CN102893434A - 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 PDF

Info

Publication number
CN102893434A
CN102893434A CN201180019531XA CN201180019531A CN102893434A CN 102893434 A CN102893434 A CN 102893434A CN 201180019531X A CN201180019531X A CN 201180019531XA CN 201180019531 A CN201180019531 A CN 201180019531A CN 102893434 A CN102893434 A CN 102893434A
Authority
CN
China
Prior art keywords
electrode material
lithium ion
lithium
metal
bidentate
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.)
Pending
Application number
CN201180019531XA
Other languages
Chinese (zh)
Inventor
N·特鲁汉
U·米勒
A·潘琴科
I·M·马尔科夫斯基
A·菲舍尔
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
Publication of CN102893434A publication Critical patent/CN102893434A/en
Pending legal-status Critical Current

Links

Images

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

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 backbone as the electrode material that is used for lithium-ions battery
The storage battery that the present invention relates to be applicable to the electrode material that comprises porous organo-metallic skeleton of lithium-ions battery, described metal-organic framework itself, its purposes and comprise described electrode material.
Lithium ion battery group or lithium-ions battery have high-energy-density and thermally-stabilised.Herein, utilized when using lithium because its high negative normal potential can obtain this fact of high cell voltage.
Yet the high response of element lithium need to provide special lithium source and electrolyte.
In nearer research and development, the porous organo-metallic skeleton that comprises lithium ion and therefore be applicable in principle lithium ion battery group or storage battery has been described.
Therefore, such as G.de Combarieu etc., Chem.Mater.21 (2009), 1602-1611 have described the electrochemistry applicability of porous-organic backbone in the lithium ion battery group based on terephthalic acid (TPA) iron.
G.Ferey etc., Angewandte Chemie 119 (2007), and 3323-3327 has described that other have can reversible redox property and the Li/Fe Base Metal-organic backbone of absorbent properties.Herein, also with terephthalic acid (TPA) as the organic ligand in the metal-organic framework.
Although prior art becomes known for the electrode material based on metal-organic framework of lithium ion battery group, just still need applicability, the especially system of the improvement with regard to its electrochemical capacitor (very especially based on quality) as electrode material.
Therefore, the purpose of this invention is to provide this electrode material.
Described purpose is by a kind of electrode material realization that is applicable to lithium-ions battery and comprises porous organo-metallic skeleton, wherein said skeleton comprises lithium ion, optional at least a other metal ions and the organic compound of at least a at least bidentate, and the organic compound of described at least a at least bidentate is based on the dihydroxy dicarboxylic acids that can reversiblely be oxidized to quinoid structure.
Another aspect of the invention is a kind of porous organo-metallic skeleton as herein described.
Found to use the dihydroxy dicarboxylic acids or derivatives thereof that can reversiblely be oxidized to quinoid structure that the skeleton that is specially adapted to lithium-ions battery and has good electric capacity/mass value can be provided.
Porous organo-metallic skeleton of the present invention at first comprises lithium ion.Herein, but described lithium ion part keyed jointing (especially ion keyed jointing) to the hydroxy functional group of deprotonation.Lithium ion also can be used for consisting of the trunk of skeleton.In this case, only exist lithium ion just enough in the described skeleton.
In addition, also can choose one or more metal ions except lithium of existence wantonly.At this moment, these ions participate in forming metal-organic framework.Therefore, except lithium ion, can there be other metal ions.Can have equally 2,3,4 or more than other metal ions of 4 kinds.At this moment, described metal ion can be derived from a kind of metal or different metal.If at least two metal ion species are derived from a kind of same metal, then these must exist with different oxidation state.
In preferred embodiments, porous organo-metallic skeleton of the present invention does not comprise other metal ions except lithium ion.
In another embodiment, porous organo-metallic skeleton of the present invention comprises at least a other metal ions except lithium ion.Described at least a other metal ions are preferably selected from the ion of following group of metal: cobalt, iron, nickel, copper, manganese, chromium, vanadium and titanium.More preferably cobalt, iron, nickel and copper.Even more preferably cobalt and copper.
The organic compound of at least a at least bidentate is that formation porous organo-metallic skeleton of the present invention is necessary.Therefore, can there be a kind of organic compound of at least bidentate or the organic compound of multiple different at least bidentate.Therefore, in porous organo-metallic skeleton of the present invention, can have 2,3,4 or the organic compound of more kinds of different at least bidentate.
The organic compound of described at least a at least bidentate is based on the dihydroxy dicarboxylic acids that can reversiblely be oxidized to quinoid structure.
Thus, " quinoid " especially means the oxidable one-tenth oxo group of described two hydroxyls." reversible " especially means after reduction, can again carry out oxidation.
For the present invention, term " derive " organic compound that means described at least a at least bidentate with respect to carboxyl functional group partially or completely the form of deprotonation exist.In addition, the organic compound of preferred described at least a at least bidentate is also to be at least part of deprotonation of reducing condition with respect to its hydroxyl and to be combined with lithium ion, usually via ionic bond.In addition, term " derives " organic compound that means described at least a at least bidentate and can have other substituting groups.Therefore, except carboxyl functional group, can exist one or more independently substituting groups such as amino, methoxyl group, halogen or methyl.Preferably there are not other substituting groups or only have the F substituting group.For the present invention, term " derives " and also means described carboxyl functional group and can be used as sulfur analogs and exist.Sulfur analogs is-C (=O) SH and dynamic isomer thereof and-C (S) SH.Preferably there is not sulfur analogs.
Except these at least the organic compound of bidentate, described metal-organic framework also can comprise one or more monodentate ligands.
The organic compound of described at least a at least bidentate must have the parent molecule that can form Quinoid systems.This especially can be by having the parent molecule with the double bond systems of oxo group conjugation, especially by existing the two keys of C-C to obtain.This class parent molecule is that those skilled in the art are known.Example is benzene, naphthalene, phenanthrene or similar parent molecule.At this moment, these molecules have hydroxyl/hydroxide radicals and carboxyl/carboxylic acid ester groups at least.
In preferred embodiments, described dihydroxy dicarboxylic acids is dihydroxy phthalic acid, especially is 2,5-Dihydroxyterephthalic acid.
Porous organo-metallic skeleton of the present invention can prepare in the mode identical with metalloid-organic backbone known in the art in principle.Herein, especially can be with reference to WO-A 2010/012715 described lithium Base Metal-organic backbone.
The preparation example of the metal-organic framework that mixes or flood is as being described among EP-B 1785428 and the EP-A1070538.Except for example such as US 5,648, the conventional method of the preparation porous organo-metallic skeleton (MOF) described in 508, these also can prepare by electrochemical method.Thus, with reference to DE-A10355087 and WO-A 2005/049892.The metal-organic framework of preparation has particularly preferred performance in this way.
Another aspect of the invention is a kind of storage battery that comprises electrode material of the present invention.
The preparation of storage battery of the present invention is known by the prior art of preparation lithium-ions battery or lithium ion battery group in principle.Herein, but reference example such as DE-A 19916043.Because thus, the structural principle of storage battery and battery pack is identical, hereinafter for easy lithium ion battery group or the battery pack of being called.
The electrode material that is suitable for the reversible storage lithium ion is fixed on the electric energy output electrode by adhesive usually.
In battery charging process, electron stream is through external voltage source, lithium cation via electrolyte flow to the anode material.When battery uses, the lithium cation electrolyte of flowing through, and electronics flow to cathode material via load from anode material.
For fear of in electrochemical cell, being short-circuited the electric insulation layer that between described two electrodes, exists lithium cation still can pass through.This can be solid electrolyte or conventional slider.
In the preparation of many electrochemical cells, for example in the situation of the lithium ion battery group that is round battery forms, with required battery pack paper tinsel/film, namely Cathode Foil, anode foils and barrier foil are combined to form the battery pack volume by rolling equipment.In the situation that conventional lithium ion battery group is connected to electric energy output electrode (for example being aluminium foil or Copper Foil form) with Cathode Foil and anode foils.This metalloid paper tinsel guarantees to have enough mechanical stabilities.
On the other hand, barrier film self must stand mechanical stress, and this should not cause problem in the used thickness situation based on for example polyolefinic conventional barrier film.
The present invention further provides porous organo-metallic skeleton of the present invention in the purposes of the electrode material that is used for lithium-ions battery.
Electrode material of the present invention is specially adapted in the storage battery.Described electrode material can be used in the electrochemical cell basically.
Therefore, the present invention further provides a kind of electrochemical cell that comprises electrode material of the present invention, the purposes of porous organo-metallic skeleton of the present invention at the electrode material that is used for electrochemical cell also is provided.
Accompanying drawing shows:
Fig. 1: Li-2, the XRD analysis of 5-dihydric para-phthalic acid MOF.Herein, as Fig. 3-5, intensity I (Lin (counting)) shows as the function of 2 Θ scales.
Fig. 2: Li-2, the sem analysis of 5-dihydric para-phthalic acid MOF.
Fig. 3: Li-Co-2, the XRD analysis of 5-dihydric para-phthalic acid MOF.
Fig. 4: Co-2, the XRD analysis of 5-dihydric para-phthalic acid MOF.
Fig. 5: Cu-2, the XRD analysis of 5-dihydric para-phthalic acid MOF.
Fig. 6: Cu-2, the sem analysis of 5-dihydric para-phthalic acid MOF.
Embodiment
Embodiment 1:Li-2,5-dihydric para-phthalic acid MOF's is synthetic
Test method:
Figure BDA00002266029600041
Figure BDA00002266029600051
In glass beaker, described 2,5-Dihydroxyterephthalic acid is dissolved among the DMF.In the second glass beaker, that lithium hydroxide is soluble in water.This solution is slowly dropped in the first yellow solution.Add to finish not long ago, described solution becomes is muddy and become green suspension.After 1 hour, with its filtration, and with solids wash 4 times, use 100ml DMF at every turn.With filter cake dried overnight under RT and decompression.
Product weight: 35.9g
Color: oyster
Solid concentration: 4.2%
Yield based on Li: 77.9%
Analyze:
Langmuir SA (in advance activation under 130 ° of C): 13m 2/ g (BET:9m 2/ g)
Chemical analysis:
Carbon: 42.1g/100g
Oxygen: 41.1g/100g
Nitrogen: 4.7g/100g
Li：9.0g/100g
Embodiment 2:Co-2, the Li of 5-dihydric para-phthalic acid MOF (Co-DHBDC MOF) mixes
Test method:
Figure BDA00002266029600052
In glass beaker, with Co-2,5-dihydric para-phthalic acid MOF (referring to 2a) is suspended among the DMF.In the second glass beaker, that lithium hydroxide is soluble in water.This solution is dropped in the first red suspension.This suspension becomes peony a little.After 2 hours, filtering suspension liquid with solids wash 4 times, uses 100ml DMF at every turn.With filter cake dried overnight under RT and decompression, under 130 ° of C and decompression dry 16 hours subsequently.
Product weight: 5.5g
Color: shallow breen
Solid concentration: 5.8%
Yield based on Li: 88%
Analyze:
Langmuir SA (in advance activation under 130 ° of C): 169m 2/ g (BET:125m 2/ g)
Chemical analysis:
Carbon: 32.0g/100g
Oxygen: 37.4g/100g
Nitrogen: 5.1g/100g
Co：21.1g/100g
Li：2.8g/100g
Embodiment 2a:Co-2,5-dihydric para-phthalic acid MOF's is synthetic
Raw material:1) 64.85g Co (NO 3) 2* 6H 2O
2) 33.25g 2,5-Dihydroxyterephthalic acid
Solvent:1) 3500ml (3325g) DMF
2)175ml?H 2O
Test method
A) synthetic: 2,5-Dihydroxyterephthalic acid and cobalt nitrate are dissolved in the 4L flask, are heated to 100 ° of C via 1.5 hours, and at 100 ° of C and N 2Lower stirring 8 hours.
B) reprocessing: at N 2Lower
Under RT, filter, with 1000ml DMF/2000ml MeOH washing, divide half with filtrate, and use in each case 600ml MeOH extracted overnight (16 hours).
C) drying: dry whole weekend under RT and decompression
Color: orange
Yield: 47.2g
Solid concentration: 1.31%
Yield based on Co: 92.0%
Analyze:
Langmuir SA (in advance activation under 130 ° of C): 1311m 2/ g (BET:961m 2/ g)
Chemical analysis:
Carbon: 30.8g/100g
Co：25.5g/100g
Embodiment 3:Cu-2, the Li of 5-dihydric para-phthalic acid MOF (Cu-DHBDC MOF) mixes
Figure BDA00002266029600071
In glass beaker, with Cu-2,5-dihydric para-phthalic acid MOF (referring to 3a) is suspended among the DMF.In the second glass beaker, that lithium hydroxide is soluble in water.This solution is dropped in the first suspension.After 2 hours, filtering suspension liquid with solids wash 4 times, uses 100ml DMF at every turn.With filter cake dried overnight under RT and decompression, under 130 ° of C and decompression dry 16 hours subsequently.
Product weight: 5.5g
Color: brown
Solid concentration: 5.8 % by weight
Analyze:
Langmuir SA (in advance activation under 200 ° of C): 577m 2/ g (BET:430m 2/ g)
Chemical analysis:
Cu：33.0g/100g
Li：3.7g/100g
Embodiment 3a:Cu-2,5-dihydric para-phthalic acid MOF's is synthetic
Raw material:2 * 34.2g Cu (NO 3) 2* 3H 2O=2 * 141.6mmol
M=241.6g/mol
2 * 13.3g 2,5-Dihydroxyterephthalic acid=2 * 67.13mmol
M=198.13g/mol
Solvent:2 * 700ml DMF, density: 0.95g/ml=1300g
2×35ml?H 2O
Test method:2 * 2L batch of material
Synthetic: as 2,5-Dihydroxyterephthalic acid and copper nitrate to be dissolved in 2 * 2L flask, to be heated to 100 ° of C through 1.5 hours, and under 100 ° of C, stirred 8 hours
Reprocessing: at N 2Lower
Under RT, filter, with 2 * 250ml DMF/4 * 250ml MeOH washing, residue 330ml MeOH extracted overnight (16 hours).
Dry: under RT and decompression, 48 hours
Activation: under 130 ° of C and decompression, 16 hours
Color: pale red brown
Yield: 40.7g
Solid concentration: 2.8%
Metal analysis Cu:39%
Analyze:
Langmuir SA (activating in advance at 130 ° of C): 1183m 2/ g (BET:879m 2/ g)
Chemical analysis:
Carbon: 26.3g/100g
Cu：39g/100g
Electrochemical Characterization
With 1.5g MOF, 0.75g Super P (conductive black additive, available from Timcal), 0.12g KS6 (the electrically conductive graphite additive is available from Timcal), 0.75g PVDF (Kynoar) mix in 50ml NMP (METHYLPYRROLIDONE) together and stirred 10 hours.
By scraper described dispersion is applied on the Al paper tinsel, drying is 10 hours under 120 ° of C and decompression.
The test of electrochemical cell of the present invention
For the electrochemical Characterization composite material, make up electrochemical cell.Anode: the Li paper tinsel, 50 μ m are thick; Slider: Freundenberg 2190 is available from Freundenberg; Negative electrode is positioned on the Al paper tinsel with above-mentioned MOF; Electrolyte: EC (ethylene carbonate)/DEC (diethyl carbonate) 3:7 volume % has lithium hexafluoro phosphate (LiPF 6), 1mol/l.
Under the 0.02mA electric current, battery is carried out charging and discharging.The result is summarised in the table 1.
Table 1
Figure BDA00002266029600091

Claims (10)

1. electrode material that is applicable to lithium-ions battery and comprises porous organo-metallic skeleton, wherein said skeleton comprises lithium ion, optional at least a other metal ions and the organic compound of at least a at least bidentate, and the organic compound of described at least a at least bidentate is based on the dihydroxy dicarboxylic acids that can reversiblely be oxidized to quinoid structure.
2. according to claim 1 electrode material wherein comprises one or more other metal ions.
3. according to claim 2 electrode material, wherein said at least a other metal ions are selected from following group metal ion: cobalt, iron, nickel, copper, manganese, chromium, vanadium and titanium.
4. each electrode material according to claim 1-3, wherein said dihydroxy dicarboxylic acids is dihydroxy phthalic acid.
5. each electrode material according to claim 1-4, wherein said dihydroxy dicarboxylic acids is 2,5-Dihydroxyterephthalic acid.
6. one kind such as each described porous organo-metallic skeleton among the claim 1-5.
7. according to claim 6 porous organo-metallic skeleton is in the purposes of the electrode material that is used for lithium-ions battery.
8. storage battery, it comprises according to claim 1 in-5 each electrode material.
9. electrochemical cell, it comprises according to claim 1 in-5 each electrode material.
10. according to claim 6 porous organo-metallic skeleton is in the purposes of the electrode material that is used for electrochemical cell.
CN201180019531XA 2010-04-21 2011-04-19 Novel metal-organic frameworks as electrode material for lithium ion accumulators Pending CN102893434A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10160560.8 2010-04-21
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

Publications (1)

Publication Number Publication Date
CN102893434A true CN102893434A (en) 2013-01-23

Family

ID=44833772

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180019531XA Pending CN102893434A (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)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103706401A (en) * 2014-01-14 2014-04-09 东北师范大学 Preparation method of cobalt metal organic frame/macroporous carbon compound
CN104393300A (en) * 2014-10-14 2015-03-04 中国科学院宁波材料技术与工程研究所 Lithium ion battery electrode material and its application in lithium ion batteries
CN105390696A (en) * 2015-12-04 2016-03-09 华南师范大学 Preparation method for high-specific-capacity lithium battery negative electrode material
CN106981661A (en) * 2017-06-05 2017-07-25 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
CN109054035A (en) * 2018-06-29 2018-12-21 中国科学院合肥物质科学研究院 A kind of nano flower-like Ti-MOF fluorescence probe material and the preparation method and application thereof
CN112334411A (en) * 2018-06-18 2021-02-05 原子能和替代能源委员会 Method for producing lithium-containing metal oxide useful as positive electrode active material

Families Citing this family (8)

* 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
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.
KR102488917B1 (en) * 2017-11-24 2023-01-17 한국재료연구원 Method of manufacturing fast chargeable electrode with 3D printed metal organic framework
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1886536A (en) * 2003-11-24 2006-12-27 巴斯福股份公司 Method for electrochemical production of a crystalline porous metal organic skeleton material
CN101434612A (en) * 2007-11-14 2009-05-20 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
US20090133366A1 (en) * 2004-11-04 2009-05-28 Viz Enterprises, Llc. Multi-chamber container and cap therefor

Family Cites Families (3)

* 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
US20090005243A1 (en) * 2007-04-23 2009-01-01 Goddard William A Doped metal organic frameworks for reversible H2 storage at ambient temperature
GB0807862D0 (en) * 2008-04-29 2008-06-04 Uni I Oslo Compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1886536A (en) * 2003-11-24 2006-12-27 巴斯福股份公司 Method for electrochemical production of a crystalline porous metal organic skeleton material
US20090133366A1 (en) * 2004-11-04 2009-05-28 Viz Enterprises, Llc. Multi-chamber container and cap therefor
CN101434612A (en) * 2007-11-14 2009-05-20 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FEREY GERARD ET AL: ""Mixed-valence Li/Fe-based metal-organic frameworks with both reversible redox and sorption properties"", 《ANGEWANDTE CHEMINE INTERNATIONAL EDITION》, vol. 46, no. 18, 27 April 2007 (2007-04-27), XP008163866, DOI: doi:10.1002/anie.200605163 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103706401A (en) * 2014-01-14 2014-04-09 东北师范大学 Preparation method of cobalt metal organic frame/macroporous carbon compound
CN104393300A (en) * 2014-10-14 2015-03-04 中国科学院宁波材料技术与工程研究所 Lithium ion battery electrode material and its application in lithium ion batteries
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
CN105390696A (en) * 2015-12-04 2016-03-09 华南师范大学 Preparation method for high-specific-capacity lithium battery negative electrode material
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
CN106981661A (en) * 2017-06-05 2017-07-25 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
CN112334411A (en) * 2018-06-18 2021-02-05 原子能和替代能源委员会 Method for producing lithium-containing metal oxide useful as positive electrode active material
CN109054035A (en) * 2018-06-29 2018-12-21 中国科学院合肥物质科学研究院 A kind of nano flower-like Ti-MOF fluorescence probe material and the preparation method and application thereof
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

Also Published As

Publication number Publication date
CA2795517A1 (en) 2011-10-27
RU2012149351A (en) 2014-05-27
EP2561568A1 (en) 2013-02-27
WO2011132147A1 (en) 2011-10-27
KR20130033369A (en) 2013-04-03
JP2013525972A (en) 2013-06-20

Similar Documents

Publication Publication Date Title
CN102893434A (en) Novel metal-organic frameworks as electrode material for lithium ion accumulators
US9780412B2 (en) Electrode materials for rechargeable zinc cells and batteries produced therefrom
US20110260100A1 (en) Novel Metal-Organic Frameworks as Electrode Material for Lithium Ion Accumulators
Gupta et al. Improving the cycle life of a high-rate, high-potential aqueous dual-ion battery using hyper-dendritic zinc and copper hexacyanoferrate
Kaveevivitchai et al. Exploration of vanadium benzenedicarboxylate as a cathode for rechargeable lithium batteries
Li et al. LiNi 1/3 Co 1/3 Mn 1/3 O 2 hollow nano-micro hierarchical microspheres with enhanced performances as cathodes for lithium-ion batteries
Sivakkumar et al. Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors
US3639174A (en) Voltaic cells with lithium-aluminum alloy anode and nonaqueous solvent electrolyte system
Gao et al. Graphene-wrapped mesoporous MnCO 3 single crystals synthesized by a dynamic floating electrodeposition method for high performance lithium-ion storage
US20090176162A1 (en) Lithium rechargeable electrochemical cell
KR20120063163A (en) Lithium air battery
Zhang et al. A multi-functional gel co-polymer bridging liquid electrolyte and solid cathode nanoparticles: An efficient route to Li–O2 batteries with improved performance
US10396349B2 (en) Semi-solid flow Li/O2 battery
Huang et al. Electrolyte formulation to enable ultra-stable aqueous Zn-organic batteries
Gou et al. Rational synthesis of Ni 3 (HCOO) 6/CNT ellipsoids with enhanced lithium storage performance: inspired by the time evolution of the growth process of a nickel formate framework
Song et al. Realizing formation and decomposition of Li2O2 on its own surface with a highly dispersed catalyst for high round-trip efficiency Li-O2 batteries
Manikandan et al. Advanced perspective on the synchronized bifunctional activities of P2-type materials to implement an interconnected voltage profile for seawater batteries
Mi et al. A pomegranate-structured sulfur cathode material with triple confinement of lithium polysulfides for high-performance lithium–sulfur batteries
Fei et al. Zinc pyridinedicarboxylate micro-nanostructures: promising anode materials for lithium-ion batteries with excellent cycling performance
TW201444167A (en) Electricity storage device, electrode used therein, and porous sheet
KR101768121B1 (en) Lithium air battery
US20220255137A1 (en) Conductive 2d metal-organic framework for aqueous rechargeable battery cathodes
CN110890504B (en) Functional diaphragm coating material for lithium-sulfur battery and preparation method thereof
CN109574078B (en) Manganese monoxide nano-particles and application and preparation method thereof
KR101592257B1 (en) Complex active material for cathode of lithium secondary cell, and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C05 Deemed withdrawal (patent law before 1993)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130123