WO2012156199A1 - Dispersion d'oxyde métallique à base d'un solvant organique - Google Patents

Dispersion d'oxyde métallique à base d'un solvant organique Download PDF

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Publication number
WO2012156199A1
WO2012156199A1 PCT/EP2012/057968 EP2012057968W WO2012156199A1 WO 2012156199 A1 WO2012156199 A1 WO 2012156199A1 EP 2012057968 W EP2012057968 W EP 2012057968W WO 2012156199 A1 WO2012156199 A1 WO 2012156199A1
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WO
WIPO (PCT)
Prior art keywords
weight
dispersion
metal oxide
oxide particles
proportion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2012/057968
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German (de)
English (en)
Inventor
Wolfgang Lortz
Gabriele Perlet
Uwe Diener
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to KR1020137030075A priority Critical patent/KR20140038409A/ko
Priority to EP12719664.0A priority patent/EP2709751A1/fr
Publication of WO2012156199A1 publication Critical patent/WO2012156199A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0047—Preparation of sols containing a metal oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the invention relates to a dispersion containing metal oxide particles, an alkanol and an ⁇ , ⁇ -unsaturated carboxylic acid, their preparation and their use in the preparation of dye solar cells.
  • metal oxide dispersions in particular of titanium dioxide dispersions, represents an important step in the production of
  • Dye solar cells The dispersion is applied to a conductive glass and subsequently the liquid phase of the dispersion is removed thermally.
  • WO93 / 18532 discloses that suitable solvents for such dispersions are alcohols, ethers, carboxylic acids or amines and the
  • Dispersions can be sterically stabilized by the addition of chelating agents such as acetylacetone.
  • propanol, 2-methyl-2-propanol and hexanol are mentioned in WO2005 / 071704.
  • a mixture of water and alcohol is used.
  • Alkylolammonium salt of a block copolymer with acidic, phosphorus-containing groups is used.
  • Dispersions of with lauric acid, caproic acid or sorbic acid Dispersions of with lauric acid, caproic acid or sorbic acid
  • Treatment step can not be completely removed, especially inorganic components
  • the object of the present invention was therefore a dispersion
  • Another object of the invention was to provide a process for producing this dispersion.
  • the invention relates to a dispersion containing metal oxide particles, in which
  • a1 are selected from one or more oxides of the group
  • a3) have an average aggregate diameter of 20 to 120 nm, preferably 30 to 100 nm, more preferably 40 to 90 nm, and b) the liquid phase
  • n 2 to 4, b2) from 0.5 to 10% by weight, preferably from 1 to 5% by weight, of one or more ⁇ , ⁇ -unsaturated alkylcarboxylic acids having 4 to 12 C atoms,
  • sum of dispersing additives selected from the group consisting of polyoxyethylenated alkyl ether phosphates, polyoxyethylenated aryl ether phosphates; Alkylolammonium salts of block copolymers with acidic groups; Polyalkylene glycols, polyalkyleneimines,
  • the metal oxide particles of the present invention are preferably aggregated primary particles whose surfaces have hydroxyl groups and which are largely free from micropores.
  • the BET surface area of these particles is generally between 20 and 200 m 2 / g, with values between 40 and 100 m 2 / g being particularly preferred.
  • Such aggregated primary particles can be obtained by pyrogenic methods such as flame hydrolysis or flame oxidation. Pyrogenic
  • Metal oxide particles in the context of the invention also include doped particles.
  • Particularly suitable as doping component are the oxides of aluminum or silicon.
  • Metal oxide particles can be between 10 ppm and 5 wt .-%.
  • Titanium dioxide particles are preferred. are commercially available, for example, ® AEROXIDE TiO2 P25 having a BET surface area of about 50 m 2 / g and
  • the titanium dioxide particles present in the dispersion according to the invention can be present in the rutile or anatase form or as a mixture of the two forms.
  • rutile and anatase modification are generally present.
  • the anatase / rutile content can be in range from 2:98 to 98: 2. Most preferably, the range can be from 70:30 to 95: 5.
  • the dispersion according to the invention may also contain cerium oxide particles, preferably pyrogenically prepared cerium oxide particles. Particularly preferred may be the ceria particles disclosed in EP-A-1757560 which have carbonate groups on their surface and in a near-surface layer.
  • the average aggregate diameter of the metal oxide particles is 20 to 120 nm, preferably 30 to 100 nm and particularly preferably 40 to 90 nm.
  • the values are determined by dynamic light scattering, for example by means of
  • the dispersion contains no particles with a diameter of more than 200 nm, determined for example by means of
  • alkanols C n H 2n + iOH with n 2 to 4.
  • Preferred is an embodiment in which at least 90% by volume, more preferably an embodiment in which at least 99% by volume of the Alkanoles is isopropanol or the alkanol is exclusively ispropanol.
  • the liquid phase contains one or more ⁇ , ⁇ -unsaturated carboxylic acids having 4 to 12 C atoms. They are completely soluble in the stated concentrations of 0.5 to 10 wt .-% at room temperature (23 ° C) in the liquid phase of the dispersion.
  • the ⁇ , ⁇ -unsaturated carboxylic acid may be monounsaturated or polyunsaturated.
  • the alkyl chain of the ⁇ , ⁇ -unsaturated carboxylic acids may be linear or branched. It can be a monocarboxylic acid or dicarboxylic acid.
  • the ⁇ , ⁇ -unsaturated carboxylic acid contains no further functional group, such as a hydroxy, alkoxy or amino group. It was found, that ⁇ , ⁇ -unsaturated carboxylic acids with trans-configured double bonds provide the best results in terms of sedimentation stability and viscosity. Particularly preferred may be trans-2-hexenoic acid and sorbic acid. Very particular preference is given to sorbic acid. With dispersions containing sorbic acid, a weight ratio of metal oxide particles / sorbic acid 20: 1 to 40: 1 has proved to be ideal.
  • the alkanediols can improve the physico-chemical properties with the addition of said small amounts.
  • the dispersion of the invention contains alkanediols, their proportion is preferably 0.01 to 1 wt .-% and particularly preferably 0.1 to 0.5 wt .-%, each based on the liquid phase.
  • the dispersion is free of water and of dispersing additives within the detection limit.
  • dispersing additives are those from the group consisting of
  • Aryletherphosphaten Alkylolammonium salts of block copolymers with acidic groups; Polyalkylene glycols, polyalkyleneimines, polyalkylene understood.
  • dispersion of the invention should be free of binders.
  • Binder means those substances which, in the absence of the liquid phase of the dispersion, the metal oxide particles, for example on a Substrate, fix. It is known to use such binders in the production of dye solar cells. You can the invention
  • Dispersion can be added after their preparation.
  • These may be inorganic or organic binders. Suitable organic binders such as polyacrylamide, styrene-butadiene copolymers, poly-N-vinylacetamide, poly-N-vinylformamide, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride or polyvinylpyridine.
  • Inorganic binders can also be used. These may be, for example, alkoxysilanes, partially hydrolyzed by acids alkoxysilanes, alkoxides of aluminum or titanium or zirconium salts.
  • the dispersion having a proportion of isopropanol of 95 to 99 wt .-% and sorbic acid of 1 to 5 wt .-%, each based on the liquid phase, and a proportion of metal oxide particles in the form of titanium dioxide particles with a BET surface area of 50 + 5 m 2 / g of 40 wt .-%, based on the dispersion, a viscosity of less than 750 mPas, more preferably less than 200 mPas, each at 23 ° C and a shear rate of 10 s "1 on.
  • Another object of the invention is a process for the preparation of the dispersion according to the invention, in which first a predispersion is prepared by
  • polyoxyethylenated aryl ether phosphates Alkylolammonium salts of block copolymers with acidic groups; polyalkylene
  • the predispersion feeds a high-pressure milling by dividing it into at least two partial streams, these partial streams under a pressure of at least 500 bar, preferably 2000 to 4000 bar, depressurized via a nozzle and in a gas- or liquid-filled reaction space
  • the preparation of the predispersion is not critical. Usually rotor / stator assemblies are used. The predispersion does not have to be special
  • Another object of the invention is the use of the
  • Dispersion according to the invention for the preparation of dye solar cells for the preparation of dye solar cells.
  • Light scattering about 0.1 to 1 ml of the dispersion are dissolved in about 50 ml of a solution of 50 g of deionized water, 0.5 g of citric acid, 0.7 g of 2-amino-2-methyl-propanol and one drop of a ordinary hand dishwashing detergent, such as Palmolive ®, Colgate-Palmolive by ultrasound at low power (20 W) dispersed.
  • a ordinary hand dishwashing detergent such as Palmolive ®, Colgate-Palmolive by ultrasound at low power (20 W) dispersed.
  • Example 1 To a solution of 41 kg of isopropanol, 770 g of sorbic acid and 56 g of ethylene glycol, 28 kg of AEROXIDE® TiO 2 P 25, Evonik Degussa, are added to the receiving container while the rotor / stator assembly (Ystral Conti-TDS 3) is being used. one hour added. After the addition, shear was carried out for a further 10 minutes at 3000 rpm. This predispersion is ground twice using a high-energy mill, Sugino Ultimaizer HJP-25050, at a pressure of 2500 bar, each 0.25 mm in diameter.
  • the dispersion has a solids content of 40% by weight.
  • the viscosity determined by means of the Physica MCR 300 rheometer, Anton Paar, at a temperature of 23 ° C. and a shear rate of 11.5 s -1 is 398 mPas and a shear rate of 108 s -1 is 97.8 mPas.
  • the average aggregate diameter determined by means of dynamic light scattering is 91 nm.
  • Example 2 To a solution of 47.9 kg of isopropanol, 1, 04 kg of sorbic acid and 76 g of ethylene glycol 21 kg of AEROXIDE ® TiO 2 P 90, Evonik Degussa, with the rotor / stator assembly (Ystral Conti- TDS 3) in the reservoir. added within about an hour. After the addition, shear was carried out for a further 10 minutes at 3000 rpm. This predispersion is ground three times using a high-energy mill, Sugino Ultimaizer HJP-25050, at a pressure of 2500 bar, each 0.25 mm in diameter.
  • the dispersion has a solids content of 30% by weight.
  • the viscosity determined by means of the rheometer Physica MCR 300, Anton Paar, at a temperature of 23 ° C and a shear rate of 1 1, 7 s "1 is 501 mPas and a shear rate of 108 s -1 is 154 mPas
  • the mean aggregate diameter determined by means of dynamic light scattering is 33 nm.
  • the examples show that the dispersions of the invention have a low viscosity at high solids concentration and low particle size. Their liquid components can be easily removed thermally.
  • the dispersion according to the invention is thus ideally suited for further processing in the production of dye-sensitized solar cells, for example by adding binders additionally to the dispersions.
  • the binder-containing dispersions then still have very good properties due to the excellent properties of the dispersion according to the invention
  • Carboxylic acids are dissolved in the liquid phase or the dispersions show high viscosities and are not sedimentation-stable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Dispersion contenant des particules d'oxyde métallique dans laquelle a) les particules d'oxyde métallique a1) sont sélectionnées dans un ou plusieurs oxydes du groupe constitué par le dioxyde de titane, l'oxyde de cérium, l'oxyde de zinc et le dioxyde de zirconium a2) sont présentes dans la dispersion à raison d'un pourcentage en poids d'au moins 25 %, a3) présentent un diamètre moyen de 20 à 120 nm et b) la phase liquide contient b1) 90 à 99,5 % en poids d'un ou de plusieurs alcanols CnH2 n+1OH où n = 2 à 4, b2) 0,5 à 10 % en poids d'un ou de plusieurs acides carboxyliques a, ß insaturés comportant 4 à 12 atomes C, b3) 0 à 2 % en poids d'un ou plusieurs alcane-diols HO(CH2)xOH où x = 2 à 4, b4) 5 % en poids maximum d'eau et b5) 2 % en poids maximum au total, d'additifs de dispersion du groupe constitué par les phosphates d'alkyléther polyoxyéthyléniques, les phosphates d'aryléther polyoxyéthyléniques; de sels d'alkylolammonium de copolymères séquencés contenant des groupes acides; de polyalkylènes glycols, de polyalkylèneimines, d'alcools de polyalkylène. La présente invention a par ailleurs pour objet l'utilisation de la dispersion pour la fabrication de cellules solaires à colorant.
PCT/EP2012/057968 2011-05-16 2012-05-02 Dispersion d'oxyde métallique à base d'un solvant organique Ceased WO2012156199A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020137030075A KR20140038409A (ko) 2011-05-16 2012-05-02 유기 용매계 금속 산화물 분산액
EP12719664.0A EP2709751A1 (fr) 2011-05-16 2012-05-02 Dispersion d'oxyde métallique à base d'un solvant organique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011075918A DE102011075918A1 (de) 2011-05-16 2011-05-16 Auf organischem Lösungsmittel basierende Metalloxid-Dispersion
DE102011075918.2 2011-05-16

Publications (1)

Publication Number Publication Date
WO2012156199A1 true WO2012156199A1 (fr) 2012-11-22

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EP (1) EP2709751A1 (fr)
KR (1) KR20140038409A (fr)
DE (1) DE102011075918A1 (fr)
WO (1) WO2012156199A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017125264A1 (fr) * 2016-01-18 2017-07-27 Evonik Degussa Gmbh Dispersion d'oxyde métallique dans du phosphate de trialkyle
CN114230864A (zh) * 2021-12-14 2022-03-25 南京大学 一种改性氧化锆纳米粒子醇分散体系及其制备方法和应用、紫外光固化树脂材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240079847A (ko) 2022-11-29 2024-06-05 고등기술연구원연구조합 산화아연 입자 및 산화아연 입자를 포함하는 분산액 제조 방법

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018532A1 (fr) 1992-03-11 1993-09-16 Ecole Polytechnique Federale De Lausanne (Epfl) Procede de fabrication d'une cellule photoelectrochimique et cellule realisee selon ledit procede
WO2005071704A2 (fr) 2004-01-22 2005-08-04 Showa Denko K.K. Dispersion d'oxyde metallique, film d'electrode d'oxyde metallique et pile solaire sensible aux colorants
WO2006010438A2 (fr) * 2004-07-30 2006-02-02 Degussa Ag Dispersion contenant du dioxyde de titane
WO2006067131A1 (fr) * 2004-12-22 2006-06-29 Degussa Gmbh Dispersion de dioxyde de zirconium et d'oxyde mixte de zirconium
WO2006108743A1 (fr) * 2005-04-14 2006-10-19 Degussa Gmbh Dispersion aqueuse d'oxyde de cerium
EP1757560A2 (fr) 2005-08-12 2007-02-28 Degussa AG Poudre d'oxyde de cérium et dispersion la contenant
DE102006057903A1 (de) * 2006-12-08 2008-06-12 Evonik Degussa Gmbh Titandioxid enthaltende Dispersion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018532A1 (fr) 1992-03-11 1993-09-16 Ecole Polytechnique Federale De Lausanne (Epfl) Procede de fabrication d'une cellule photoelectrochimique et cellule realisee selon ledit procede
WO2005071704A2 (fr) 2004-01-22 2005-08-04 Showa Denko K.K. Dispersion d'oxyde metallique, film d'electrode d'oxyde metallique et pile solaire sensible aux colorants
WO2006010438A2 (fr) * 2004-07-30 2006-02-02 Degussa Ag Dispersion contenant du dioxyde de titane
WO2006067131A1 (fr) * 2004-12-22 2006-06-29 Degussa Gmbh Dispersion de dioxyde de zirconium et d'oxyde mixte de zirconium
WO2006108743A1 (fr) * 2005-04-14 2006-10-19 Degussa Gmbh Dispersion aqueuse d'oxyde de cerium
EP1757560A2 (fr) 2005-08-12 2007-02-28 Degussa AG Poudre d'oxyde de cérium et dispersion la contenant
DE102006057903A1 (de) * 2006-12-08 2008-06-12 Evonik Degussa Gmbh Titandioxid enthaltende Dispersion

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GENG ET AL., JOURNAL OF ELECTRONIC MATERIALS, vol. 39, 2010, pages 1 - 7
MORI ET AL., J. MATER. SCI., vol. 46, 2010, pages 1341 - 1350
RYOHEI MORI ET AL: "Organic solvent based TiOdispersion paste for dye-sensitized solar cells prepared by industrial production level procedure", JOURNAL OF MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS, BO, vol. 46, no. 5, 28 September 2010 (2010-09-28), pages 1341 - 1350, XP019872487, ISSN: 1573-4803, DOI: 10.1007/S10853-010-4925-2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017125264A1 (fr) * 2016-01-18 2017-07-27 Evonik Degussa Gmbh Dispersion d'oxyde métallique dans du phosphate de trialkyle
CN114230864A (zh) * 2021-12-14 2022-03-25 南京大学 一种改性氧化锆纳米粒子醇分散体系及其制备方法和应用、紫外光固化树脂材料

Also Published As

Publication number Publication date
EP2709751A1 (fr) 2014-03-26
KR20140038409A (ko) 2014-03-28
DE102011075918A1 (de) 2012-11-22

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