Classifications

• • 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
  • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
  • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
• • 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
  • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic 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
  • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
  • C07F1/02—Lithium 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
  • H01M10/05—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
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • 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
  • H01M4/362—Composites
• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • 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 present invention relates to electrode materials which are suitable for a lithium ion accumulator and comprise a porous metal-organic framework, the metal-organic framework as such, the use thereof and also accumulators comprising the electrode material.
• Lithium ion batteries or lithium ion accumulators have a high energy density and are thermally stable.
• the fact that a high cell voltage can be obtained when using lithium because of its high negative standard potential is exploited.
• the high reactivity of elemental lithium requires the provision of special lithium sources and electrolytes.
• porous metal-organic frameworks which comprise lithium ions and are thus in principle suitable for lithium ion batteries or accumulators are described.
• G. de Combarieu et al., Chem. Mater. 21 (2009), 1602-161 1 describes the electrochemical suitability of a porous metal-organic framework based on iron terephthalate in lithium ion batteries.
• Li/Fe-based metal-organic frameworks having reversible redox properties and sorption properties are described by G. Ferey et al., Angewandte Chemie 1 19 (2007), 3323-3327.
• terephthalic acid serves as organic ligand in the metal-organic framework.
• an electrode material which is suitable for a lithium ion accumulator and comprises a porous metal-organic framework, wherein the framework comprises lithium ions and optionally at least one further metal ion and at least one at least bidentate organic compound and the at least one at least bidentate organic compound is based on a dihydroxydicarboxylic acid which can be reversibly oxidized to a quinoid structure.
• a further aspect of the present invention is a porous metal-organic framework as set forth here.
• the porous metal-organic framework of the invention comprises, firstly, lithium ions.
• the lithium ions can here be partly bound, in particular ionically, to deprotonated hydroxyl functions.
• Lithium ions can also serve to make up the skeleton of a framework. In this case, it is sufficient for only lithium ions to be present in the framework.
• one or more metal ions other than lithium can optionally be present. These then participate in formation of the metal-organic framework.
• a further metal ion can be present in addition to lithium ions. It is likewise possible for two, three, four or more than four further metal ions to be present.
• the metal ions can be derived from one metal or various metals. If at least two metal ions are derived from one and the same metal, these have to be present in different oxidation states.
• the porous metal-organic framework of the invention comprises no further metal ions in addition to lithium ions.
• the porous metal-organic framework of the invention comprises at least one further metal ion in addition to lithium ions.
• the at least one further metal ion is preferably selected from the group consisting of the metals cobalt, iron, nickel, copper, manganese, chromium, vanadium and titanium. Greater preference is given to cobalt, iron, nickel and copper. Cobalt and copper are even more preferred.
• At least one at least bidentate organic compound is necessary to build up the porous metal-organic framework of the invention. It is therefore possible for either one at least bidentate organic compound or a plurality of different at least bidentate organic compounds to be present.
• the at least one at least bidentate organic compound is based on a dihydroxydicarboxylic acid which can be reversibly oxidized to a quinoid structure.
• quinoid means, in particular, that the two hydroxy groups can be oxidized to oxo groups.
• Reversibly means, in particular, that, after reduction, the oxidation can be carried out again.
• the term "derived" means that the at least one at least bidentate organic compound is present in partially or completely deprotonated form in respect of the carboxy functions. Furthermore, it is preferred that the at least one at least bidentate organic compound is also at least partially deprotonated in the reduced state in respect of its hydroxy groups and binds lithium ions, usually via an ionic bond. Furthermore, the term “derived” means that the at least one at least bidentate organic compound can have further substituents. Thus, one or more independent substituents such as amino, methoxy, halogen or methyl groups can be present in addition to the carboxyl function. Preference is given to no further substituents or only F substituents being present.
• the term "derived" also means that the carboxyl function can be present as a sulfur analogue.
• the metal-organic framework can also comprise one or more monodentate ligands.
• the at least one at least bidentate organic compound has to have a parent molecule which is capable of forming the quinoid system. This is achieved, in particular, by the parent molecule having a double bond system conjugated with the oxo groups, in particular by the presence of C-C double bonds.
• parent molecules are known to those skilled in the art. Examples are benzene, naphthalene, phenanthrene or similar parent molecules. These then bear at least the hydroxy/hydroxide groups and the carboxy/carboxylate groups.
• the dihydroxydicarboxylic acid is a dihydroxybenzenedicarboxylic acid, in particular 2, 5-dihydroxyterephthalic acid.
• the porous metal-organic frameworks of the invention can in principle be prepared in the same way as comparable metal-organic frameworks which are known from the prior art.
• the preparation of doped or impregnated metal-organic frameworks is described, for example, in EP-B 1 785 428 and EP-A 1 070 538.
• the porous metal-organic frameworks (MOFs) as described, for example, in US 5,648,508, these can also be prepared by an electrochemical route. In this respect, reference is made to DE-A 103 55 087 and WO-A 2005/049892.
• the metal- organic frameworks prepared by this route have particularly good properties.
• a further aspect of the present invention is an accumulator comprising the electrode material of the invention.
• accumulators The production of accumulators according to the invention is known in principle from the prior art for the production of lithium ion accumulators or lithium ion batteries.
• reference may be made, for example, to DE-A 199 16 043. Since the structural principle for accumulators and batteries is the same in this respect, reference will hereinafter be made to a lithium ion battery or battery in the interest of simplicity.
• the electrode material which is suitable for the reversible storage of lithium ions is usually fixed to power outlet electrodes by means of a binder.
• electrons flow through an external voltage source and lithium cations flow through the electrolyte to the anode material.
• the lithium cations flow through the electrolyte while the electrons flow through a load from the anode material to the cathode material.
• an electrically insulating layer through which lithium cations can nevertheless pass is present between the two electrodes. This can be a solid electrolyte or a conventional separator.
• the required battery foils/films i.e. cathode foils, anode foils and separator foils
• the cathode and anode foils are connected to power outlet electrodes in the form of, for example, an aluminum or copper foil.
• Such metal foils ensure sufficient mechanical stability.
• the separator film on the other hand, must on its own withstand the mechanical stresses, which in the case of conventional separator films based on, for example, polyolefins in the thickness used does not present a problem.
• the present invention further provides for the use of a porous metal-organic framework according to the invention in an electrode material for lithium ion accumulators.
• the electrode material of the invention is particularly suitable for use in an accumulator.
• the electrode material can basically be used in electrochemical cells.
• the present invention therefore further provides an electrochemical cell comprising an electrode material according to the invention and also provides for the use of a porous metal-organic framework according to the invention in an electrode material for electrochemical cells.
• Fig. 1 XRD analysis of an Li-2,5-dihydroxyterephthalic acid MOF.
• the intensity I (Lin(Counts)) is shown as a function of the 2 theta scale (2 ⁇ ).
• the 2,5-dihydroxyterephthalic acid is dissolved in DMF.
• the lithium hydroxide is dissolved in water. This solution is slowly added dropwise to the first yellow solution. Shortly before the end of the addition, the solution becomes turbid and changes into a green suspension. This is filtered after 1 hour and the solid is washed 4 times with 100 ml each time of DMF. The filtercake is dried overnight at RT under reduced pressure.
• Example 2 Li Doping of a Co-2,5-dihydroxyterephthalic acid MOF (Co-DHBDC MOF)
• the Co-2,5-dihydroxyterephthalic acid MOF (see 2a) is suspended in DMF.
• the lithium hydroxide is dissolved in water. This solution is added dropwise to the first red suspension. The suspension becomes slightly dark red. After 2 hours, the suspension is filtered and the solid is washed 4 times with 100 ml each time of DMF. The filtercake is dried overnight at RT under reduced pressure and subsequently at 130°C for 16 hours under reduced pressure.
• Example 3 Li Doping of a Cu-2,5-dihydroxyterephthalic acid MOF (Cu-DHBDC MOF)
• the Cu-2,5-dihydroxyterephthalic acid MOF (see 3a) is suspended in DMF.
• the lithium hydroxide is dissolved in water. This solution is added dropwise to the first suspension. After 2 hours, the suspension was filtered and the solid was washed 4 times with 100 ml each time of DMF. The filtercake is dried overnight at RT under reduced pressure and subsequently at 130°C under reduced pressure for 16 hours.
• the dispersion was applied to Al foil by means of a doctor blade and dried at 120°C under reduced pressure for 10 hours.
• An electrochemical cell was constructed.
• Anode Li foil 50 ⁇ thick, separator: Freundenberg 2190, from Freundenberg; cathode on Al foil with MOF as described above; electrolyte: EC (ethylene carbonate)/DEC(diethyl carbonate) 3 : 7% by volume with lithium hexafluorophosphate (LIPF 6 ) 1 mol/l.
• EC ethylene carbonate
• DEC diethyl carbonate

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• 2011
  • 2011-04-19 WO PCT/IB2011/051696 patent/WO2011132147A1/en active Application Filing
  • 2011-04-19 KR KR1020127029801A patent/KR20130033369A/ko not_active Application Discontinuation
  • 2011-04-19 JP JP2013505590A patent/JP2013525972A/ja not_active Withdrawn
  • 2011-04-19 CN CN201180019531XA patent/CN102893434A/zh active Pending
  • 2011-04-19 EP EP11771672A patent/EP2561568A1/de not_active Withdrawn
  • 2011-04-19 RU RU2012149351/04A patent/RU2012149351A/ru not_active Application Discontinuation
  • 2011-04-19 CA CA2795517A patent/CA2795517A1/en not_active Abandoned

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