporation). 3 low-order titanium oxide and acetylene black mixed powder was obtained.
Ｂ．粉体物性測定：
［Ｘ線回折分析］
Ｘ線回折分析は、実施例及び比較例で得た粉末状のサンプルを加圧成型した後、Ｘ線回折装置（Ｘ’Ｐｅｒｔ ＰＲＯ，スペクトリス社製）により、ＣｕＫα線を用いて印加電圧４５ｋＶ，印加電流４０ｍＡの条件で測定を行った。また、Ｔｉ４Ｏ７の純度は、Ｘ線回折分析により得られたデータをリートベルト解析（解析ソフト名：Ｘ’Ｐｅｒｔ Ｈｉｇｈ Ｓｃｏｒｅ Ｐｌｕｓ）による結晶構造解析を行うことにより決定した。
B. Powder physical property measurement:
[X-ray diffraction analysis]
X-ray diffraction analysis was performed by pressure-molding the powdered samples obtained in Examples and Comparative Examples, and then using an X-ray diffractometer (X'Pert PRO, manufactured by Spectris Co., Ltd.) with an applied voltage of 45 kV using CuKα rays. Measurement was performed under an applied current of 40 mA. The purity of Ti 4 O 7 was determined by performing crystal structure analysis on the data obtained by X-ray diffraction analysis by Rietveld analysis (analysis software name: X′Pert High Score Plus).
［比表面積］
ＢＥＴ法を使用し、Ｍａｃｓｏｒｂ ＨＭ−１２０８（マウンテック社製）で測定を行った。
[Specific surface area]
Measurement was performed with Macsorb HM-1208 (Mounttech) using the BET method.
［粉体抵抗率測定］
粉体抵抗測定システムＭＣＰ−ＰＤ−５１（三菱アナリティカル社製）を用い測定を行った。測定方法は、粉体専用プローブ（４探針、リング電極）を具備した容器にサンプルを投入後、１０ｋＮの圧力をかけた時の粉体抵抗と厚みを測定し、下記の式で粉体抵抗率を算出した。
・粉体抵抗率（Ω・ｃｍ）＝抵抗（Ω）×厚み（ｃｍ）×抵抗率補正係数（ＲＣＦ）
[Measurement of powder resistivity]
Measurement was performed using a powder resistance measurement system MCP-PD-51 (manufactured by Mitsubishi Analytical). The measurement method is to measure the powder resistance and thickness when a pressure of 10 kN is applied after putting the sample into a container equipped with a powder dedicated probe (4 probes, ring electrode). The rate was calculated.
・ Powder resistivity (Ω · cm) = resistance (Ω) × thickness (cm) × resistivity correction coefficient (RCF)
［カーボン量測定］
サンプルを秤量し容器に入れ、有機元素分析装置（ＭＡＣＲＯ ＣＯＲＤＥＲ ＪＭ１０００ＣＮ，ジェイ・サイエンス・ラボ社製）で測定を行った。
[Measurement of carbon content]
The sample was weighed and placed in a container, and measurement was performed with an organic element analyzer (MACRO CORDER JM1000CN, manufactured by J Science Laboratories).
［一次粒子径］
１次粒子径は、ＳＥＭ（走査型電子顕微鏡）から１００個の一次粒子についてその粒子径を計測し、計測値を算術平均し算出した。
[Primary particle size]
The primary particle size was calculated by measuring the particle size of 100 primary particles from an SEM (scanning electron microscope) and arithmetically averaging the measured values.
図１には、本発明の低次酸化チタンの代表的な例として、実施例１で得られた低次酸化チタンのＸ線回折パターンが示されており、図２には、比較例の低次酸化チタンの代表的な例として、比較例１で得られた低次酸化チタンのＸ線回折パターンが示されている。 FIG. 1 shows an X-ray diffraction pattern of the low-order titanium oxide obtained in Example 1 as a typical example of the low-order titanium oxide of the present invention, and FIG. As a typical example of titanium suboxide, the X-ray diffraction pattern of the low-order titanium oxide obtained in Comparative Example 1 is shown.
また、図３，４には、本発明の低次酸化チタンの代表的な例として、実施例１で得られた低次酸化チタンのＳＥＭ写真（×１０ｋ，×１００ｋ）が示されており、図５には、比較例の低次酸化チタンの代表的な例として、比較例１で得られた低次酸化チタンのＳＥＭ写真（×１０ｋ）が示されている。 Moreover, in FIG.3, 4, the SEM photograph (x10k, x100k) of the low order titanium oxide obtained in Example 1 as a typical example of the low order titanium oxide of this invention is shown, FIG. 5 shows an SEM photograph (× 10 k) of the low-order titanium oxide obtained in Comparative Example 1 as a representative example of the low-order titanium oxide of the comparative example.
実施例１〜８の低次酸化チタンおよび比較例１〜３の低次酸化チタンのＸ線回折分析を行った結果、得られたピークパターンより、いずれもＴｉ４Ｏ７に帰属することが確認された。また、実施例６ではＴｉ４Ｏ７の低次酸化チタンの他にＴｉ５Ｏ９やＴｉ６Ｏ１１の低次酸化チタンが生成されており、実施例７ではＴｉ３Ｏ５の低次酸化チタンが生成されていることが確認された。 As a result of X-ray diffraction analysis of the low-order titanium oxides of Examples 1 to 8 and the low-order titanium oxides of Comparative Examples 1 to 3, it was confirmed that all belong to Ti 4 O 7 from the obtained peak patterns. It was done. In Example 6, in addition to Ti 4 O 7 low-order titanium oxide, Ti 5 O 9 and Ti 6 O 11 low-order titanium oxide are produced. In Example 7, Ti 3 O 5 low-order titanium oxide is produced. It was confirmed that titanium was produced.
また、実施例１の低次酸化チタンのＳＥＭ写真と比較例１の低次酸化チタンのＳＥＭ写真とを比較すると、比較例１の低次酸化チタンは表面が滑らかな不規則形状をしているのに対して、実施例１の低次酸化チタンは表面に無数の凹凸を有する不規則形状をしている。このため、実施例１の低次酸化チタンは、比較例１の低次酸化チタンに対して極めて高い比表面積を有していることが確認される。 Further, comparing the SEM photograph of the low-order titanium oxide of Example 1 and the SEM photograph of the low-order titanium oxide of Comparative Example 1, the low-order titanium oxide of Comparative Example 1 has an irregular shape with a smooth surface. In contrast, the low-order titanium oxide of Example 1 has an irregular shape having numerous irregularities on the surface. For this reason, it is confirmed that the low-order titanium oxide of Example 1 has a very high specific surface area with respect to the low-order titanium oxide of Comparative Example 1.
実施例１〜８の低次酸化チタン−カーボン複合体および比較例１〜３の低次酸化チタンの比表面積と粉体抵抗率の測定結果を表１に示す。 Table 1 shows the measurement results of the specific surface area and powder resistivity of the low-order titanium oxide-carbon composites of Examples 1 to 8 and the low-order titanium oxides of Comparative Examples 1 to 3.
比較例１と比較例２の結果より、比表面積と粉体抵抗率はトレードオフの関係となっており、各々の特性を両立することが困難であることが確認された。また、比較例３では、比較例２に導電性カーボンであるアセチレンブラックを混合し粉体抵抗率の低減効果を確認したが、無添加の比較例２よりも粉体抵抗率が低減したが、実施例１〜８に示した粉体抵抗率までには至らなかった。ところが、実施例１〜８で得られた低次酸化チタンの場合、高い比表面積を有するにも拘らず粉体抵抗率の上昇が抑制されており、従来の製造方法では達成し得なかった高い比表面積と低い粉体抵抗率を両立させることが可能であることが判った。 From the results of Comparative Example 1 and Comparative Example 2, it was confirmed that the specific surface area and the powder resistivity had a trade-off relationship, and it was difficult to achieve both properties. In Comparative Example 3, acetylene black, which is conductive carbon, was mixed with Comparative Example 2 to confirm the effect of reducing powder resistivity, but the powder resistivity was reduced as compared with Comparative Example 2 without addition. It did not reach the powder resistivity shown in Examples 1-8. However, in the case of the low-order titanium oxide obtained in Examples 1 to 8, the increase in the powder resistivity is suppressed despite having a high specific surface area, which is high that cannot be achieved by the conventional manufacturing method. It was found that it is possible to achieve both a specific surface area and a low powder resistivity.
Ｃ．蓄電デバイス評価（キャパシタ評価）
実施例９
実施例１の低次酸化チタン８０ｗｔ％、アセチレンブラック（電気化学工業社製）１０ｗｔ％、バインダーとしてポリフッ化ビニリデン（クレハ社製）１０ｗｔ％と適量のＮ−メチルピロリドン（キシダ化学社製）を加え、混練機で十分に混練してスラリーを作製した。そのスラリーをアルミニウム箔にドクターブレードで塗布、乾燥して評価用電極を得た。
評価用電極と対極との間に、ポリプロピレン製セパレーターを介して電極を構成し、コイン型の電池容器に入れた後、エチレンカーボネート（ＥＣ）とジメチルカーボネート（ＤＭＣ）が容量比で１：２に混合されている混合溶媒中に電解質である１ＭのＬｉＰＦ６を溶解させた電解液を注入後、電池容器を封口することで、実施例９のキャパシタ評価用電池を作製した。
C. Storage device evaluation (capacitor evaluation)
Example 9
80 wt% of low-order titanium oxide of Example 1, 10 wt% of acetylene black (manufactured by Denki Kagaku Kogyo), 10 wt% of polyvinylidene fluoride (manufactured by Kureha) and an appropriate amount of N-methylpyrrolidone (manufactured by Kishida Chemical) were added. The slurry was sufficiently kneaded with a kneader. The slurry was applied to an aluminum foil with a doctor blade and dried to obtain an electrode for evaluation.
An electrode is formed between the evaluation electrode and the counter electrode via a polypropylene separator and placed in a coin-type battery container, and then ethylene carbonate (EC) and dimethyl carbonate (DMC) are in a capacity ratio of 1: 2. After injecting an electrolytic solution in which 1M LiPF 6 as an electrolyte was dissolved in the mixed solvent, the battery container was sealed to produce a capacitor evaluation battery of Example 9.
測定条件は電圧を１．０〜２．５Ｖ、電流密度を０．１Ｃ、１Ｃと変更した条件で充放電を行い、測定を行った。電池評価は下記の式を用いて放電率を算出し、効果の確認を行った。
・放電率（％）＝（１Ｃ放電容量／０．１Ｃ放電容量）×１００
Measurement conditions were measured by charging and discharging under the condition that the voltage was changed to 1.0 to 2.5 V and the current density was changed to 0.1 C and 1 C. Battery evaluation calculated the discharge rate using the following formula, and confirmed the effect.
Discharge rate (%) = (1 C discharge capacity / 0.1 C discharge capacity) × 100
比較例４
実施例１の低次酸化チタンを比較例１の低次酸化チタンへ変更した以外は実施例９と同様の操作を行い、比較例４のキャパシタ評価用電池を作製し、評価を行った。
Comparative Example 4
The same operation as in Example 9 was performed except that the low-order titanium oxide of Example 1 was changed to the low-order titanium oxide of Comparative Example 1, and a capacitor evaluation battery of Comparative Example 4 was produced and evaluated.
実施例９と比較例４のキャパシタ評価用電池の測定結果を表２に示す。 Table 2 shows the measurement results of the capacitor evaluation batteries of Example 9 and Comparative Example 4.
実施例９と比較例４のキャパシタ評価用電池の測定結果より、実施例９のキャパシタ評価用電池の方は大幅な放電率の向上を示す結果となった。このことから、本発明で得られた低次酸化チタンは、キャパシタのみならず、燃料電池やリチウム電池等の蓄電デバイスへの適用可能であることが示唆される。
From the measurement results of the capacitor evaluation batteries of Example 9 and Comparative Example 4, the capacitor evaluation battery of Example 9 showed a significant improvement in discharge rate. This suggests that the low-order titanium oxide obtained in the present invention can be applied not only to capacitors but also to power storage devices such as fuel cells and lithium batteries.
実施例１〜８の低次酸化チタンおよび比較例１〜３の低次酸化チタンの比表面積と粉体抵抗率の測定結果を表１に示す。 Table 1 shows the measurement results of specific surface area and powder resistivity of low-order titanium oxides of Examples 1 to 8 and low-order titanium oxides of Comparative Examples 1 to 3.
Claims (7)
The method for producing low-order titanium oxide according to any one of claims 1 to 4, wherein a mixture of titanium dioxide and an organic compound as a carbon source is baked in an inert gas atmosphere.
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