US20050000824A1 - Phosphorus-borates with low melting points - Google Patents

Phosphorus-borates with low melting points Download PDF

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Publication number
US20050000824A1
US20050000824A1 US10/496,663 US49666304A US2005000824A1 US 20050000824 A1 US20050000824 A1 US 20050000824A1 US 49666304 A US49666304 A US 49666304A US 2005000824 A1 US2005000824 A1 US 2005000824A1
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United States
Prior art keywords
radical
salts
borate
salt
radicals
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Abandoned
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US10/496,663
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English (en)
Inventor
Michael Schmidt
Urs Welz-Biermann
Julian Vaughan-Spickers
Ken Seddon
Andrew Downard
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Merck Patent GmbH
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Merck Patent 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.)
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Publication date
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Assigned to MERCK PATENTS GMBH reassignment MERCK PATENTS GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOWNARD, ANDREW, SCHMIDT, MICHAEL, SEDDON, KEN, VAUGHAN-SPICKERS, JULIAN, WELZ-BIERMANN, URS
Publication of US20050000824A1 publication Critical patent/US20050000824A1/en
Abandoned legal-status Critical Current

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute

Definitions

  • the present invention relates to phosphorous borates, methods for their preparation and to the use of these salts in primary batteries, secondary batteries, capacitors, supercapacitors and/or galvanic cells. Furthermore, the present invention relates to the use of these salts as hydraulic liquid, conducting salt, catalyst, solvent, electrolyte or starting compound.
  • Weakly associated salts are the basis of many electrolytes. They are useful in electrochemical cells such as batteries, electronic parts such as capacitors, double layer capacitors, super or ultra capacitors as well as for organic synthesis, especially catalysis.
  • Solvent-free ionic liquids or “room temperature molten salts” were first disclosed in U.S. Pat. No. 2,446,331.
  • a disadvantage of these first molten salts and a serious problem with any solvent-free ionic liquid containing strong Lewis acids such as AlCl 3 is the liberation of toxic gases upon exposure to moisture. Work in room temperature melts has been dominated by the use of AlCl 3 and 1-ethyl-3-methylimidazolium (EMI) chloride.
  • Wilkes and Zaworotko presented new solvent-free ionic liquids in 1992, EMI BF 4 and EMI O 2 CCH 3 (J. Chem. Soc. Commun., 1992, S. 965).
  • these ionic media suffer from the same problems with moisture as previous compounds. Because BF 4 ⁇ - and CH 3 CO 2 ⁇ -anions oxidize at relatively low potentials, they are unsuitable for use in electrochemical cells.
  • U.S. Pat. No. 5,827,602 teaches ionic liquids comprising a number of heterocyclic organic cations and imides or methanides as counteranion. These ionic liquids demonstrate good conducting properties. A disadvantage of these salts lies with the costly preparation of the starting compounds, in particular the preparation of the anions.
  • a further problem underlying the present invention is the provision of more powerful and more stable primary and secondary batteries, capacitors, supercapacitors and galvanic cells.
  • the present invention relates to salts wherein at least two of the radicals R 1 , R 2 , R 3 , R 4 are identical and/or bound to each other by single or double bonds.
  • a further preferred embodiment relates to salts, wherein at least two of the radicals R 5 , R 6 , R 7 , R 8 are identical and/or bound to each other by single or double bonds.
  • More preferred salts are those, wherein at least one of the radicals, R 5 , R 6 , R 7 and R 8 denotes, in each case independently of one another, a radical selected from the group consisting of phenyl-, naphthyl-, anthracenyl, phenanthrenyl, pyridyl-, pyracyl- or pyrimidyl-radicals, that may be further substituted by at least one halogen radical, preferably a F- or Cl-radical and/or at least one radical of the formula —C q F (2q+1 ⁇ x) H x , wherein 1 ⁇ q ⁇ 6 and 0 ⁇ x ⁇ 2q+1.
  • the present invention relates to salts, wherein at least two of the radicals R 5 , R 6 , R 7 or R 8 denote a 2,2′-biphenyl-diolato(2′)O,O′-, a 1,2-benzen-diolato(2-)O,O′- or a salicylato(2-)-radical.
  • the salts of the present invention provide a number of advantages. They are not sensitive to hydrolysis. Their tendency to decompose is very small. They have a high thermal stability and they are soluble in most standard aprotic solvents, even in unpolar solvents of low viscosity such as toluene or hexane. In addition, these salts demonstrate a very large temperature range of up to several hundred degrees Celcius in which they are in a stable molten state. For example, [P(C 6 H 13 ) 3 Cl 4 H 29 )][B(OC(O)(C 6 H 4 )O) 2 ] is a liquid from ⁇ 150 to +300° C.
  • these salts are suitable for a number of applications, such as electrochemical applications or as hydraulic liquid, or for the catalysis of organic reactions or as inert solvent for highly reactive chemicals. They are especially useful as salts for electrolytes. Electrolytes comprising said salts are electrochemically stable, temperature and humidity resistant. Also, such electrolytes demonstrate an excellent cyclic behavior and performance in electrical cells.
  • a further aspect of the present invention relates to a method for the preparation of salts, wherein a salt of the general formula [II] [PR 1 R 2 R 3 R 4 ] a + A a ⁇ [II] and a salt of the general formula [III] K b+ [B(OR 5 ) n (OR 6 ) m (OR 7 ) o (OR 8 ) p ] b ⁇ [III] wherein
  • the resulting salt is purified by separating the byproduct K + A ⁇ by precipitation, ionic exchange chromatography or by evaporation, if K + denotes hydrogen.
  • aprotic solvents are available for the preparation of the salts, such as, for example, esters, ethers, carbonates, nitrites, sulfonicacidesters, toluene, methylenechloride, CHCl 3 .
  • Preferred suitable solvents are acetonitrile, THF (tetrahydrofurane) or a mixture of at least two of these solvents.
  • More preferred suitable solvent are aprotic solvents, preferably acetonitrile or THF (tetrahydrofurane) or a mixture of at least two aprotic solvents, wherein the resulting salt K + A ⁇ is unsoluble.
  • aprotic solvents preferably acetonitrile or THF (tetrahydrofurane) or a mixture of at least two aprotic solvents, wherein the resulting salt K + A ⁇ is unsoluble.
  • a preferred temperature range for mixing the salts of formula [II] and [III] is 0 to 100° C., more preferably 0 to 50° C. and most preferably 10 to 40° C.
  • reaction is carried out in a solvent or solvent mixture that is directly suitable for use in a secondary or primary battery, a capacitor, a supercapacitor or a galvanic cell.
  • Preferred solvents or solvent mixtures that are directly suitable for use in a secondary or primary battery, a capacitor or a galvanic cell are organic carbonates, preferably an ethylenecarbonate, propylenecarbonate, butylene-carbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate or a mixture of at least two of these solvents.
  • the method according to the present invention provides almost pure salts in high yield with little impurities. Often the reaction proceeds to give quantitative yields and only traces of impurities. If necessary, the salts may be further purified according to standard methods, for example, by recrystallisation in a suitable solvent or solvent mixture. A suitable solvent or solvent mixture can easily be selected by preliminary experiments.
  • the method for preparing the salts according to the invention is simply, efficient and without any complicated or dangerous steps.
  • the present invention relates to the use of at least one of the salts according to the invention alone or in combination with further salts and/or additives in primary batteries, secondary batteries, capacitors, supercapacitors and/or galvanic cells.
  • the salts are suitable for preparing electrolytes, preferably electrolytes for primary batteries, secondary batteries, capacitors, supercapacitors and/or galvanic cells.
  • Such an electrolyte comprises at least one compound of the present invention.
  • the preparation of soluble or solid electrolytes is well known to the average expert in the field of electrochmistry (for example: D. Linden, Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995; J. Barthel and H.-J. Gores, Solution Chemistry: A Cutting Edge in Modern Electrochemical Technology in G. Mamantov and A. I. Popov (publishers) Chemistry of Nonaquous Solutions, Current Progress, VCH Verlagstician, Weinheim 1994).
  • Electrolytes can be prepared as a solution or a solid material.
  • a solid electrolyte may be a polymer electrolyte optionally comprising a cross-linked polymer and at least one conducting salt or a gel electrolyte that comprises at least one solvent in addition to at least one conducting salt and an optional cross-linked polymer.
  • these electrolytes have a salt concentration of the electrolyte of 0.01-3 mol/l, preferably of 0.01-2 mol/l, most preferably of 0.1-1.5 mol/l.
  • Electrolytes according to the present invention provide excellent electrochemical properties for most uses in batteries, conductors and galvanic cells. These electrolytes provide excellent conductivity as well as stability and safety.
  • a hydraulic liquid comprising at least one compound of the general formula [I].
  • Primary batteries, secondary batteries, capacitors, supercapacitors, galvanic cells or hydraulic liquids according to the present invention are suitable to be employed under extreme conditions such as high temperatures or high humidity without an effect on the performance or life span of the device or liquid.
  • the present invention relates to the use of a salt according to the present invention as a solvent or as a conducting salt in an electrolyte of electrochemical devices.
  • salts of the present invention are used as a catalyst solvent, electrolyte or starting compound for the preparation of organic compounds.
  • Viscosity was measured using an LVDV-II Brookfield Cone and Plate Viscometer (1% accuracy, 0.2 repeatability).
  • the sample cup of the viscometer was fitted with luer and purge fittings, so that a positive current of dry dinitrogen was maintained at all times during the measurements, thus avoiding absorption of atmospheric moisture.
  • the sample cup was jacketed with a circulating water bath that was controlled by a circulator bath Grant LTD 6G (+0.1° C. accuracy).
  • the electrochemical cell was constructed from materials purchased from Bioanalytical Systems, Inc. (BAS).
  • the non-aqueous reference electrode was a silver wire immersed in a glass tube containing a 0.100 mol L-1 solution of AgNO 3 in the [bmim][NO 3 ] ionic liquid which was separated from the bulk solution by a Vycor plug. All potentials reported are referenced against the Ag(I)/Ag couple.
  • the counter electrode was a platinum coil immersed directly in the bulk solution.
  • the solution was held in a glass vial fitted with a Teflon cap with holes for the electrodes and a nitrogen line.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Lubricants (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Primary Cells (AREA)
US10/496,663 2001-11-28 2002-10-31 Phosphorus-borates with low melting points Abandoned US20050000824A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP01127468 2001-11-28
EP01127468.5 2001-11-28
PCT/EP2002/012163 WO2003045960A1 (en) 2001-11-28 2002-10-31 Phosphorus-borates with low melting points

Publications (1)

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US20050000824A1 true US20050000824A1 (en) 2005-01-06

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US10/496,663 Abandoned US20050000824A1 (en) 2001-11-28 2002-10-31 Phosphorus-borates with low melting points

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US (1) US20050000824A1 (ja)
EP (1) EP1448574B1 (ja)
JP (1) JP2005515194A (ja)
KR (1) KR20040061002A (ja)
CN (1) CN1596262A (ja)
AT (1) ATE297938T1 (ja)
AU (1) AU2002346813B2 (ja)
BR (1) BR0214490A (ja)
CA (1) CA2468416A1 (ja)
DE (1) DE60204719T2 (ja)
IN (1) IN2004KO00858A (ja)
TW (1) TW529199B (ja)
WO (1) WO2003045960A1 (ja)
ZA (1) ZA200405023B (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170332096A1 (en) * 2016-05-11 2017-11-16 Advanced Micro Devices, Inc. System and method for dynamically stitching video streams

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9650586B2 (en) * 2013-07-23 2017-05-16 The Boeing Company Redox couple-based mitigation of fluid-flow-driven electrochemical surface degradation

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4422975A (en) * 1981-08-03 1983-12-27 Exxon Research And Engineering Co. Organic salt compositions in extraction processes
US5660947A (en) * 1993-05-13 1997-08-26 Wuhr; Manfred Electrolyte for use in a galvanic cell
US5824602A (en) * 1996-10-21 1998-10-20 The United States Of America As Represented By The United States Department Of Energy Helicon wave excitation to produce energetic electrons for manufacturing semiconductors
US20010033964A1 (en) * 1999-12-10 2001-10-25 Merck Patent Gesellschaft Mit Beschrankter Haftung Alkylspiroborate salts for use in electrochemical cells
US20030120006A1 (en) * 1998-12-09 2003-06-26 The B.F. Goodrich Company In mold addition polymerization of norbornene-type monomers using group 10 metal complexes
US6783896B2 (en) * 2000-10-03 2004-08-31 Central Glass Company, Limited Electrolyte for electrochemical device
US7166724B2 (en) * 2000-05-30 2007-01-23 Merck Patent Gmbh Ionic liquids

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5827602A (en) * 1995-06-30 1998-10-27 Covalent Associates Incorporated Hydrophobic ionic liquids
JP4782903B2 (ja) * 1998-02-03 2011-09-28 エイシーイーピー インコーポレイテッド 電解溶質として有用な新規な物質

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4422975A (en) * 1981-08-03 1983-12-27 Exxon Research And Engineering Co. Organic salt compositions in extraction processes
US5660947A (en) * 1993-05-13 1997-08-26 Wuhr; Manfred Electrolyte for use in a galvanic cell
US5824602A (en) * 1996-10-21 1998-10-20 The United States Of America As Represented By The United States Department Of Energy Helicon wave excitation to produce energetic electrons for manufacturing semiconductors
US20030120006A1 (en) * 1998-12-09 2003-06-26 The B.F. Goodrich Company In mold addition polymerization of norbornene-type monomers using group 10 metal complexes
US20010033964A1 (en) * 1999-12-10 2001-10-25 Merck Patent Gesellschaft Mit Beschrankter Haftung Alkylspiroborate salts for use in electrochemical cells
US7166724B2 (en) * 2000-05-30 2007-01-23 Merck Patent Gmbh Ionic liquids
US6783896B2 (en) * 2000-10-03 2004-08-31 Central Glass Company, Limited Electrolyte for electrochemical device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170332096A1 (en) * 2016-05-11 2017-11-16 Advanced Micro Devices, Inc. System and method for dynamically stitching video streams

Also Published As

Publication number Publication date
IN2004KO00858A (ja) 2006-05-19
EP1448574A1 (en) 2004-08-25
DE60204719T2 (de) 2006-05-18
ZA200405023B (en) 2005-05-31
BR0214490A (pt) 2004-09-14
AU2002346813B2 (en) 2008-03-20
WO2003045960A1 (en) 2003-06-05
AU2002346813A1 (en) 2003-06-10
TW529199B (en) 2003-04-21
CA2468416A1 (en) 2003-06-05
DE60204719D1 (de) 2005-07-21
KR20040061002A (ko) 2004-07-06
JP2005515194A (ja) 2005-05-26
ATE297938T1 (de) 2005-07-15
CN1596262A (zh) 2005-03-16
EP1448574B1 (en) 2005-06-15

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