WO2017125264A1 - Dispersion d'oxyde métallique dans du phosphate de trialkyle - Google Patents

Dispersion d'oxyde métallique dans du phosphate de trialkyle Download PDF

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Publication number
WO2017125264A1
WO2017125264A1 PCT/EP2017/050137 EP2017050137W WO2017125264A1 WO 2017125264 A1 WO2017125264 A1 WO 2017125264A1 EP 2017050137 W EP2017050137 W EP 2017050137W WO 2017125264 A1 WO2017125264 A1 WO 2017125264A1
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WO
WIPO (PCT)
Prior art keywords
polyvinylidene fluoride
phosphate
dispersion
group
metal oxide
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/EP2017/050137
Other languages
German (de)
English (en)
Inventor
Wolfgang Lortz
Claudia SEVERIN
Daniel ESKEN
Gabriele BERGMANN
Christoph Batz-Sohn
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
Publication of WO2017125264A1 publication Critical patent/WO2017125264A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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

Definitions

  • the invention relates to a dispersion of a metal oxide in an alkyl phosphate, their preparation and use.
  • polymer membranes are used. Their essential task is to separate the cathode and anode from each other and to maintain the ion conduction. The heat resistance of the polymer membrane is limited. You try to increase them by coating them.
  • anode active material such as graphite is coated with a metal oxide. This leads to the formation of a defined SEI (solid electrolyte interface), which is Li-ion conductive and resistant to possible electrolyte decomposition products.
  • SEI solid electrolyte interface
  • Titanium dioxides should be as nanoscale.
  • WO2009 / 079889 discloses a process for the production of a nonwoven-reinforced polymembrane which comprises forming a colloidal polymer emulsion
  • the mixture is milled for several hours in a ball mill and coarse fractions separated.
  • the invention relates to a dispersion containing
  • Binders are understood to mean polymers in dissolved or emulsified form known to those skilled in the art of energy storage devices, in particular for membranes or anode active materials. Examples are polyethylene oxide, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, polyacrylonitrile, polyamides, polyimides,
  • Polyether ether ketone polymethyl methacrylate, polytetraethylene glycol diacrylate, polyvinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride / chlorotrifluoroethylene copolymer, polysulfones and polyethersulfones.
  • the liquid phase of the dispersion according to the invention contains at least 90% by weight, preferably at least 99% by weight, of the trialkyl phosphate.
  • the selected trialkyl phosphates have the advantage that they are water-soluble and thus purification steps are simplified.
  • the liquid phase of the dispersion according to the invention can furthermore, in total, contain up to 10% by weight of further constituents.
  • These may be solvents selected from the group consisting of water, dimethylsulfoxide, tetramethylurea, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and acetone. The proportion of these solvents should, however, be minimal or they should be completely absent.
  • Another component of the liquid phase is a dispersant in question. Especially when it comes to keeping the dispersion stable against sedimentation and low viscosity.
  • the proportion of the dispersant is preferably 1 to 10 wt .-%, based on the liquid phase.
  • the dispersants are preferably polymers which have as functional groups acid groups and / or amine groups or in each case their salts.
  • Acid groups are phosphoric acid groups or sulfonic acid groups in question.
  • the acidic functional groups are preferably in the form of an alkylammonium salt or a
  • Alkanolammonium salt Preferably, the polymer contains a variety of functional groups.
  • the number average molecular weight is at least 500, more preferably 500 to 1000.
  • copolymers in the form of block copolymers or random structures.
  • the acid number of the dispersant is preferably from 70 to 180 KOH / g, more preferably from 80 to 120 KOH / g.
  • the amine number of the dispersant is preferably from 40 mg KOH / g to 140 mg KOH / g, more preferably from 80 to 120 mg / KOH / g.
  • Suitable dispersants are available from Byk Chemie under the trade name Disperbyk®. For the preparation of suitable dispersants, reference is also made to WO2010 / 025889 and EP-A-893155.
  • Particularly suitable metal oxide particles are those which have been produced pyrogenically.
  • pyrogenic metal oxides are meant those obtained by flame hydrolysis or flame oxidation of metal compounds, for example AICI3 or TiCU.
  • the metal oxides carry on their surface hydroxyl groups.
  • the fumed metal oxides produced in the dispersion according to the invention are in the form of aggregates of particles which form a three-dimensional structure with cavities and pores.
  • the particles, according to their genesis in the flame, are called primary particles.
  • the primary particles have a diameter of about 5 to 15 nm.
  • the mean aggregate diameter corresponds to the mean particle diameter dso. It is determined by dynamic light scattering.
  • AEROXIDE® Alu 130 AEROXIDE® Alu 65
  • AEROXIDE® Alu C AEROXIDE® T1O2 P 25
  • AEROXIDE® ⁇ 2 P 90 all from Evonik Industries.
  • Another object of the invention is a process for the preparation of the dispersion.
  • the trialkyl phosphate and optionally the dispersant is introduced and the
  • Dispersing to counter, by means of a heat exchanger, a temperature increase to about 30 ° C are limited. With such systems, dispersions having a mean aggregate diameter of up to 80 nm, typically 80 to 200 nm, can be prepared.
  • a metal oxide particles and trialkyl phosphate-containing predispersion for example the dispersion obtained by means of a rotor / stator system or a toothed disk, is divided into at least two partial streams and these partial streams are released in a high-energy mill under a pressure of at least 500 bar a nozzle and makes the partial streams in a gas- or liquid-filled reaction space meet. It may be advantageous to repeat the high energy milling one or more times.
  • a suitable high energy mill for example, the Ultimaizer system, model HJP-25050, the company Sugino Machine Ltd.
  • the material of the nozzle is preferably diamond. With this method it is possible to produce dispersions with a mean aggregate diameter d 50 of 50 to 80 nm.
  • Another object of the invention is a coating composition containing the dispersion of the invention and a binder.
  • the binder is preferably selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, Polyacrylonitrile, polyamides, polyimides, polyetheretherketone, polymethylmethacrylate,
  • Another object of the invention is a method for producing a
  • Dispersion and a binder selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, polyacrylonitrile, polyamides, polyimides, polyetheretherketone, polymethylmethacrylate, polytetraethylene glycol diacrylate, polyvinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride / chlorotrifluoroethylene copolymer, polysulfones and polyethersulfones combined.
  • a binder selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, polyacrylonitrile, polyamides, polyimides, polyetheretherketone, polymethylmethacrylate, polytetraethylene glycol diacrylate, polyvinylidene fluoride / hexafluoropropylene
  • trialkyl phosphate present in the dispersion and the trialkyl phosphate present in the solution may be identical or different.
  • Another object of the invention is a method for coating a membrane, comprising the steps
  • Polytetrafluoroethylene polyacrylonitrile, polyamides, polyimides, polyetheretherketone,
  • Polysulfones and polyethersulfones to give a coating composition b) applying the coating composition to a membrane and removing the liquid phase.
  • the membrane is preferably a respective microporous polyolefin membrane, polyvinylidene fluoride membrane or a polyolefin / polyvinylidene fluoride composite membrane.
  • the inventive method is particularly suitable for the production of membranes with an applied layer thickness of less than 10 ⁇ , in particular from 1 to 3 ⁇ .
  • Another object of the invention is a method for coating a
  • Anode active material comprising the steps
  • Polytetrafluoroethylene polyacrylonitrile, polyamides, polyimides, polyetheretherketone,
  • anode active material for example, graphite, soft carbon or hard carbon come into question. Examples
  • Example 1 Dispersion of alumina in triethyl phosphate
  • Disperbyk® 180, Altana (P-containing alkylolammonium salt of copolymers with acidic
  • This predispersion is now ground with a high-energy mill at 2500 bar. After two passes, finally, in addition, based on the total amount, 1% by weight of Disperbyk® 180 was stirred in with the aid of a dissolver.
  • the dispersion obtained has a content of Al2O3 of 30 wt .-%. Its viscosity is about 20 mPas over a shear range of 1 to 1000 s ⁇ and a temperature of 25 ° C. The mean aggregate diameter is 52 nm.
  • Example 2 Dispersion of titanium dioxide in triethyl phosphate
  • This predispersion will now be ground with a high-energy mill in two passes at 2500 bar.
  • the dispersion obtained has a content of T1O2 of 30% by weight. Its viscosity is about 15 mPas over a shear range of 1 to 1000 s ⁇ and a temperature of 25 ° C. The average aggregate diameter is 169 nm.
  • Example 3 Coating Compositions
  • Example 4 Separator Coatings
  • Example 3 The coating compositions from Example 3 are applied by means of a slot die method to a polypropylene LIB separator, Celgard® 2500, thickness 25 ⁇ m. The separator is adjusted with a distance of 10 ⁇ to the slot.
  • the slit die is then run over the separator at a rate of 0.4 m / min and the coating composition applied at a flow rate of 0.5 to 1 ml / min, depending on the desired layer thickness. It is then dried at a temperature of 50 ° C for 2 hours.
  • coated separators are examined by conventional methods and with
  • the separators coated with the dispersion according to the invention have significantly lower values.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Cell Separators (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une dispersion contenant a) 20 à 40 % en poids d'oxyde métallique choisi dans le groupe constitué par l'oxyde d'aluminium et le dioxyde de titane, présentant à chaque fois une surface BET de 30 à 150 m2/g et un diamètre moyen d'agrégat des particules d'oxyde métallique dans la dispersion de 50 -180 nm, et b) dans la phase liquide, au moins 90 % en poids d'un phosphate de trialkyle choisi dans le groupe constitué par le phosphate de triméthyle, le phosphate de triéthyle, le phosphate de tri-n-propyle, le phosphate de triisopropyle et le phosphate de méthyldiéthyle, c) 1 à 10 % en poids, par rapport à la phase liquide, d'un dispersant, d) la dispersion étant sensiblement exempte de liants, ce qui signifie que la proportion de liants est inférieure à 1,0 % en poids. L'invention concerne également un procédé pour la préparation d'une composition de revêtement, dans lequel on rassemble la dispersion et un liant, choisi dans le groupe constitué par le poly(oxyde d'éthylène), le poly(fluorure de vinylidène), le poly(chlorure de vinylidène), le polytétrafluoroéthylène, le polyacrylonitrile, les polyamides, les polyimides, la polyétheréthercétone, le poly(méthacrylate de méthyle), le poly(diacrylate de tétraéthylèneglycol), le copolymère de poly(fluorure de vinylidène)/hexafluoropropylène, le copolymère de poly(fluorure de vinylidène)/chlorotrifluoroéthylène, les polysulfones et les polyéthersulfones.
PCT/EP2017/050137 2016-01-18 2017-01-04 Dispersion d'oxyde métallique dans du phosphate de trialkyle Ceased WO2017125264A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16151671 2016-01-18
EP16151671.1 2016-01-18

Publications (1)

Publication Number Publication Date
WO2017125264A1 true WO2017125264A1 (fr) 2017-07-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220289572A1 (en) * 2021-03-15 2022-09-15 Evonik Operations Gmbh Dispersion and coating composition containing lithium metal phosphate
CN117165126A (zh) * 2023-08-30 2023-12-05 湖南立方新能源科技有限责任公司 一种极耳用安全涂层和二次电池
WO2024175389A1 (fr) * 2023-02-21 2024-08-29 Evonik Operations Gmbh Dispersions d'oxyde d'aluminium destinées à être utilisées en tant que revêtement de séparateur dans des batteries secondaires

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100178545A1 (en) * 2007-12-21 2010-07-15 Changzhou Zhongke Laifang Power Science & Technology Co., Ltd. Microporous polymer separators for lithium ion batteries and method for producing the same
WO2012156199A1 (fr) * 2011-05-16 2012-11-22 Evonik Degussa Gmbh Dispersion d'oxyde métallique à base d'un solvant organique
WO2013092576A1 (fr) * 2011-12-21 2013-06-27 Agfa-Gevaert Dispersion comprenant des nanoparticules métalliques, d'oxyde de métal ou de précurseurs de métal, dispersant polymère et additif de frittage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100178545A1 (en) * 2007-12-21 2010-07-15 Changzhou Zhongke Laifang Power Science & Technology Co., Ltd. Microporous polymer separators for lithium ion batteries and method for producing the same
WO2012156199A1 (fr) * 2011-05-16 2012-11-22 Evonik Degussa Gmbh Dispersion d'oxyde métallique à base d'un solvant organique
WO2013092576A1 (fr) * 2011-12-21 2013-06-27 Agfa-Gevaert Dispersion comprenant des nanoparticules métalliques, d'oxyde de métal ou de précurseurs de métal, dispersant polymère et additif de frittage

Non-Patent Citations (3)

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Title
BOTTINO A ET AL: "Preparation and characterization of novel porous PVDF-ZrO2 composite membranes", DESALINATION, ELSEVIER, AMSTERDAM, NL, vol. 146, no. 1-3, 10 September 2002 (2002-09-10), pages 35 - 40, XP004386331, ISSN: 0011-9164, DOI: 10.1016/S0011-9164(02)00469-1 *
MELANIE LEE ET AL: "Formation of micro-channels in ceramic membranes - Spatial structure, simulation, and potential use in water treatment", JOURNAL OF MEMBRANE SCIENCE, vol. 483, 1 June 2015 (2015-06-01), pages 1 - 14, XP055208520, ISSN: 0376-7388, DOI: 10.1016/j.memsci.2015.02.023 *
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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220289572A1 (en) * 2021-03-15 2022-09-15 Evonik Operations Gmbh Dispersion and coating composition containing lithium metal phosphate
EP4060780A1 (fr) * 2021-03-15 2022-09-21 Evonik Operations GmbH Composition de dispersion et de revêtement contenant du phosphate métallique au lithium
JP2022141612A (ja) * 2021-03-15 2022-09-29 エボニック オペレーションズ ゲーエムベーハー リチウム金属リン酸塩を含有する分散液及びコーティング組成物
US12378117B2 (en) * 2021-03-15 2025-08-05 Evonik Operations Gmbh Dispersion and coating composition containing lithium metal phosphate
WO2024175389A1 (fr) * 2023-02-21 2024-08-29 Evonik Operations Gmbh Dispersions d'oxyde d'aluminium destinées à être utilisées en tant que revêtement de séparateur dans des batteries secondaires
CN117165126A (zh) * 2023-08-30 2023-12-05 湖南立方新能源科技有限责任公司 一种极耳用安全涂层和二次电池

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