EP2561568A1 - Novel metal-organic frameworks as electrode material for lithium ion accumulators - Google Patents

Novel metal-organic frameworks as electrode material for lithium ion accumulators

Info

Publication number
EP2561568A1
EP2561568A1 EP11771672A EP11771672A EP2561568A1 EP 2561568 A1 EP2561568 A1 EP 2561568A1 EP 11771672 A EP11771672 A EP 11771672A EP 11771672 A EP11771672 A EP 11771672A EP 2561568 A1 EP2561568 A1 EP 2561568A1
Authority
EP
European Patent Office
Prior art keywords
electrode material
metal
lithium ion
lithium
porous metal
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.)
Withdrawn
Application number
EP11771672A
Other languages
German (de)
French (fr)
Inventor
Natalia Trukhan
Ulrich Müller
Alexander Panchenko
Itamar Michael Malkowsky
Andreas Fischer
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP11771672A priority Critical patent/EP2561568A1/en
Publication of EP2561568A1 publication Critical patent/EP2561568A1/en
Withdrawn legal-status Critical Current

Links

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

Abstract

The present invention discloses an electrode material which is suitable for a lithium ion accumulator and comprises a porous metal-organic framework, wherein the framework comprises lithium ions, 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. The present invention further discloses such a porous metal-organic framework, the use thereof and also lithium ion accumulators comprising such electrode materials.

Description

Novel metal-organic frameworks as electrode material for lithium ion accumulators Description
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. Here, the fact that a high cell voltage can be obtained when using lithium because of its high negative standard potential is exploited. However, the high reactivity of elemental lithium requires the provision of special lithium sources and electrolytes.
In a relatively recent development, porous metal-organic frameworks which comprise lithium ions and are thus in principle suitable for lithium ion batteries or accumulators are described.
Thus, for example, 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.
Further 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. Here too, terephthalic acid serves as organic ligand in the metal-organic framework.
Despite the electrode materials based on metal-organic frameworks which are known from the prior art for lithium ion batteries, there is still a need for improved systems in respect of suitability as electrode material, in particular with regard to the electrochemical capacity thereof (very particularly based on the mass).
It is therefore an object of the present invention to provide such an electrode material.
The object is achieved by 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.
It has been found that the use of a dihydroxydicarboxylic acid which can be reversibly oxidized to a quinoid structure or a derivative thereof enables frameworks which are particularly suitable for lithium ion accumulators and have good capacity/mass values to be provided.
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.
In addition, one or more metal ions other than lithium can optionally be present. These then participate in formation of the metal-organic framework. Thus, for example, 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. Here, 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. In a preferred embodiment, the porous metal-organic framework of the invention comprises no further metal ions in addition to lithium ions.
In an alternative embodiment, 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. Thus, two, three, four or more different at least bidentate organic compounds can be present in the porous metal-organic framework of the invention. The at least one at least bidentate organic compound is based on a dihydroxydicarboxylic acid which can be reversibly oxidized to a quinoid structure.
In this context, "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.
For the purposes of the present invention, 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. For the purposes of the present invention, the term "derived" also means that the carboxyl function can be present as a sulfur analogue. Sulfur analogues are -C(=0)SH and the tautomer thereof and -C(S)SH. Preference is given to no sulfur analogues being present.
In addition to these at least bidentate organic compounds, 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. Such 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.
In a preferred embodiment, 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. In particular, reference may here be made to lithium-based metal-organic frameworks as described in WO-A 2010/012715. 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. Apart from the conventional method of preparing 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.
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. Here, 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. In the charging of the cell, electrons flow through an external voltage source and lithium cations flow through the electrolyte to the anode material. When the cell is utilized, the lithium cations flow through the electrolyte while the electrons flow through a load from the anode material to the cathode material. To avoid a short circuit within the electrochemical cell, 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.
In the production of many electrochemical cells, e.g. in the case of a lithium ion battery in the form of a round cell, the required battery foils/films, i.e. cathode foils, anode foils and separator foils, are combined by means of a rolling device to form a battery roll. In the case of conventional lithium ion batteries, 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.
The figures show: Fig. 1 : XRD analysis of an Li-2,5-dihydroxyterephthalic acid MOF. Here, as in figures 3 to 5, the intensity I (Lin(Counts)) is shown as a function of the 2 theta scale (2Θ).
Fig. 2 SEM analysis of an Li-2,5-dihydroxyterephthalic acid MOF.
Fig. 3 XRD analysis of an Li-Co-2,5-dihydroxyterephthalic acid MOF.
Fig. 4 XRD analysis of a Co-2,5-dihydroxyterephthalic acid MOF.
Fig. 5 XRD analysis of a Cu-2,5-dihydroxyterephthalic acid MOF.
Fig. 6 SEM analysis of a Cu-2,5-dihydroxyterephthalic acid MOF. Examples
Example 1 : Synthesis of an Li-2,5-dihydroxyterephthalic acid MOF
Experimental method:
Starting material Mol Calculated Experimental
1 ) 2,5-Dihydroxyterephthalic acid 151 .5 mmol 30.0 g 30.0 g
2) Lithium hydroxide 606.0 mmol 14.3 g 14.3 g
3) DMF 8.17 mol 600.0 g 600.0 g
4) Water 1 1 .6 mol 210.0 g 210.0 g
In a glass beaker, the 2,5-dihydroxyterephthalic acid is dissolved in DMF. In a second glass beaker, 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.
Product weight: 35.9 g
Color: yellowish green
Solids concentration: 4.2%
Yield based on Li: 77.9% Analyses:
Langmuir SA (preactivation at 130°C): 13 m2/g (BET: 9 m2/g)
Chemical analysis:
Carbon 42.1 g/100 g
Oxygen 41 .1 g/100 g
Nitrogen 4.7 g/100 g
Li 9.0 g/100 g
Example 2: Li Doping of a Co-2,5-dihydroxyterephthalic acid MOF (Co-DHBDC MOF)
Experimental method: Starting material Mol Calculated Experimental
1 ) Co-DHBDC MOF 5.0 g 5.0 g
2) Lithium hydroxide 25 mmol 0.6 g 0.6 g
3) DMF 1.09 mol 80.0 g 80.0 g
4) Water 0.5 mol 9.0 g 9.0 g
In a glass beaker, the Co-2,5-dihydroxyterephthalic acid MOF (see 2a) is suspended in DMF. In a second glass beaker, 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.
Product weight: 5.5 g
Color: brownish green
Solids concentration: 5.8%
Yield based on Li: 88%
Analyses:
Langmuir SA (preactivation at 130°C): 169 m2/g (BET: 125 m2/g)
Chemical analysis:
Carbon 32.0 g/100 g
Oxygen 37.4 g/100 g
Nitrogen 5.1 g/100 g
Co 21 .1 g/100 g
Li 2.8 g/100 g Example 2a: Synthesis of a Co-2,5-dihydroxyterephthalic acid MOF
Starting materials: 1 ) 64.85 g of Co(N03)2 x 6 H20
2) 33.25 g of 2,5-dihydroxyterephthalic acid
Solvents: 1 ) 3500 ml (3325 g) of DMF
2) 175 ml of H20
Experimental method
a) Synthesis: 2,5-Dihydroxyterephthalic acid and Co nitrate were dissolved in a 4 I flask, heated to 100°C over a period of 1 .5 hours and stirred at 100°C under N2 for 8 hours
b) Work-up: under N2
filtered at RT, washed with 1000 ml of DMF/2000 ml of MeOH filtrate halved and extracted with 600 ml in each case of MeOH overnight (16 h).
c) Drying: over the weekend at RT under reduced pressure
Color: orange
Yield: 47.2 g
Solids concentration: 1.31 %
Yield based on Co: 92.0%
Analyses:
Langmuir SA (preactivation at 130°C): 131 1 m2/g (BET: 961 m2/g) Chemical analysis:
Carbon 30.8 g/100 g
Co 25.5 g/100 g Example 3: Li Doping of a Cu-2,5-dihydroxyterephthalic acid MOF (Cu-DHBDC MOF)
Starting material Mol Calculated Experimental
5) Cu-DHBDC MOF 5.0 g 5.0 g
6) Lithium hydroxide 80.8 mmol 0.6 g 0.6 g
7) DMF 1.09 mol 80.0 g 80.0 g
8) Water 0.5 mol 9.0 g 9.0 g
In a glass beaker, the Cu-2,5-dihydroxyterephthalic acid MOF (see 3a) is suspended in DMF. In a second glass beaker, 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.
Product weight: 5.5 g
Color: brown
Solids concentration: 5.8% by weight
Analyses:
Langmuir SA (preactivation at 200°C): 577 m2/g (BET: 430
Chemical analysis:
Cu 33.0 g/100 g
Li 3.7 g/100 g Example 3a: Synthesis of a Cu-2,5-dihydroxyterephthalic acid MOF
Starting materials: 2 x 34.2 g of Cu(N03)2 x 3 H20 = 2 x 141 .6
M = 241 .6 g/mol
2 x 13.3 g of 2,5-dihydroxyterephthalic acid
67.13 mmol
M = 198.13 g/mol
Solvents: 2 x 700 ml of DMF, density: 0.95 g/ml = 1300 g
2 x 35 ml of H20
Experimental method: 2 x 2 I batches
Synthesis: 2,5-dihydroxyterephthalic acid and Cu nitrate were dissolved in 2 x 2 I flasks, heated to 100°C over a period of 1 .5 hours and stirred at 100°C for 8 hours
Work-up: under N2
filtered at RT, washed with 2 x 250 ml of DMF/4 x 250 ml of MeOH residue extracted with 330 ml of MeOH overnight (16 h).
Drying: 48 h at RT under reduced pressure
Activation: 16 h at 130°C under reduced pressure
Color: reddish brown
Yield: 40.7 g
Solids concentration: 2.8%
Metal analysis Cu: 39% Analyses:
Langmuir SA (preactivation at 130°C): 1 183 m2/g (BET: 879 m2/g) Chemical analysis:
Carbon .26.3 g/100 g
Cu 39 g/100 g
Electrochemical characterization
1 .5 g of MOF, 0.75 g of Super P (conductive carbon black additive, from Timcal), 0.12 g of KS 6 (conductive graphite additive, from Timcal), 0.75 g of PVDF (polyvinylidene fluoride) were mixed together in 50 ml of NMP (N-methyl-2-pyrrolidone) and stirred for 10 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.
Testing of the electrochemical cell according to the invention To characterize the composite electrochemically, an electrochemical cell was constructed. Anode: Li foil 50 μηη 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 (LIPF6) 1 mol/l.
Charging and discharging of the cell were carried out at a current of 0.02 mA. The results are summarized in table 1 .
Table 1
MOF material Potential window, V Capacity, mAh/g of MOF
Example 1 1 .5 - 4.8 240
Example 2 1 .5 - 4.8 175
Example 3 1 .5 - 4.8 260

Claims

Claims
1 . 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.
2. The electrode material according to claim 1 , wherein one or more further metal ions are comprised.
3. The electrode material according to claim 2, wherein the at least one further metal ion is selected from the group consisting of the metals cobalt, iron, nickel, copper, manganese, chromium, vanadium and titanium.
4. The electrode material according to any of claims 1 to 3, wherein the dihydroxydicarboxylic acid is a dihydroxybenzenedicarboxylic acid.
5. The electrode material according to any of claims 1 to 4, wherein the dihydroxydicarboxylic acid is 2,5-dihydroxyterephthalic acid.
6. A porous metal-organic framework as set forth in any of claims 1 to 5.
7. The use of a porous metal-organic framework according to claim 6 in an electrode material for lithium ion accumulators.
8. An accumulator comprising an electrode material according to any of claims 1 to 5.
9. An electrochemical cell comprising an electrode material according to any of claims 1 to 5.
10. The use of a porous metal-organic framework according to claim 6 in an electrode material for electrochemical cells.
EP11771672A 2010-04-21 2011-04-19 Novel metal-organic frameworks as electrode material for lithium ion accumulators Withdrawn EP2561568A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11771672A EP2561568A1 (en) 2010-04-21 2011-04-19 Novel metal-organic frameworks as electrode material for lithium ion accumulators

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10160560 2010-04-21
PCT/IB2011/051696 WO2011132147A1 (en) 2010-04-21 2011-04-19 Novel metal-organic frameworks as electrode material for lithium ion accumulators
EP11771672A EP2561568A1 (en) 2010-04-21 2011-04-19 Novel metal-organic frameworks as electrode material for lithium ion accumulators

Publications (1)

Publication Number Publication Date
EP2561568A1 true EP2561568A1 (en) 2013-02-27

Family

ID=44833772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11771672A Withdrawn EP2561568A1 (en) 2010-04-21 2011-04-19 Novel metal-organic frameworks as electrode material for lithium ion accumulators

Country Status (7)

Country Link
EP (1) EP2561568A1 (en)
JP (1) JP2013525972A (en)
KR (1) KR20130033369A (en)
CN (1) CN102893434A (en)
CA (1) CA2795517A1 (en)
RU (1) RU2012149351A (en)
WO (1) WO2011132147A1 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9340884B2 (en) 2010-12-15 2016-05-17 Basf Se Process for the electrochemical fluorination of organic compounds
US9527751B2 (en) 2011-11-11 2016-12-27 Basf Se Organotemplate-free synthetic process for the production of a zeolitic material of the CHA-type structure
CN103165912A (en) * 2013-02-28 2013-06-19 北京化工大学常州先进材料研究院 Catalytic agent for lithium-air battery cathode and preparation method
CN103706401B (en) * 2014-01-14 2016-04-13 东北师范大学 A kind of preparation method of cobalt metal organic frame/macropore carbon complex
CN104393300B (en) * 2014-10-14 2017-09-29 中国科学院宁波材料技术与工程研究所 The electrode material of lithium ion battery and its application in lithium ion battery
CN105390696B (en) * 2015-12-04 2018-01-23 华南师范大学 A kind of preparation method of height ratio capacity lithium cell cathode material
FR3063180A1 (en) * 2017-02-21 2018-08-24 Commissariat Energie Atomique USE OF A MIXED ORGANIC-INORGANIC MATRIX COMPOUND, SAID MOF, AS AN ELECTRODE ACTIVE MATERIAL.
CN106981661B (en) * 2017-06-05 2019-08-23 南京工业大学 A kind of preparation method of lithium ion battery electrode material
CN107887599A (en) * 2017-11-01 2018-04-06 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application
KR102488917B1 (en) * 2017-11-24 2023-01-17 한국재료연구원 Method of manufacturing fast chargeable electrode with 3D printed metal organic framework
FR3082513B1 (en) * 2018-06-18 2020-09-25 Commissariat Energie Atomique PROCESS FOR THE PREPARATION OF A LITHIA METAL OXIDE THAT CAN BE USED AS AN ACTIVE MATERIAL FOR A POSITIVE ELECTRODE
CN109054035B (en) * 2018-06-29 2020-11-10 中国科学院合肥物质科学研究院 Nanometer flower-shaped Ti-MOF fluorescent probe material and preparation method and application thereof
CN110491686A (en) * 2019-08-28 2019-11-22 齐鲁工业大学 A kind of preparation method and application of bimetallic organic coordination compounds electrode material
CN112490412B (en) * 2019-09-11 2022-10-04 肇庆市华师大光电产业研究院 Novel sodium-ion battery negative electrode material and preparation method thereof
JP7354740B2 (en) 2019-10-01 2023-10-03 株式会社豊田中央研究所 Method for manufacturing electricity storage device and method for activating electrode for electricity storage device
CN115947325A (en) * 2022-12-14 2023-04-11 湖北亿纬动力有限公司 Composite lithium manganese iron phosphate cathode material and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3942063B2 (en) * 1999-06-28 2007-07-11 株式会社カネカ Novel polyimide composition and novel acid dianhydride used in the same
DE10355087A1 (en) * 2003-11-24 2005-06-09 Basf Ag Process for the electrochemical preparation of a crystalline porous organometallic framework
RU2007120575A (en) * 2004-11-04 2008-12-10 Виз Энтерпрайсиз MULTI-CAMERA CAPACITY AND CAP FOR HER
US20090005243A1 (en) * 2007-04-23 2009-01-01 Goddard William A Doped metal organic frameworks for reversible H2 storage at ambient temperature
CN101434612B (en) * 2007-11-14 2011-06-22 中国科学院大连化学物理研究所 Metal organic framework compound material, as well as preparation and application thereof
GB0807862D0 (en) * 2008-04-29 2008-06-04 Uni I Oslo Compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011132147A1 *

Also Published As

Publication number Publication date
WO2011132147A1 (en) 2011-10-27
JP2013525972A (en) 2013-06-20
RU2012149351A (en) 2014-05-27
KR20130033369A (en) 2013-04-03
CA2795517A1 (en) 2011-10-27
CN102893434A (en) 2013-01-23

Similar Documents

Publication Publication Date Title
WO2011132147A1 (en) Novel metal-organic frameworks as electrode material for lithium ion accumulators
US20110260100A1 (en) Novel Metal-Organic Frameworks as Electrode Material for Lithium Ion Accumulators
Zhao et al. Metal-organic frameworks for batteries
US9780412B2 (en) Electrode materials for rechargeable zinc cells and batteries produced therefrom
Hu et al. Cobalt-based metal organic framework with superior lithium anodic performance
US9972867B2 (en) Cosolvent electrolytes for electrochemical devices
JP6039180B2 (en) Lithium air battery
US20190288331A1 (en) Solid-state electrolytes with biomimetic ionic channels for batteries and methods of making same
Kaveevivitchai et al. Exploration of vanadium benzenedicarboxylate as a cathode for rechargeable lithium batteries
CN103123998A (en) Preparation method for water-based lithium-air battery
KR101334186B1 (en) Electrolyte Solution and magnesium battery using the same
Manikandan et al. Advanced perspective on the synchronized bifunctional activities of P2-type materials to implement an interconnected voltage profile for seawater batteries
US20220328825A1 (en) Positive electrode active material for sodium ion secondary battery
JP2022506400A (en) Hydrogen-based battery
US20220255137A1 (en) Conductive 2d metal-organic framework for aqueous rechargeable battery cathodes
US20200112025A1 (en) Positive electrode active material for sodium-ion secondary battery
EP3244472A1 (en) Composites comprising hollow microspheres of a vanadium oxide for lithium sulfur cells
WO2019136087A1 (en) Potassium secondary battery
WO2001001505A1 (en) Positive electrode material for lithium secondary cell, positive electrode for lithium secondary cell and lithium secondary cell
JP2020031011A (en) Negative electrode active material
Devic The Potential of MOFs in the Field of Electrochemical Energy Storage
JP6778673B2 (en) Lithium air secondary battery
JP2018092831A (en) Separator and lithium air secondary battery
KR20220153207A (en) MOF gel membrane and method for fabricating the same, MOF gel membrane separator and rechargeable organic battery
CN116349078A (en) Organic-inorganic hybrid composite, and coating composition, separator, secondary battery, battery module, battery pack, and electric device including the same

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121121

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20140516