WO2011010631A1 - 酸化スズ粒子及びその製造方法 - Google Patents
酸化スズ粒子及びその製造方法 Download PDFInfo
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- WO2011010631A1 WO2011010631A1 PCT/JP2010/062162 JP2010062162W WO2011010631A1 WO 2011010631 A1 WO2011010631 A1 WO 2011010631A1 JP 2010062162 W JP2010062162 W JP 2010062162W WO 2011010631 A1 WO2011010631 A1 WO 2011010631A1
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- C01G19/00—Compounds of tin
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- the present invention relates to a novel tin oxide particle and a method for producing the same.
- a method for imparting conductivity to a non-conductive material such as plastic a method of adding conductive powder to the plastic is known.
- the conductive powder for example, tin powder doped with metal powder, carbon black, antimony or the like is known.
- the resulting plastic becomes black, which may limit the use of the plastic.
- tin oxide doped with antimony or the like is added to the plastic, the plastic becomes blue-black, and the use of the plastic may be limited as in the case of carbon black.
- antimony There is also a problem of environmental load caused by the use of antimony. Therefore, various studies have been made on tin oxide not containing a dopant such as antimony.
- Patent Document 1 describes an alkali-stable tin oxide sol having a particle diameter of 30 nm or less and containing tetramethylammonium hydroxide in an NH 3 / SnO 2 molar ratio in the range of 0.01 to 0.3.
- This tin oxide sol is produced by adding tetramethylammonium hydroxide to an alkali-type tin oxide sol having a tin oxide concentration of SnO 2 of 15% by mass or less and concentrating.
- Tin dioxide precursor particles have been proposed (see Patent Document 3).
- This precursor particle has a sharp peak at about 9 ° in the XRD measurement. According to the document, this peak is derived from a flaky particle shape.
- the tin oxide particles produced by the above-described technologies have sufficient transparency and conductivity when they are used as a film.
- divalent tin oxide having an orthorhombic crystal structure with an a-axis of 0.5 nm, a b-axis of 0.572 nm, and a c-axis of 0.1112 nm has been reported.
- Refer nonpatent literature 1 There is also a report on the space group of tin oxide in this document. Based on these data, when the present inventors calculated the X-ray diffraction peak of this tin oxide, it turned out that it shows a peak at about 28 degrees. It was also found that there was a peak due to the internal structure at about 60 ° or more. However, the document states that this tin oxide is unstable and easily changes to tin oxide having other structures. In addition, the literature does not report any conductivity or transparency of the tin oxide.
- An object of the present invention is to provide tin oxide particles that can eliminate the various drawbacks of the above-described conventional technology and a method for producing the same.
- the present invention is also a preferred method for producing the tin oxide particles.
- An object of the present invention is to provide a method for producing tin oxide particles, which comprises mixing an aqueous solution containing tin (II) and an organic compound having a hydroxyl group with an alkali and heating.
- the present invention is another preferred method for producing the tin oxide particles, It is characterized by mixing an alkali in such an amount that 0.1 to 1.6 times the number of moles of OH ⁇ is produced with respect to the number of moles of tin (II) while the aqueous solution containing tin (II) is heated.
- a method for producing tin oxide particles is provided.
- tin oxide particles having high conductivity and transparency when formed into a film are provided.
- FIG. 1 is an XRD measurement diagram of tin oxide particles obtained in Examples 1 to 5.
- FIG. 2 shows the results of X-ray diffraction measurement of the tin oxide particles obtained in Example 1 using the large synchrotron radiation facility SPring-8.
- FIG. 3 is an XRD measurement diagram of tin oxide particles obtained in each comparative example.
- FIG. 4 is a graph showing a charge / discharge state of a lithium secondary battery using the tin oxide particles obtained in Example 1 as a negative electrode active material.
- FIG. 5 is a graph showing a charge / discharge state of a lithium secondary battery in which tin oxide particles obtained in Example 1 and lithium nitrate are mixed and baked in the atmosphere at 400 ° C. as a positive electrode active material.
- FIG. 6 is an XRD measurement diagram of the tin oxide particles obtained in Examples 10 to 18.
- Conventionally known tin oxides such as SnO 2 and SnO do not have diffraction peaks at all these angles. That is, tin oxide particles having diffraction peaks at these angles have not been known so far, and the tin oxide particles of the present invention are extremely novel.
- Conventionally known conductive tin oxide is generally doped with tetravalent tin by doping with dopant elements such as antimony, niobium and tantalum.
- dopant elements such as antimony, niobium and tantalum.
- the crystalline state of tin oxide is controlled. By doing so, conductivity is increased.
- An oxide composed only of divalent tin has conductivity but becomes black, and cannot be used for applications requiring transparency, such as a transparent conductive film.
- an oxide made of only tetravalent tin cannot have higher conductivity than an oxide made of only divalent tin.
- the tin oxide particles of the present invention are white, can be used for a transparent conductive film and the like, and have high conductivity, so that the conductivity of the transparent conductive film and the like can be increased. .
- the strong peaks are the 9 ⁇ 1 ° and 28 ⁇ 1 ° peaks described above.
- the inventors of the present invention believe that the tin oxide of the present invention has a crystal structure of a layer structure that has a spatial fluctuation with a long period structure or the like existing in the crystal plane as a trigger. I guess.
- the distance between crystal planes corresponding to the first-order system reflection described above was measured.
- the value was 0.94 to 0.95 nm, and the standard deviation was less than 1 ⁇ 10 ⁇ 4 nm. It turned out to be. This strongly suggests that the crystal structure of the tin oxide particles of the present invention is the above-described layer structure.
- Another feature of the tin oxide particles of the present invention is that the 9 ⁇ 1 ° and 28 ⁇ 1 ° peaks described above are very sharp. The sharpness of the peak reflects the high crystallinity. That is, the tin oxide particles of the present invention are highly crystalline. Despite the high crystallinity, regarding the above-described system reflection, the tin oxide particles of the present invention do not show higher-order reflection than the sixth order in the XRD measurement. This unique observation result is also mentioned as a feature of the tin oxide particles of the present invention.
- Another feature of the tin oxide particles of the present invention is thermal behavior in a reducing atmosphere. Specifically, when heating is performed at 400 ° C. for 2 hours in a nitrogen atmosphere containing 1 to 4% hydrogen, a peak of metal Sn that has not been observed until then is observed in the XRD measurement. In some cases, SnO 2 and SnO peaks are also observed. On the other hand, even if SnO 2 or SnO is heated under the same conditions, no change is observed in the peak in the XRD measurement. As described above, the tin oxide particles of the present invention are reduced in part of tin to metallic tin by heat treatment in a reducing atmosphere, and the crystallinity of SnO 2 and SnO is improved. It has a unique property that valence Sn and tetravalent Sn coexist.
- the procedure for XRD measurement is as follows.
- RINT-TTRIII manufactured by Rigaku Corporation
- a powder X-ray glass holder dedicated to the apparatus was filled with, for example, powder prepared by the method of Example 1 described later, and XRD measurement was performed.
- the tin oxide particles of the present invention are so-called non-doped particles that contain only tin as a metal and contain only oxygen (in some cases, only oxygen and hydrogen) as other elements and do not substantially contain a dopant element. Preferably there is.
- highly conductive tin oxide particles can be obtained without using various dopant elements which are expensive and inferior in economic efficiency or have a large environmental load.
- the dopant element include those conventionally used in the technical field. Examples of such elements include Nb, Ta, Sb, W, P, Ni, and Bi.
- substantially does not contain is intended to exclude intentionally adding a dopant element, and a small amount of dopant element is inevitably mixed in the production process of tin oxide particles. This is an acceptable purpose.
- the tin oxide particles of the present invention preferably do not contain a dopant element.
- a dopant element may be contained.
- the dopant element is contained in the tin oxide particles, the amount thereof is 0.01 to 20 mol%, particularly 0.05 to 15 mol% with respect to the total amount of tin, without impairing the economy. From the point that the conductivity of the tin oxide particles can be improved.
- the dopant element that can be contained in this case include one or more of the above-described elements.
- the tin oxide particles of the present invention preferably have an average primary particle diameter of 1 to 5000 nm, particularly 3 to 3000 nm, particularly 3 to 1000 nm, as observed with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the tin oxide particles of the present invention are also characterized by high conductivity.
- the powder has a low resistance of a powder volume resistivity of 10 5 ⁇ ⁇ cm or less, particularly 10 4 ⁇ ⁇ cm or less, particularly 10 3 ⁇ ⁇ cm or less under 500 kgf. A method for measuring the powder volume resistivity will be described later.
- the tin oxide particles of the present invention are highly transparent when formed into a film.
- the total light transmittance of visible light of this film is 85% or more, particularly 90% or more, which is highly transparent. It will be a thing. The method for forming the film will be described in detail in Examples described later.
- divalent tin is used as a raw material, and this is dissolved in water together with an organic compound having a hydroxyl group to obtain a mixed aqueous solution.
- the mixed aqueous solution is heated and mixed with an alkali.
- a divalent tin water-soluble compound is prepared as a raw material.
- a water-soluble compound for example, tin (II) dichloride can be used.
- concentration of divalent tin ions in the mixed aqueous solution can be 0.01 to 3 mol / L, particularly 0.05 to 1.5 mol / L.
- tetravalent tin may be used as a raw material, with divalent tin and tetravalent tin, the target oxide can be obtained with bivalent tin than with tetravalent tin. Since it became clear as a result of examination of the present inventors that it is easy, this manufacturing method uses divalent tin as a raw material.
- an organic compound having a hydroxyl group is prepared.
- a low molecular weight compound and a high molecular compound can be used.
- a monohydric alcohol can be used.
- This monohydric alcohol may be aliphatic, alicyclic, or aromatic.
- the aliphatic monohydric alcohol include methanol, ethanol, n-butanol and n-hexanol, which are monohydric alcohols having 1 to 6 carbon atoms.
- Examples of the alicyclic monohydric alcohol include cyclohexanol and terpineol.
- aromatic monovalent alcohols include benzyl alcohol.
- examples of the polymer organic compound having a hydroxyl group include polyvinyl alcohol and polyol.
- polyvinyl alcohol unmodified polyvinyl alcohol itself and modified polyvinyl alcohol can be used.
- modified polyvinyl alcohol for example, carboxyl group-modified, alkyl-modified, acetoacetyl-modified, acrylic acid-modified, methacrylic acid-modified, pyrrolidone-modified, vinylidene-modified or silanol-modified polyvinyl alcohol can be used.
- SEC size exclusion chromatography
- the polyol ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, hexanediol, glycerol, hexanetriol, butanetriol, and petriol can be used.
- Cellosolves such as methoxyethanol, ethoxyethanol, propoxyethanol, and butoxyethanol
- carbitols such as methoxyethoxyethanol, ethoxyethoxyethanol, propoxyethoxyethanol, and butoxyethoxyethanol
- the concentration of the organic compound having a hydroxyl group in the mixed aqueous solution is preferably 0.005 to 30% by weight, particularly 0.01 to 10% by weight. Within this range, the effect of the organic compound having a hydroxyl group is sufficiently exhibited, and problems such as thickening are unlikely to occur, and target tin oxide particles having a uniform particle size can be successfully obtained. For the same reason, when the organic compound having a hydroxyl group is a polymer compound, the concentration of the organic compound is preferably 0.005 to 10% by weight, particularly 0.01 to 5% by weight.
- the ratio of divalent tin to the organic compound having a hydroxyl group in the mixed aqueous solution is preferably 0.01 to 150, particularly preferably 0.03 to 75, expressed as Sn / OH (molar ratio). Within this range, it is difficult for unreacted Sn ions to remain in the liquid, and SnO 2 or tin oxyhydroxide [Sn 3 O 2 (OH) 2 ] as a by-product is difficult to precipitate.
- the mixed aqueous solution is heated.
- the heating temperature is preferably 50 to 105 ° C, particularly 70 to 100 ° C. If the heating temperature is within this range, the target tin oxide particles can be obtained without using a pressurizing device such as an autoclave and while preventing the generation of unintended products SnO and SnO 2. .
- alkali basic substance
- divalent tin is neutralized.
- alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide, carbonates such as NaHCO 3 and NH 4 HCO 3 , ammonia, and the like. Can be mentioned.
- the pH of the aqueous alkali solution is preferably such that the pH of the mixed aqueous solution after addition of the alkali is 2 to 9, particularly 2.5 to 7. If the pH of the mixed aqueous solution is within this range, target tin oxide particles can be obtained in a single phase.
- the aqueous alkali solution When adding an aqueous alkali solution to a mixed aqueous solution of divalent tin and an organic compound having a hydroxyl group, the aqueous alkali solution is preferably added gradually over a predetermined time. When alkaline aqueous solutions are added all at once, the target tin oxide particles may not be generated, so care must be taken. When the alkaline aqueous solution is gradually added, it is preferable to adjust the addition rate of the alkaline aqueous solution so that the pH of the mixed aqueous solution is maintained within the above-described range.
- target tin oxide particles are produced in the liquid.
- tin oxyhydroxide may coexist as a by-product. Therefore, it is preferable to add hydrogen peroxide to the liquid for the purpose of removing this by-product.
- hydrogen peroxide By the addition of hydrogen peroxide, the oxidation of tin oxyhydroxide proceeds to produce tin dioxide.
- the produced tin dioxide is fine and can be separated by a water tank using the difference in sedimentation speed. In this case, the precipitate is the target tin oxide particles, and the supernatant suspension is SnO 2 .
- SnO 2 is alkaline and disperses, for example, NH 4 OH is used to adjust the pH of the solution to 8 or more and less than 11, and when SnO 2 is highly dispersed by high-speed stirrer or ultrasonic irradiation and water pouring is performed, the separation efficiency increases.
- hydrogen peroxide is preferably added as an aqueous solution diluted to a predetermined concentration. From this viewpoint, the concentration of diluted hydrogen peroxide is preferably about 1 to 15% by weight.
- the tin oxide particles obtained in this way can be easily removed with impurities by, for example, repulp washing. Cleaning is preferably performed until the conductivity of water as a dispersion medium is 2000 ⁇ S or less, particularly 1000 ⁇ S or less, from the viewpoint of sufficient removal of impurities.
- tin oxide sol is obtained.
- a media mill such as a bead mill can be used.
- tin oxide particles can be easily brought close to a monodispersed state by adding various pH adjusters to the liquid and performing a granulation operation.
- pH adjusters examples include acids such as inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, etc.) and carboxylic acids (acetic acid, propionic acid, etc.), and alkalis such as organic amines represented by aqueous ammonia and ethanolamine.
- acids such as inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, etc.) and carboxylic acids (acetic acid, propionic acid, etc.)
- alkalis such as organic amines represented by aqueous ammonia and ethanolamine.
- a tin oxide sol using water as a dispersion medium is obtained.
- This tin oxide sol is in a state of a transparent dispersion having high storage stability.
- the concentration of tin oxide particles in the tin oxide sol is preferably 0.1 to 50% by weight, particularly 1 to 40% by weight. In this tin oxide sol, tin oxide particles are highly dispersed.
- the oxide of tin is generated in the liquid (in water), there is less aggregation and high dispersibility compared to the conventional method in which the tin oxide obtained by firing is pulverized and then solated. A tin oxide sol can be easily obtained.
- a monodispersed transparent dispersion liquid can be prepared by dispersing the tin oxide particles of the present invention in an organic solvent.
- an organic solvent for example, polyhydric alcohol, monoalcohol, cellosolve, carbitol, ketone, or a mixed solvent thereof can be used.
- the concentration of tin oxide particles in the transparent dispersion is preferably 0.1 to 50% by weight, particularly 1 to 40% by weight.
- This transparent dispersion has high storage stability.
- This transparent dispersion can be used as an ink raw material, for example, by adding a binder thereto.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, hexanediol, glycerol, hexanetriol, butanetriol, petriol, glycerin and the like.
- monoalcohol examples include methanol, ethanol, propanol, pentanol, hexanol, octanol, nonanol, decanol, terpineol, benzyl alcohol, and cyclohexanol.
- Examples of cellosolve include methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol and the like.
- carbitol examples include methoxyethoxyethane, ethoxyethoxyethanol, propoxyethoxyethanol, butoxyethoxyethanol and the like.
- Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diacetone alcohol and the like.
- the heat treatment is performed in an oxygen-containing atmosphere such as an air atmosphere, preferably at 60 to 350 ° C., more preferably 120 to 300 ° C., preferably 0.5 to 24 hours, more preferably 1 to 10 hours.
- This heat treatment does not change the crystal structure of the tin oxide particles of the present invention (for example, see XRD of Example 1 in FIG. 1 and XRD of Example 18 in FIG. 6 described later).
- an organic compound having a hydroxyl group is used in combination in the synthesis of the target tin oxide, but instead of this method, a method not using an organic compound having a hydroxyl group can be employed.
- the aqueous solution containing tin (II) is heated, preferably 0.1 to 1.6 times, more preferably 0.3 to 1.4 times the number of moles of tin (II).
- An amount of alkali (base) is mixed in such an amount that doubles the number of moles of OH ⁇ is produced.
- the aqueous solution containing tin (II) used in this production method the same aqueous solution containing tin (II) used in the production method described above can be used. The same applies to the alkali.
- an aqueous solution containing tin (II) (this aqueous solution does not contain an organic compound having a hydroxyl group) is heated.
- the heating temperature is preferably 50 to 105 ° C, particularly 70 to 100 ° C.
- An alkali is added while the aqueous solution is heated to a temperature in this range.
- divalent tin is neutralized.
- the amount of alkali added when neutralizing divalent tin is important. In detail, it is necessary to add the alkali of the range mentioned above. This addition amount is smaller than the addition amount of alkali used in the above-described method in which the organic compound having a hydroxyl group is used in combination.
- aqueous alkali solution When adding an aqueous alkali solution to a divalent tin aqueous solution, it is preferable to gradually add the aqueous alkali solution over a predetermined period of time in the same manner as described above in combination with the organic compound having a hydroxyl group. . In this case, it is preferable to maintain the pH of the divalent tin aqueous solution at 2 to 9, particularly 2.5 to 7.
- the tin oxide particles obtained in this way can be used, for example, in the fields of printers and copier-related charging rollers, photosensitive drums, toners, electrostatic brushes, flat panel displays, CRTs, Can be applied to a wide range of applications such as paints, inks, and emulsions. Further, taking advantage of the fact that the crystal structure of tin oxide is a layered structure, it can be used as a raw material for a positive electrode active material, a negative electrode active material, and a gas fixing material of a lithium secondary battery.
- the tin oxide particles are used as a raw material for the positive electrode active material
- the tin oxide particles are mixed with a lithium-containing compound (for example, lithium nitrate) and then baked in an air atmosphere to form a lithium tin composite oxide.
- a lithium-containing compound for example, lithium nitrate
- This lithium tin composite oxide is used as the positive electrode active material.
- Example 1 4.51 g of sodium hydroxide was dissolved in 418 g of pure water to prepare an aqueous alkali solution for neutralization.
- 383 g of pure water was placed in a beaker, and 14.97 g of tin dichloride dihydrate was dissolved to obtain a tin aqueous solution.
- the PVA aqueous solution prepared previously was added in total to the tin aqueous solution and mixed well. A mother liquor was thus obtained.
- the mother liquor was heated to 90 ° C. while stirring with a paddle blade, and the entire amount of the previously prepared alkaline aqueous solution was fed with a tube pump over 90 minutes (feed rate: about 5 mL / min). At this time, the pH of the mother liquor was 3-4. After completion of the addition of the alkaline aqueous solution, aging was performed for 5 minutes, and then a total amount of an aqueous solution in which 7.5 g of 30% hydrogen peroxide solution was diluted with 30 g of pure water was fed at a rate of 5 mL / min. Thereafter, aging was performed for 5 minutes to obtain a target sol of tin oxide particles. The pH of the sol at this time was 2 to 3.
- the sol was filtered using a filter paper (Advantech 5C). After filtration, 1 L of pure water was added and washed with water. The cake thus obtained was repulped into pure water, and again filtered and washed with water. This operation was repeated three times to wash the target product.
- the washed cake was dried in the air with a hot air dryer set at 120 ° C. for 10 hours, crushed with an agate mortar, and then classified with a SUS mesh having an opening of 75 ⁇ m. Elemental analysis was performed on the powder thus obtained. The results are shown in Table 1 below. In this elemental analysis, tin, silicon and iron were quantified using ICP (SPS-3000 / SII Nanotechnology).
- X-ray diffraction measurement was performed using a large synchrotron radiation facility SPring-8 of the Research Center for High-Intensity Optical Science for the purpose of examining the internal structure of the crystal. .
- the wavelength of the X-ray used for the measurement is 0.0501326 nm.
- the measurement sample was filled in a glass capillary tube. At this time, the sample was loosely filled without being oriented in a specific direction.
- the diffraction lines were recorded using a Debye-Scherrer camera and converted to 2 ⁇ and intensity. The result is shown in FIG. In the figure, the peak at the position indicated by the downward triangle corresponds to the peak at the position indicated by the white circle in FIG.
- Example 2 Tin oxide particles were obtained in the same manner as in Example 1 except that 0.5 g of ethanol was used instead of PVA used in Example 1. The same measurement as in Example 1 was performed on the tin oxide particles. The results are shown in FIG.
- Example 3 Tin oxide particles were obtained in the same manner as in Example 1 except that 0.5 g of n-butanol was used instead of PVA used in Example 1. The same measurement as in Example 1 was performed on the tin oxide particles. The results are shown in Table 2.
- Example 4 Tin oxide particles were obtained in the same manner as in Example 1 except that 0.5 g of hexanol was used instead of PVA used in Example 1. The same measurement as in Example 1 was performed on the tin oxide particles. The results are shown in FIG.
- Example 5 Tin oxide particles were obtained in the same manner as in Example 1 except that 0.5 g of benzyl alcohol was used instead of PVA used in Example 1. The same measurement as in Example 1 was performed on the tin oxide particles. The results are shown in FIG.
- Example 1 Tin oxide particles were obtained in the same manner as in Example 1 except that PVA used in Example 1 was not used. The same measurement as in Example 1 was performed on the tin oxide particles. The results are shown in FIG.
- Comparative Example 2 In Comparative Example 1, tin oxide particles were obtained in the same manner as in Example 1 except that the reaction was performed at room temperature (25 ° C.) without heating the mother liquor. The same measurement as in Example 1 was performed on the tin oxide particles. The results are shown in FIG. Further, the elemental analysis described above was performed on the tin oxide particles. The results are shown in Table 3.
- the tin oxide particles obtained in each example have five peaks at the same position.
- the tin oxide particles obtained in each comparative example show only the SnO 2 diffraction peak as shown in FIG. 3 (Comparative Example 2), or the SnO 2 diffraction peak and other diffraction peaks. (Comparative Example 1).
- the tin oxide particles obtained in each example have higher conductivity than the tin oxide particles obtained in each comparative example.
- the thin film obtained from the tin oxide particle obtained by each Example has high transparency compared with the thin film obtained from the tin oxide particle obtained by each comparative example.
- Example 6 it is clarified that the tin oxide particles of the present invention are useful as a negative electrode active material for a lithium secondary battery.
- 2.85 g of tin oxide particles obtained in Example 1, 0.15 g of acetylene black, and 0.33 g of polyvinylidene fluoride were weighed and mixed, and then 3 g of N-methyl-2-pyrrolidinone was added.
- a slurry was obtained by mixing with a stirring defoamer (manufactured by Sinky Corporation). This slurry was applied to one side of a 18 ⁇ m thick Cu foil and then dried at 120 ° C. After drying, it was cut into a width of 6 cm and pressed with a roll press for 2 tons.
- a negative electrode was punched into a circle of ⁇ 14 mm and vacuum dried at 120 ° C. overnight to obtain a negative electrode.
- the amount of tin oxide particles (negative electrode active material) in the negative electrode was equivalent to 6 mg / cm 2 .
- Li foil was used for the counter electrode, and a solution of 1 mol / L LiPF 6 dissolved in a 1: 1 volume% mixed solvent of ethylene carbonate and diethyl carbonate was used as the electrolyte.
- a CR2032-type coin cell was produced in a glove box in an Ar atmosphere. A charge / discharge test was performed on the obtained coin cell.
- the charging condition is that the battery is charged to 0.0 V (vs.
- Example 7 it is clarified that the tin oxide particles of the present invention are useful as a raw material for a positive electrode active material of a lithium secondary battery. 6.00 g of tin oxide particles obtained in Example 1 and 2.61 g of LiNO 3 were mixed well in a mortar and filled into an alumina boat. Firing in the atmosphere at 400 ° C. for 5 hours gave a positive electrode active material composed of a lithium tin composite oxide.
- this positive electrode active material 0.15 g of acetylene black and 0.33 g of polyvinylidene fluoride were weighed and mixed, and then 3 g of N-methyl-2-pyrrolidinone was added, followed by stirring and defoaming machine (Sinky To obtain a slurry.
- the slurry was applied to one surface of an Al foil having a thickness of 18 ⁇ m and then dried at 120 ° C. After drying, it was cut into a width of 6 cm and pressed with a roll press for 2 tons. Next, it was punched into a circle of ⁇ 14 mm and vacuum dried at 120 ° C. overnight to obtain a positive electrode.
- the amount of the positive electrode active material in this positive electrode was equivalent to 6 mg / cm 2 .
- a CR2032-type coin cell was produced in a glove box in an Ar atmosphere. A charge / discharge test was performed on the obtained coin cell. As charging conditions, the battery was charged to 4.8 V (vs.
- Example 8 a transparent dispersion using an organic solvent as a dispersion medium was prepared using the tin oxide particles of the present invention.
- a 50 mL sealed container made of polypropylene 1.57 g of the tin oxide particles obtained in Example 1, 18 g of ethylene glycol, and 140 g of zirconia beads having a diameter of 0.1 mm were pulverized for 3 hours using a paint shaker. After pulverization, the bead and the slurry were solid-liquid separated by filtration under reduced pressure to obtain a transparent dispersion having a beige color. This solution remained in a highly dispersed state without precipitation even after being stored at room temperature for 1 month. The solid concentration when dried at 200 ° C. was 8% by weight, and a glassy solid remained.
- Example 9 a transparent dispersion using water as a dispersion medium was prepared using the tin oxide particles of the present invention.
- a transparent dispersion using water as a dispersion medium was prepared using the tin oxide particles of the present invention.
- 1.39 g of the tin oxide particles obtained in Example 1 16 g of water, and 140 g of zirconia beads having a diameter of 0.1 mm were pulverized for 3 hours using a paint shaker. After pulverization, the beads and the slurry were separated into solid and liquid by vacuum filtration.
- the pH of the obtained dispersion was 5.4. When a small amount of acetic acid was added to this slurry and the pH was adjusted to 3.0, a light beige transparent dispersion was obtained. This solution remained in a highly dispersed state without precipitation even after being stored at room temperature for 1 month.
- the solid content concentration when dried at 200 ° C. was 7% by weight, and a vitreous solid content remained.
- Example 10 Tin oxide particles were obtained in the same manner as in Example 1 except that 12.58 g of anhydrous tin dichloride was used instead of 14.97 g of tin dichloride dihydrate of Example 1. The XRD measurement similar to Example 1 was performed about this tin oxide particle. The result is shown in FIG.
- Example 11 In Example 10, tin oxide particles were obtained in the same manner as in Example 10 except that the amount of PVA added was increased to 5.0 g. The XRD measurement similar to Example 1 was performed about this tin oxide particle. The result is shown in FIG.
- Example 15 tin oxide particles were obtained in the same manner as in Example 10 except that PVA was not added and the amount of sodium hydroxide used was reduced to 2.65 g. The XRD measurement similar to Example 1 was performed about this tin oxide particle. The result is shown in FIG.
- Example 16 In Example 13, instead of the tin aqueous solution, tantalum was obtained in the same manner as in Example 13 except that 12.57 g of anhydrous tin dichloride and 0.016 g of tantalum pentachloride were dissolved and a mixed aqueous solution containing tin and tantalum was used. Doped tin oxide particles were obtained. The obtained particles were dried at 120 ° C. in the air for 10 hours, and classified with a SUS mesh having an opening of 75 ⁇ m. The XRD measurement similar to that in Example 1 was performed on the powder thus obtained. The crystal spacing, dust resistance, and total light transmittance of the thin film were measured in the same manner as in Example 1. The results are shown in FIG.
- Example 17 The powder obtained in Example 16 was baked in an electric furnace at 300 ° C. for 2 hours in the air. The XRD measurement similar to Example 1 was performed about the powder after baking. The crystal spacing, dust resistance, and total light transmittance of the thin film were measured in the same manner as in Example 1. The results are shown in FIG.
- Example 18 This example was performed for the purpose of comparison with Example 17.
- the powder obtained in Example 1 was baked in an electric furnace at 300 ° C. for 2 hours in the air.
- the XRD measurement similar to Example 1 was performed about the powder after baking.
- the crystal spacing, dust resistance, and total light transmittance of the thin film were measured in the same manner as in Example 1. The results are shown in FIG.
- Example 18 Comparing the dust resistance of Example 18 shown in Table 4 with the dust resistance of Example 1 shown in Table 2 above, Example 18 obtained by heat-treating the tin oxide of Example 1 at a high temperature was obtained. It can be seen that tin oxide shows better conductivity. Moreover, when the dust resistance of Example 16 shown in Table 4 is compared with the dust resistance of Example 17, it turns out that the electroconductive improvement by high temperature heat processing becomes more remarkable by doping with tantalum.
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Abstract
Description
スズ(II)及び水酸基を有する有機化合物を含む水溶液とアルカリとを混合し、加熱を行うことを特徴とする酸化スズ粒子の製造方法を提供するものである。
スズ(II)を含む水溶液を加熱した状態下に、スズ(II)のモル数に対して0.1~1.6倍のモル数のOH-が生じる量のアルカリを混合することを特徴とする酸化スズ粒子の製造方法を提供するものである。
い。つまり、これらの角度に回折ピークを有する酸化スズ粒子はこれまで知られておらず、本発明の酸化スズ粒子は極めて新規なものである。
・測定範囲 2θ(deg./CuKα)=5~90°
・管電圧=50kV
・管電流=300mA
・サンプリング角=0.02°
・走査速度=4°/min
4.51gの水酸化ナトリウムを418gの純水に溶解し、中和用のアルカリ水溶液を調製した。これとは別に、純水100gが入った200mLのビーカーに、ポリビニルアルコール(平均重合度 n=1500~1800 部分けん化型、以下「PVA」という。)0.5gを加え、60℃に加熱しながら溶解させてPVA水溶液を得た。別にビーカーに383gの純水を入れ、二塩化スズ二水和物14.97gを溶解させてスズ水溶液を得た。次いで、先に準備したPVA水溶液を、このスズ水溶液に全量加え、十分に混合した。このようにして母液を得た。
2θ=9°から59°までの範囲に観察される上述の5本のピークを、それぞれ001、002、003、005、006であると解釈することにより、面間隔を最小二乗法により決定した。
得られた酸化スズ粒子を圧力500kgfで圧縮して得られたサンプルについて、三菱化学株式会社製ロレスタPAPD-41を用い、四端子法に従い抵抗を測定した。
酸化スズ粒子7.4gを市販のアクリル樹脂6.4gとともにトルエン:ブタノール=7:3(重量比)混合溶液10gに添加し、ペイントシェーカを用いてビーズ分散して分散液を調製した。この分散液をPETフィルムに塗布し、1時間風乾して透明薄膜を形成した。この薄膜の膜厚を電子顕微鏡で観察したところ2μmであった。この薄膜を日本電色工業社の光線透過率測定装置NDH-1001DPを用いて全光線透過率を測定した。
実施例1で用いたPVAに代えて、0.5gのエタノールを用いた以外は実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様の測定を行った。その結果を図1及び表2に示す。
実施例1で用いたPVAに代えて、0.5gのn-ブタノールを用いた以外は実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様の測定を行った。その結果を表2に示す。
実施例1で用いたPVAに代えて、0.5gのヘキサノールを用いた以外は実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様の測定を行った。その結果を図1及び表2に示す。
実施例1で用いたPVAに代えて、0.5gのベンジルアルコールを用いた以外は実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様の測定を行った。その結果を図1及び表2に示す。
実施例1で用いたPVAを用いなかった以外は実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様の測定を行った。その結果を図3及び表2に示す。
比較例1において母液を加熱せず室温(25℃)で反応を行った以外は実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様の測定を行った。その結果を図3及び表2に示す。また、この酸化スズ粒子について、先に述べた元素分析を行った。その結果を表3に示す。
本実施例では、本発明の酸化スズ粒子が、リチウム二次電池の負極活物質として有用であることを明らかにする。実施例1で得られた酸化スズ粒子2.85gと、アセチレンブラック0.15gと、ポリフツ化ビニリデン0.33gとを秤量し、これらを混合した後に3gのN-メチル-2-ピロリジノンを加え、攪拌脱泡機(シンキー社製)で混合してスラリーを得た。このスラリーを18μm厚のCu箔の一面に塗布した後、120℃で乾燥させた。乾燥後、6cm幅に裁断し、ロールプレスで2ton加圧した。次いでφ14mmの円形に打ち抜き、120℃で一晩真空乾燥して負極を得た。この負極における酸化スズ粒子(負極活物質)の量は6mg/cm2に相当した。対極にLi箔を用い、また電解液として、エチレンカーボネートとジエチルカーボネートの1:1体積%混合溶媒に1mol/LのLiPF6を溶解した溶液を用いた。これらを用いて、CR2032タイプのコインセルを、Ar雰囲気中のグローブボックス内で作製した。得られたコインセルについて充放電試験を行った。充電条件は、定電流(0.175mA/cm2)にて0.0V(対Li+/Li)まで充電し、その後、0.0Vの定電圧にて、電流密度が0.035mA/cm2以下となるまで充電した。放電条件は、定電流(0.175mA/cm2)にて2.5V(対Li+/Li)まで放電した。その結果を図4に示す。同図に示すように、本発明の酸化スズ粒子は充放電容量を有し、リチウム二次電池の負極活物質として有用であることが明らかとなった。
本実施例では、本発明の酸化スズ粒子が、リチウム二次電池の正極活物質の原料として有用であることを明らかにする。実施例1で得られた酸化スズ粒子6.00gと、2.61gのLiNO3とを乳鉢でよく混合し、アルミナボートに充填した。大気中で400℃×5時間焼成し、リチウムスズ複合酸化物からなる正極活物質を得た。この正極活物質2.85gと、アセチレンブラック0.15gと、ポリフツ化ビニリデン0.33gとを秤量し、これらを混合した後に3gのN-メチル-2-ピロリジノンを加え、攪拌脱泡機(シンキー社製)で混合してスラリーを得た。このスラリーを18μm厚のAl箔の一面に塗布した後、120℃で乾燥させた。乾燥後、6cm幅に裁断し、ロールプレスで2ton加圧した。次いでφ14mmの円形に打ち抜き、120℃で一晩真空乾燥して正極を得た。この正極における正極活物質の量は6mg/cm2に相当した。これを正極活物質とし、対極にLi箔を用い、また電解液として、エチレンカーボネートとジエチルカーボネートの1:1体積%混合溶媒に1mol/LのLiPF6を溶解した溶液を用いた。これらを用いて、CR2032タイプのコインセルを、Ar雰囲気中のグローブボックス内で作製した。得られたコインセルについて充放電試験を行った。充電条件は、定電流(0.175mA/cm2)にて4.8V(対Li+/Li)まで充電し、その後、4.8Vの定電圧にて、電流密度が0.035mA/cm2以下となるまで充電した。放電条件は、定電流(0.175mA/cm2)にて2.7V(対Li+/Li)まで放電した。その結果を図5に示す。同図に示すように、本発明の酸化スズ粒子は充放電容量を有し、リチウム二次電池の正極活物質として有用であることが明らかとなった。
本実施例では、本発明の酸化スズ粒子を用いて有機溶媒を分散媒とする透明分散液を調製した。50mLのポリプロピレン製の密閉容器に、実施例1で得られた酸化スズ粒子1.57gとエチレングリコール18gとφ0.1mmのジルコニアビーズ140gとを入れ、ペイントシェーカを用いて3時間粉砕した。粉砕後、減圧濾過によってビーズとスラリーを固液分離し、ベージュ色をした透明分散液を得た。この液は、常温中で1ケ月保存した後も沈殿を生じることなく高分散状態を維持したままであった。200℃で乾燥させたときの固形分濃度は8重量%であり、ガラス質の固形分が残存していた。
本実施例では、本発明の酸化スズ粒子を用いて水を分散媒とする透明分散液を調製した。50mLのポリプロビレン製の密閉容器に、実施例1で得られた酸化スズ粒子1.39gと水16gとφ0.1mmのジルコニアビーズ140gとを入れ、ペイントシェーカを用いて3時間粉砕した。粉砕後、減圧濾過によってビーズとスラリーを固液分離した。得られた分散液のpHは5.4であった。このスラリーに酢酸を少量添加し、pHを3.0に調整したところ、淡いベージュ色をした透明分散液を得た。この液は、常温中で1ケ月保存した後も沈殿を生じることなく高分散状態を維持したままであった。200℃で乾燥させたときの固形分濃度は7重量%であり、ガラス質の固形分が残存していた。
実施例1の二塩化スズ二水和物14.97gの代わりに、無水二塩化スズ12.58gを使用した以外は、実施例1と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様のXRD測定を行った。その結果を図6に示す。
実施例10において、PVAの添加量を5.0gに増量した以外は、実施例10と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様のXRD測定を行った。その結果を図6に示す。
実施例11において、PVAとして平均重合度n=500の部分けん化型PVA(けん化度=)を用いた以外は、実施例11と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様のXRD測定を行った。その結果を図6に示す。
実施例11において、PVAとして平均重合度n=400~600の完全けん化型PVAを用いた以外は、実施例11と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様のXRD測定を行った。その結果を図6に示す。
実施例11において、PVAとして平均重合度n=900~1100の完全けん化型PVAを用いた以外は、実施例11と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様のXRD測定を行った。その結果を図6に示す。
実施例10において、PVAを添加せず、水酸化ナトリウムの使用量を2.65gに減量した以外は、実施例10と同様にして酸化スズ粒子を得た。この酸化スズ粒子について実施例1と同様のXRD測定を行った。その結果を図6に示す。
実施例13において、スズ水溶液に代えて、無水二塩化スズ12.57gと五塩化タンタル0.016gを溶解させてスズとタンタルを含む混合水溶液を用いた以外は、実施例13と同様にしてタンタルドープ酸化スズ粒子を得た。得られた粒子を120℃で大気中において10時間乾燥させ、目開き75μmのSUSメッシュで分級した。このようにして得られた粉末について、実施例1と同様のXRD測定を行った。また結晶の面間隔、圧粉抵抗及び薄膜の全光透過率を実施例1と同様に測定した。それらの結果を、図6及び表4に示す。
実施例16で得られた粉末を、電気炉で大気中300℃で2時間焼成した。焼成後の粉末について、実施例1と同様のXRD測定を行った。また結晶の面間隔、圧粉抵抗及び薄膜の全光透過率を実施例1と同様に測定した。それらの結果を、図6及び表4に示す。
本実施例は、実施例17との比較の目的で行った。実施例1で得られた粉末を、電気炉で大気中300℃で2時間焼成した。焼成後の粉末について、実施例1と同様のXRD測定を行った。また結晶の面間隔、圧粉抵抗及び薄膜の全光透過率を実施例1と同様に測定した。それらの結果を、図6及び表4に示す。
Claims (11)
- XRD測定(Cu/Kα)において、少なくとも2θ(deg)=9±1°及び28±1°に回折ピークを示す構造を有することを特徴とする酸化スズ粒子。
- 導電性を有する請求項1記載の酸化スズ粒子。
- 更に2θ(deg)=19±1°、48±1°及び59±1°に回折ピークを示す請求項1又は2記載の酸化スズ粒子。
- 前記回折ピークは、前記酸化スズの特定の結晶面に系統反射に基づくものであり、該系統反射の一次反射に対応する結晶面間隔が0.94~0.95nmである請求項1ないし3のいずれか一項に記載の酸化スズ粒子。
- ドーパント元素を実質的に含まない請求項1ないし4のいずれか一項に記載の酸化スズ粒子。
- リチウム二次電池の正極活物質材料の原料、又は負極活物質材料として用いられる請求項1ないし5のいずれか一項に記載の酸化スズ粒子。
- 請求項1記載の酸化スズ粒子が水又は有機溶媒に分散してなる透明分散液。
- 請求項1記載の酸化スズ粒子の製造方法であって、
スズ(II)及び水酸基を有する有機化合物を含む水溶液を加熱した状態下にアルカリとを混合することを特徴とする酸化スズ粒子の製造方法。 - 水酸基を有する有機化合物が、ポリビニルアルコール、ポリオール又は一価の低級アルコールである請求項8記載の酸化スズ粒子の製造方法。
- アルカリと混合した後に、更に過酸化水素を添加する請求項8又は9記載の酸化スズ粒子の製造方法。
- 請求項1記載の酸化スズ粒子の製造方法であって、
スズ(II)を含む水溶液を加熱した状態下に、スズ(II)のモル数に対して0.1~1.6倍のモル数のOH-が生じる量のアルカリを混合することを特徴とする酸化スズ粒子の製造方法。
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WO2012124499A1 (ja) * | 2011-03-16 | 2012-09-20 | 三井金属鉱業株式会社 | 塩素ドープ酸化スズ粒子及びその製造方法 |
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JP2014229539A (ja) * | 2013-05-24 | 2014-12-08 | 日本電気硝子株式会社 | 蓄電デバイス用負極活物質およびその製造方法 |
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JP2000195505A (ja) * | 1998-12-25 | 2000-07-14 | Tokuyama Corp | 非水電解液二次電池負極材料の製造方法 |
JP2008150258A (ja) * | 2006-12-19 | 2008-07-03 | Ishihara Sangyo Kaisha Ltd | 二酸化スズ前駆体粒子及びその製造方法並びにそれを用いてなる二酸化スズの製造方法 |
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WO2012098948A1 (ja) * | 2011-01-19 | 2012-07-26 | 三井金属鉱業株式会社 | 酸化スズ粒子及びその製造方法 |
US8916070B2 (en) | 2011-01-19 | 2014-12-23 | Mitsui Mining & Smelting Co., Ltd. | Tin oxide particles and method for producing same |
WO2012124499A1 (ja) * | 2011-03-16 | 2012-09-20 | 三井金属鉱業株式会社 | 塩素ドープ酸化スズ粒子及びその製造方法 |
US20140093734A1 (en) * | 2011-03-16 | 2014-04-03 | Mitsui Mining & Smelting Co., Ltd. | Fluorine-doped tin-oxide particles and manufacturing method therefor |
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JP2014169218A (ja) * | 2013-02-05 | 2014-09-18 | Mitsui Mining & Smelting Co Ltd | リンを含む酸化スズ粒子及びリンを含む酸化スズゾルの製造方法 |
JP2014229539A (ja) * | 2013-05-24 | 2014-12-08 | 日本電気硝子株式会社 | 蓄電デバイス用負極活物質およびその製造方法 |
JP2014232680A (ja) * | 2013-05-30 | 2014-12-11 | 日本電気硝子株式会社 | 蓄電デバイス用負極活物質およびその製造方法 |
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US8491822B2 (en) | 2013-07-23 |
JPWO2011010631A1 (ja) | 2012-12-27 |
JP5373884B2 (ja) | 2013-12-18 |
US20120085979A1 (en) | 2012-04-12 |
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