JP5021106B2 - 酸化チタンゾル、その製造方法、超微粒子状酸化チタン、その製造方法及び用途 - Google Patents
酸化チタンゾル、その製造方法、超微粒子状酸化チタン、その製造方法及び用途 Download PDFInfo
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- JP5021106B2 JP5021106B2 JP2012507199A JP2012507199A JP5021106B2 JP 5021106 B2 JP5021106 B2 JP 5021106B2 JP 2012507199 A JP2012507199 A JP 2012507199A JP 2012507199 A JP2012507199 A JP 2012507199A JP 5021106 B2 JP5021106 B2 JP 5021106B2
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- titanium oxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 162
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 136
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 claims description 50
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011164 primary particle Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000003989 dielectric material Substances 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 238000002296 dynamic light scattering Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006298 dechlorination reaction Methods 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011882 ultra-fine particle Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 BaTiOP 3 Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/0475—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
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Description
以上のように、従来の方法では高分散かつ高純度のアナターゼ型酸化チタンを得ることは困難であった。
(1)液相法で四塩化チタンを加水分解して酸化チタンゾルを製造する方法において、80℃以上の水にその温度を維持しながら四塩化チタン水溶液を100秒以内に混合し、混合完了後15分以内に60℃未満に冷却する工程を含むことを特徴とする酸化チタンゾルの製造方法。
(2)80℃以上の温度に維持した水にその温度を維持しながら四塩化チタン水溶液を60秒以内に混合し、混合完了後15分以内に60℃未満に冷却する工程を含む前項1に記載の酸化チタンゾルの製造方法。
(3)限外ろ過膜、逆浸透膜、イオン交換樹脂、及び電気透析膜の少なくとも一つを使用して、加水分解反応で生成した酸化チタンと塩酸を分離する脱塩素工程を含む前項1または2に記載の酸化チタンゾルの製造方法。
(4)前項1〜3の方法で得られた、酸化チタン粒子BET比表面積から換算した平均一次粒子径(DBET)が3〜8nmであり、動的光散乱法によって測定した50%累積個数粒度分布径(D50DLS)とDBETとが次式(1)
で示される関係を有することを特徴とする酸化チタンゾル。
(5)アナターゼの含有率が70%以上である前項4に記載の酸化チタンゾル。
(6)塩素(Cl)の含有率が0.1質量%以下である前項4または5に記載の酸化チタンゾル。
(7)炭素(C)、硫黄(S)、アルミニウム(Al)、珪素(Si)、及び鉄(Fe)の含有率が、それぞれ0.01質量%以下である前項4〜6のいずれかに記載の酸化チタンゾル。
(8)前項1〜3いずれかにいずれかに記載の方法で得られた酸化チタンゾル、または請求項4〜7のいずれかに記載の酸化チタンゾルを乾燥すること特徴とする超微粒子状酸化チタンの製造方法。
(9)前項8に記載の方法で得られた超微粒子状酸化チタン。
(10)前項9に記載の酸化チタンを含むことを特徴とする組成物。
(11)前項9に記載の酸化チタンを含むことを特徴とする太陽電池用材料。
(12)前項9に記載の酸化チタンを含むことを特徴とするリチウムイオン電池用電極材原料。
(13)前項9に記載の酸化チタンを含むことを特徴とする誘電体原料。
本発明による超微粒子状酸化チタンは、光触媒用途、太陽電池用途、誘電体原料用途、Liイオン電池用電極材用途などに好適であり、特別な解砕処理や分散剤が不要であり、工業的に大きな価値のあるものである。
BET1点法により、酸化チタンの比表面積S(m2/g)を測定し、下式(2)
液相法による一般的な酸化チタンの製造方法は公知であり、例えば、特許文献2(特開2004−43304号公報)などに報告されているように、四塩化チタン水溶液を、50℃以上に加熱して加水分解を行うことにより超微粒子酸化チタンゾルが得られる。
混合時間が長すぎると、反応液中の加水分解反応に時間差が生じ、1次粒子の均一性が低下するため好ましくない。
塩素(Cl):酸化チタンにフッ酸水溶液を添加しマイクロウェーブで加熱溶解させた液を硝酸銀による電位差滴定法で測定、
炭素(C):高周波誘導炉燃焼・赤外線吸収法、
硫黄(S):高周波誘導炉燃焼・赤外線吸収法、
鉄(Fe):原子吸光法、
アルミニウム(Al)及びSi:XRF(蛍光X線分析)法。
イオン交換水690mLを櫛形撹拌機付き反応槽に入れ、95℃に予熱した。撹拌は約300rpmで、加熱して温度を95℃に保ちながら、ここに室温(20℃)の四塩化チタン水溶液50g(Ti濃度18質量%)を30秒間かけて滴下し、反応槽内で撹拌混合した。水に対して四塩化チタンを滴下した直後に均一に混合されるため、滴下時間が混合時間と近似できる。投入後も混合液は95℃を4分間維持した。その反応槽を氷浴中で1分未満で50℃まで冷却した(60℃まで40秒を要した。)。反応で生じた塩酸を電気透析装置にて除去し、酸化チタンゾルを得て、100℃の乾燥機で乾燥させた後に、乳鉢にて解砕し酸化チタン粉末とした。得られた酸化チタンゾルはpH=3.5(25℃)に調整し、酸化チタン濃度を2質量%とした。この調整ゾルを動的光散乱法で平均粒子径D50 DLS の測定に使用した。酸化チタン粉末はBET比表面積測定、結晶型の同定、及び塩素(Cl)、炭素(C)、硫黄(S)、鉄(Fe)、アルミニウム(Al)、珪素(Si)の測定に使用した。測定結果をまとめて表1に示す。
イオン交換水の予熱温度80℃を保ちながら四塩化チタンを滴下したこと以外は実施例1と同様にして酸化チタンを得た。
混合液を95℃で維持する時間を混合完了後10分間としたこと以外は、実施例1と同様にして酸化チタンを得た。
反応槽のイオン交換水に四塩化チタン水溶液を60秒間かけて滴下したこと以外は、実施例1と同様にして酸化チタンを得た。
イオン交換水の予熱温度70℃を保って混合したこと以外は、実施例1と同様にして酸化チタンを得た。
混合液を95℃で維持する時間を混合完了後20分間としたこと以外は、実施例1と同様にして酸化チタンを得た。
反応槽のイオン交換水に四塩化チタン水溶液を120秒間かけて滴下したこと以外は、実施例1と同様にして酸化チタンを得た。
混合液を95℃から50℃まで冷却する時間を30分とした(1.5℃/分の一定速度で冷却した。60℃まで23分要した。)こと以外は、実施例1と同様にして酸化チタンを得た。
混合液を氷浴中で1分未満で95℃から70℃まで冷却し(70℃まで20秒要した。)、70℃のまま15分保持した後、50℃まで1分未満で冷却した(60℃まで15分以上要した。)こと以外は、実施例1と同様にして酸化チタンを得た。
石原産業株式会社製の超微粒子酸化チタンゾルSTS−01を分析した。この酸化チタンゾルはpH=2.5(25℃)に調整し、酸化チタン濃度を2質量%とした。この調整ゾルを動的光散乱法で平均粒子径D50DLSの測定に使用し、酸化チタンゾルを100℃で乾燥させて得られた酸化チタン粉末はBET比表面積測定、結晶型の同定、及びCl、C、S、Fe、Al、Siの測定に使用した。それらの分析結果をまとめて表1に示す。
Claims (12)
- 液相法で四塩化チタンを加水分解して酸化チタンゾルを製造する方法において、80℃以上の温度に維持した水にその温度を維持しながら四塩化チタン水溶液を100秒以内に混合し、混合完了後15分以内に60℃未満に冷却する工程を含むことを特徴とする酸化チタンゾルの製造方法。
- 80℃以上の温度に維持した水にその温度を維持しながら四塩化チタン水溶液を60秒以内に混合し、混合完了後15分以内に60℃未満に冷却する工程を含む請求項1に記載の酸化チタンゾルの製造方法。
- 限外ろ過膜、逆浸透膜、イオン交換樹脂、及び電気透析膜の少なくとも一つを使用して、加水分解反応で生成した酸化チタンと塩酸を分離する脱塩素工程を含む請求項1または2に記載の酸化チタンゾルの製造方法。
- 塩素(Cl)の含有率が0.1質量%以下である請求項4に記載の酸化チタンゾル。
- 炭素(C)、硫黄(S)、アルミニウム(Al)、珪素(Si)、及び鉄(Fe)の含有率が、それぞれ0.01質量%以下である請求項4または5に記載の酸化チタンゾル。
- 請求項1〜3のいずれかに記載の方法で得られた酸化チタンゾル、または請求項4〜6のいずれかに記載の酸化チタンゾルを乾燥することを特徴とする超微粒子状酸化チタンの製造方法。
- 請求項7に記載の方法で得られた超微粒子状酸化チタン。
- 請求項8に記載の超微粒子状酸化チタンを含むことを特徴とする組成物。
- 請求項8に記載の超微粒子状酸化チタンを含むことを特徴とする太陽電池用材料。
- 請求項8に記載の超微粒子状酸化チタンを含むことを特徴とするリチウムイオン電池用電極材原料。
- 請求項8に記載の超微粒子状酸化チタンを含むことを特徴とする誘電体原料。
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2017114700A (ja) * | 2015-12-21 | 2017-06-29 | 昭和電工株式会社 | 酸化チタン及びその製造方法 |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013161749A1 (ja) * | 2012-04-27 | 2013-10-31 | 昭和電工株式会社 | 二次電池用負極およびその製造方法、ならびに二次電池 |
EP3048082B1 (en) * | 2013-09-05 | 2018-05-02 | Showa Denko K.K. | Ultrafine particles of titanium dioxide and method for producing same |
JP6607407B2 (ja) * | 2014-07-02 | 2019-11-20 | 石原産業株式会社 | 微粒子酸化チタン及びその製造方法 |
CN104466147B (zh) * | 2014-11-06 | 2017-01-25 | 浙江大学 | 碳原位复合二氧化钛锂离子电池负极体材料的制备方法 |
JP6200529B2 (ja) * | 2016-01-27 | 2017-09-20 | 太平洋セメント株式会社 | 二次電池用負極活物質の製造方法 |
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KR101883076B1 (ko) * | 2016-11-30 | 2018-07-27 | 군산대학교산학협력단 | 아나타제 졸을 이용한 다공성 코팅층 형성방법 |
KR101883077B1 (ko) * | 2016-11-30 | 2018-07-27 | 군산대학교산학협력단 | 아나타제 졸 제조 장치 |
CN106892454A (zh) * | 2017-04-27 | 2017-06-27 | 合肥科佳高分子材料科技有限公司 | 一种利用电渗析技术制备水分散性二氧化钛溶胶的方法 |
CN108212033B (zh) * | 2018-01-23 | 2019-02-01 | 佛山优维士光电科技有限公司 | 一种可屏蔽185nm谱线的溶胶及其制备方法和应用 |
JP7102462B2 (ja) * | 2020-06-12 | 2022-07-19 | 日本化学工業株式会社 | シュウ酸バリウムチタニル、その製造方法及びチタン酸バリウムの製造方法 |
CN112174197B (zh) * | 2020-09-29 | 2022-05-24 | 攀钢集团研究院有限公司 | 以四氯化钛为原料制备锂电负极材料钛酸锂的方法 |
JP7110306B2 (ja) * | 2020-11-19 | 2022-08-01 | 日本化学工業株式会社 | シュウ酸バリウムチタニルの製造方法及びチタン酸バリウムの製造方法 |
JP7110305B2 (ja) * | 2020-11-19 | 2022-08-01 | 日本化学工業株式会社 | シュウ酸バリウムチタニルの製造方法及びチタン酸バリウムの製造方法 |
KR20230109634A (ko) * | 2020-11-19 | 2023-07-20 | 니폰 가가쿠 고교 가부시키가이샤 | 옥살산바륨티타닐의 제조 방법 및 티타늄산바륨의 제조 방법 |
US11253842B1 (en) | 2021-04-02 | 2022-02-22 | TiCoat, Inc. | Titanium dioxide containing peroxo titanium complex and methods of manufacturing and application of the same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0967125A (ja) * | 1995-08-30 | 1997-03-11 | Showa Denko Kk | 酸化チタン微粉末及びその製造法 |
JP2006083363A (ja) * | 2004-04-26 | 2006-03-30 | Showa Denko Kk | コーティング材とその用途 |
JP2006093037A (ja) * | 2004-09-27 | 2006-04-06 | Nippon Oil Corp | リチウム二次電池 |
JP2006179444A (ja) * | 2004-01-22 | 2006-07-06 | Showa Denko Kk | 金属酸化物分散物及びその塗布方法 |
JP2010528967A (ja) * | 2007-06-06 | 2010-08-26 | コミサリア、ア、レネルジ、アトミク、エ、オ、エネルジ、アルテルナティブ | 遷移金属酸化物のカーボンコーティングされたナノ粒子の製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4843331A (en) * | 1987-08-28 | 1989-06-27 | Hughes Aircraft Company | Coherent digital signal blanking, biphase modulation and frequency doubling circuit and methodology |
JPH0477495A (ja) * | 1990-07-18 | 1992-03-11 | Nippon Kayaku Co Ltd | オキセタノシン―3’―カルボン酸類およびその製造法 |
JP4187632B2 (ja) | 1996-08-30 | 2008-11-26 | 昭和電工株式会社 | 二酸化チタン薄膜の形成方法およびその二酸化チタン薄膜を有する触媒等 |
US6544493B1 (en) * | 1999-08-30 | 2003-04-08 | Showa Denko Kabushiki Kaisha | Ultrafine particulate titanium oxide and production process therof |
US7449166B2 (en) * | 1999-09-27 | 2008-11-11 | Showa Denko K.K. | Particulate titanium oxide and production process therefor |
US6824758B2 (en) * | 2000-09-15 | 2004-11-30 | Showa Denko K.K. | Particulate titanium oxide and production process therefor |
US7591991B2 (en) * | 2002-03-06 | 2009-09-22 | Showa Denko K.K. | Ultrafine particulate titanium oxide with low chlorine and low rutile content, and production process thereof |
WO2005071704A2 (en) | 2004-01-22 | 2005-08-04 | Showa Denko K.K. | Metal oxide dispersion, metal oxide electrode film, and dye sensitized solar cell |
ATE538073T1 (de) | 2004-04-26 | 2012-01-15 | Showa Denko Kk | Beschichtungsstoff und dessen verwendung |
TWI314919B (en) | 2005-02-28 | 2009-09-21 | Showa Denko Kk | Fine particulate titanium dioxide, and production process and uses thereof |
JP2006335619A (ja) * | 2005-06-03 | 2006-12-14 | Showa Denko Kk | 酸化チタン粒子、その製造方法及び応用 |
JP4077495B1 (ja) | 2006-11-10 | 2008-04-16 | ゆかコラボレーション株式会社 | 酸化チタン粒子分散液の製造方法 |
-
2011
- 2011-06-24 CN CN201180004458.9A patent/CN102596814B/zh active Active
- 2011-06-24 KR KR1020127007188A patent/KR101233703B1/ko active IP Right Grant
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0967125A (ja) * | 1995-08-30 | 1997-03-11 | Showa Denko Kk | 酸化チタン微粉末及びその製造法 |
JP2006179444A (ja) * | 2004-01-22 | 2006-07-06 | Showa Denko Kk | 金属酸化物分散物及びその塗布方法 |
JP2006083363A (ja) * | 2004-04-26 | 2006-03-30 | Showa Denko Kk | コーティング材とその用途 |
JP2006093037A (ja) * | 2004-09-27 | 2006-04-06 | Nippon Oil Corp | リチウム二次電池 |
JP2010528967A (ja) * | 2007-06-06 | 2010-08-26 | コミサリア、ア、レネルジ、アトミク、エ、オ、エネルジ、アルテルナティブ | 遷移金属酸化物のカーボンコーティングされたナノ粒子の製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017114700A (ja) * | 2015-12-21 | 2017-06-29 | 昭和電工株式会社 | 酸化チタン及びその製造方法 |
WO2017111150A1 (en) | 2015-12-21 | 2017-06-29 | Showa Denko K. K. | Titanium oxide and method of producing the same |
US11124427B2 (en) | 2015-12-21 | 2021-09-21 | Showa Denko K.K. | Method of producing titanium oxide |
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