WO2011132147A1 - Novel metal-organic frameworks as electrode material for lithium ion accumulators - Google Patents
Novel metal-organic frameworks as electrode material for lithium ion accumulators Download PDFInfo
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- WO2011132147A1 WO2011132147A1 PCT/IB2011/051696 IB2011051696W WO2011132147A1 WO 2011132147 A1 WO2011132147 A1 WO 2011132147A1 IB 2011051696 W IB2011051696 W IB 2011051696W WO 2011132147 A1 WO2011132147 A1 WO 2011132147A1
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- Prior art keywords
- electrode material
- metal
- lithium ion
- lithium
- porous metal
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QXGJCWSBOZXWOV-UHFFFAOYSA-N 3,4-dihydroxyphthalic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1C(O)=O QXGJCWSBOZXWOV-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- -1 amino, methoxy Chemical group 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004043 oxo group Chemical group O=* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- XTWMRBJKMXZQDS-UHFFFAOYSA-N iron;terephthalic acid Chemical compound [Fe].OC(=O)C1=CC=C(C(O)=O)C=C1 XTWMRBJKMXZQDS-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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 Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table 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 Table
- 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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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127029801A KR20130033369A (en) | 2010-04-21 | 2011-04-19 | Novel metal-organic frameworks as electrode material for lithium ion accumulators |
RU2012149351/04A RU2012149351A (en) | 2010-04-21 | 2011-04-19 | NEW METAL-ORGANIC FRAME-BASED STRUCTURES AS ELECTRODE MATERIAL FOR LITHIUM-ION BATTERIES |
JP2013505590A JP2013525972A (en) | 2010-04-21 | 2011-04-19 | Novel metal-organic structures as electrode materials for lithium ion batteries |
CA2795517A CA2795517A1 (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 |
CN201180019531XA CN102893434A (en) | 2010-04-21 | 2011-04-19 | Novel metal-organic frameworks as electrode material for lithium ion accumulators |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP10160560 | 2010-04-21 | ||
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JP (1) | JP2013525972A (en) |
KR (1) | KR20130033369A (en) |
CN (1) | CN102893434A (en) |
CA (1) | CA2795517A1 (en) |
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Cited By (7)
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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 |
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. |
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 |
FR3082513A1 (en) * | 2018-06-18 | 2019-12-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR THE PREPARATION OF A LITHIA METAL OXIDE THAT CAN BE USED AS A POSITIVE ELECTRODE ACTIVE MATERIAL |
CN112490412A (en) * | 2019-09-11 | 2021-03-12 | 肇庆市华师大光电产业研究院 | Novel sodium-ion battery negative electrode material and preparation method thereof |
WO2023207421A1 (en) * | 2022-12-14 | 2023-11-02 | 湖北亿纬动力有限公司 | Composite lithium manganese iron phosphate positive electrode material, and preparation method and application thereof |
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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 |
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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 |
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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 |
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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 |
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. |
FR3082513A1 (en) * | 2018-06-18 | 2019-12-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR THE PREPARATION OF A LITHIA METAL OXIDE THAT CAN BE USED AS A POSITIVE ELECTRODE ACTIVE MATERIAL |
WO2019243729A1 (en) * | 2018-06-18 | 2019-12-26 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for producing a lithium-containing metal oxide that can be used as an active material for a positive electrode |
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 |
CN112490412A (en) * | 2019-09-11 | 2021-03-12 | 肇庆市华师大光电产业研究院 | Novel sodium-ion battery negative electrode material and preparation method thereof |
WO2023207421A1 (en) * | 2022-12-14 | 2023-11-02 | 湖北亿纬动力有限公司 | Composite lithium manganese iron phosphate positive electrode material, and preparation method and application thereof |
Also Published As
Publication number | Publication date |
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CA2795517A1 (en) | 2011-10-27 |
KR20130033369A (en) | 2013-04-03 |
RU2012149351A (en) | 2014-05-27 |
JP2013525972A (en) | 2013-06-20 |
EP2561568A1 (en) | 2013-02-27 |
CN102893434A (en) | 2013-01-23 |
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