CN101870658A - Keggin polyoxometallate-based ion liquid and synthesis method thereof - Google Patents

Keggin polyoxometallate-based ion liquid and synthesis method thereof Download PDF

Info

Publication number
CN101870658A
CN101870658A CN201010174134A CN201010174134A CN101870658A CN 101870658 A CN101870658 A CN 101870658A CN 201010174134 A CN201010174134 A CN 201010174134A CN 201010174134 A CN201010174134 A CN 201010174134A CN 101870658 A CN101870658 A CN 101870658A
Authority
CN
China
Prior art keywords
ionic liquid
polyoxometallate
keggin
octyl group
pmo
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.)
Granted
Application number
CN201010174134A
Other languages
Chinese (zh)
Other versions
CN101870658B (en
Inventor
刘术侠
蒋云霞
苗俊
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.)
Northeast Normal University
Original Assignee
Northeast Normal University
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 Northeast Normal University filed Critical Northeast Normal University
Priority to CN2010101741347A priority Critical patent/CN101870658B/en
Publication of CN101870658A publication Critical patent/CN101870658A/en
Application granted granted Critical
Publication of CN101870658B publication Critical patent/CN101870658B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention belongs to the technical field of chemical material, and relates to Keggin polyoxometallate-based ion liquid and a preparation method thereof. The ion liquid consists of positive-tetraoctylammonium cation and Keggin polyoxometallate anion. The preparation method is characterized in that: positive-tetraoctylammonium bromide and Keggin polyoxometallate are measured according to a given chemical ratio to be respectively configured to dichloromethane solution and water solution, then the dichloromethane solution of the positive-tetraoctylammonium bromide is dropped into the water solution of Keggin polyoxometallate to be mixed at the room temperature so as to have the ion exchanging reaction, and the organic phase is separated and the solvent is eliminated, so the ion liquid is prepared. The preparation method is simple, the preparation cost is low, and the environmental pollution is small.

Description

One class is based on the ionic liquid and the synthetic method thereof of Keggin type polyoxometallate
Technical field
The invention belongs to the chemical material technical field, be specifically related to a class based on ionic liquid of Keggin type polyoxometallate and preparation method thereof.
Background technology
Ionic liquid is brand-new medium and the supple-virtuosity energy material that grows up under the framework of Green Chemistry in recent years, because it has low melting point, low-steam pressure, do not burn, Heat stability is good, liquid state wide ranges, advantages such as good ionic conductivity form the research focus rapidly in fields such as catalysis, the energy, optics.Traditional ionic liquid generally comprises organic cation and inorganic anion two parts, and new ionic liquid constantly appears in continually developing and multiple compatibility of zwitterion, and system is grown in strength gradually.In most cases, the design of new functional ion liquid is to give cationic moiety with functional group, and anionicsite often is left in the basket.The multi-metal oxygen cluster anions is a class polynuclear coordination compound, because its structure determines that kind is various, size adjustable is considered to important inorganic building block.An important factor that influences the ionic compound fusing point is the coulomb interaction power that constitutes between the zwitterion of compound.When lower and ion volume was big when zwitterion electric density, interionic distance increased, and helps producing low melting point salt.Because polyanionic surface charge delocalization at anionic surface, compares with inorganic anion, polyoxometallic acid salt anionic surfactant electric density reduces greatly, is to form the good negatively charged ion of low melting point ionic compound to select.Therefore with multi-metal oxygen cluster as ion liquid anionicsite, can produce unique ionic liquid.
Summary of the invention
The objective of the invention is to propose a class novel based on ionic liquid of Keggin type polyoxometallate and preparation method thereof.
Provided by the invention based on Keggin type polyoxometallate ionic liquid, to form by just-four octyl group ammonium cation and Keggi type polyoxometallate negatively charged ion, be respectively concrete the composition: [(n-C 8H 17) 4N] nXM 12O 40, wherein X is P, Si, Ge, B, As, and M is W, Mo, and n is the natural number of 1-7; [(n-C 8H 17) 4N] nPMo xV yO 40, wherein when x=11, y=1, n=4; When x=10, y=2, n=5; When x=9, y=3, n=6; [(n-C 8H 17) 4N] 7PTi 2W 10O 40[(n-C 8H 17) 4N] 7SiW 9Nb 3O 43
Provided by the invention is just to take by weighing-four octyl group brometo de amonios and Keggin type polyoxometallate by certain stoichiometric ratio based on Keggin type polyoxometallate preparation method of ionic liquid, be mixed with the dichloromethane solution and the aqueous solution respectively, then will be just the dichloromethane solution of-four octyl group brometo de amonios be added drop-wise in the aqueous solution of Keggin polyoxometallate, stir under the room temperature, ion exchange reaction takes place, and tells organic phase and obtains target product except that desolvating.Specifically may further comprise the steps:
The first step: press the synthetic required Keggin type polyoxometallate of literature method, be mixed with the certain density aqueous solution.
Second step: just taking by weighing-four octyl group brometo de amonios by certain stoichiometric ratio and be mixed with dichloromethane solution, the dichloromethane solution of octyl group brometo de amonio just-four is added drop-wise in the aqueous solution of Keggin polyoxometallate, stir under the room temperature, ion exchange reaction takes place, and tells organic phase and also obtains except that desolvating.
The present invention compared with prior art has following unusual effect:
1, provided by the present invention is a class novel ion liquid, has developed ion liquid new variety.
2,, can prepare the ionic liquid based on polyoxometallate of different structure and function according to the ion liquid preparation thinking of this class provided by the present invention.
3, ion exchange reaction is adopted in ion liquid preparation provided by the invention, and equipment used is few, and step is simple.In addition, with the organic solvent of water and conventional low toxicity as reaction solvent, the reaction conditions gentleness, cost is lower, environmental pollution is few, is suitable for industrial production.
4, provided by the invention some based on Keggin type polyoxometallate ionic liquid since anionicsite be polyoxometallate with catalytic activity, can some organic reaction of catalysis.
5, provided by the invention some mesomorphous phase can appear in heating in the process of cooling based on Keggin type polyoxometallate ionic liquid.
6, provided by the invention some can be used as the electrolytic solution of solar cell or lithium ion battery based on Keggin type polyoxometallate ionic liquid.
Embodiment
Embodiment 1:[(n-C 8H 17) 4N] 3PW 12O 40Ion liquid preparation
Prepare H by literature method 7P (W 2O 7) 6XH 2O.(North, E.O.Inorg.Synth.1939,1,132.) takes by weighing H by stoichiometric ratio at 1: 3 7P (W 2O 7) 6XH 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 7P (W 2O 7) 6XH 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 3PW 12O 40Ionic liquid.
Embodiment 2:[(n-C 8H 17) 4N] 3AsW 12O 40Ion liquid preparation
Prepare Na by literature method 3AsW 12O 40XH 2O.(Rocchiccioli-Deltcheff et al.Inorg.Chem.1983,22,207-216.) take by weighing Na at 1: 3 by stoichiometric ratio 3AsW 12O 40XH 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to Na 3AsW 12O 40XH 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 3AsW 12O 40Ionic liquid.
Embodiment 3:[(n-C 8H 17) 4N] 4SiW 12O 40Ion liquid preparation
Prepare H by literature method 4SiW 12O 40XH 2O.(North, E.O.Inorg.Synth.1939,1,129.) takes by weighing H by stoichiometric ratio at 1: 4 4SiW 12O 40XH 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 4SiW 12O 40XH 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4SiW 12O 40Ionic liquid.
Embodiment 4:[(n-C 8H 17) 4N] 4GeW 12O 40Ion liquid preparation
Prepare H by literature method 4GeW 12O 4014H 2O.(Rocchiccioli-Deltcheff et al.Inorg.Chem.1983,22,207-216.) take by weighing H at 1: 4 by stoichiometric ratio 4GeW 12O 4014H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 4GeW 12O 4014H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4GeW 12O 40Ionic liquid.
Embodiment 5:[(n-C 8H 17) 4N] 5BW 12O 40Ion liquid preparation
Prepare K by literature method 5BW 12O 40XH 2O.(Rocchiccioli-Deltcheff et al.Inorg.Chem.1983,22,207-216.) take by weighing K at 1: 5 by stoichiometric ratio 5BW 12O 40XH 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to K 5BW 12O 40XH 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 5BW 12O 40Ionic liquid.
Embodiment 6:[(n-C 8H 17) 4N] 3PMo 12O 40Ion liquid preparation
Prepare H by literature method 3PMo 12O 4014H 2O.(Rocchiccioli-Deltcheff et al.Inorg.Chem.1983,22,207-216.) take by weighing H at 1: 3 by stoichiometric ratio 3PMo 12O 4014H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 3PMo 12O 4014H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4PMo 12O 40Ionic liquid.
Embodiment 7:[(n-C 8H 17) 4N] 3AsMo 12O 40Ion liquid preparation
Prepare Li by literature method 3AsMo 12O 40XH 2O.(Rocchiccioli-Deltcheff et al.Inorg.Chem.1983,22,207-216.) take by weighing Li at 1: 3 by stoichiometric ratio 3AsMo 12O 40XH 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to Li 3AsMo 12O 40XH 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4AsMo 12O 40Ionic liquid.
Embodiment 8:[(n-C 8H 17) 4N] 4SiMo 12O 40Ion liquid preparation
Prepare H by literature method 4SiMo 12O 40XH 2O.(North, E.O.Inorg.Synth.1939,1,129.) takes by weighing H by stoichiometric ratio at 1: 4 4SiMo 12O 40XH 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 4SiMo 12O 40XH 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4SiMo 12O 40Ionic liquid.
Embodiment 9:[(n-C 8H 17) 4N] 4GeMo 12O 40Ion liquid preparation
Prepare H by literature method 4GeMo 12O 4014H 2O.(Rocchiccioli-Deltcheff et al.Inorg.Chem.1983,22,207-216.) take by weighing H at 1: 4 by stoichiometric ratio 4GeMo 12O 4014H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 4GeMo 12O 4014H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4GeMo 12O 40Ionic liquid.
Embodiment 10:[(n-C 8H 17) 4N] 4PMo 11V O 40Ion liquid preparation
Prepare H by literature method 4PMo 11VO 4034H 2O.(George A.Tsigdinos, C.J.Hallada, Inorg.Chem.1968,7,437-441.) take by weighing H at 1: 4 by stoichiometric ratio 3PMo 11VO 4034H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 3PMo 11VO 4034H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 4PMo 11V O 40Ionic liquid.
Embodiment 11:[(n-C 8H 17) 4N] 5PMo 10V 2O 40Ion liquid preparation
Prepare H by literature method 5PMo 10V 2O 4032H 2O.(George A.Tsigdinos, C.J.Hallada, Inorg.Chem.1968,7,437-441.) take by weighing H at 1: 5 by stoichiometric ratio 5PMo 10V 2O 4032H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 5PMo 10V 2O 4032H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 5PMo 10V 2O 40Ionic liquid.
Embodiment 12:[(n-C 8H 17) 4N] 6PMo 9V 3O 40Ion liquid preparation
Prepare H by literature method 6PMo 9V 3O 4034H 2O.(George A.Tsigdinos, C.J.Hallada, Inorg.Chem.1968,7,437-441.) take by weighing H at 1: 6 by stoichiometric ratio 6PMo 9V 3O 4034H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to H 6PMo 9V 3O 4034H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 6PMo 9V 3O 40Ionic liquid.
Embodiment 13:[(n-C 8H 17) 4N] 7PTi 2W 10O 40Ion liquid preparation
Prepare K by literature method 7PTi 2W 10O 406H 2O.(P.J.Domaille, W.H.Knoth, Inorg.Chem.1983,22,818-822.) take by weighing K at 1: 7 by stoichiometric ratio 7PTi 2W 10O 406H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to K 7PTi 2W 10O 406H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 7PTi 2W 10O 40Ionic liquid.
Embodiment 14:[(n-C 8H 17) 4N] 7SiW 9Nb 3O 43Ion liquid preparation
Prepare Cs by literature method 6HSiW 9Nb 3O 438H 2O.(Gyu-Shik Kim, Huadong Zeng, Wade A.Neiwert, Jennifer J.Cowan, Donald VanDerveer, Craug L.Hill, Ira A.Weinstock, Inorg.Chem.2003,42,5537-5544.) take by weighing Cs at 1: 7 by stoichiometric ratio 6HSiW 9Nb 3O 438H 2O and octyl group brometo de amonio just-four are mixed with the aqueous solution and dichloromethane solution respectively, and the dichloromethane solution with four octyl group brometo de amonios under the vigorous stirring dropwise is added to Cs 6HSiW 9Nb 3O 438H 2In the O aqueous solution, mixing solutions stirred 30 minutes, and standing demix is told lower floor's organic phase and removed methylene dichloride with separating funnel, promptly obtains [(n-C 8H 17) 4N] 7GeW 9Nb 3O 43Ionic liquid.

Claims (6)

1. a class is based on the ionic liquid of Keggin type polyoxometallate, it is characterized in that this ionic liquid is made up of just-four octyl group ammonium cation and Keggin type polyoxometallate negatively charged ion, and be respectively concrete the composition: [(n-C 8H 17) 4N] nXM 12O 40, wherein X is P, Si, Ge, B, As, and M is W, Mo, and n is the natural number of 1-7; [(n-C 8H 17) 4N] nPMo xV yO 40, wherein when x=11, y=1, n=4; When x=10, y=2, n=5; When x=9, y=3, n=6; [(n-C 8H 17) 4N] 7PTi 2W 10O 40[(n-C 8H 17) 4N] 7SiW 9Nb 3O 43
2. the ionic liquid described in claim 1 is characterized in that anionicsite is saturated Keggin type polyoxometallic acid salt anionic, and general formula is MX 12O 40 N-, concrete formula composed as follows:
[(n-C 8H 17) 4N] nXM 12O 40, wherein X is P, Si, Ge, B, As, and M is W, Mo, and n is the natural number of 1-7.
3. the ionic liquid described in claim 1 is characterized in that anionicsite is that vanadium replaces Keggin type polyoxometallic acid salt anionic, and general formula is PMo xV yO 40 N-, concrete formula composed as follows:
[(n-C 8H 17) 4N] nPMo xV yO40, wherein when x=11, y=1, n=4; When x=10, y=2, n=5; When x=9, y=3, n=6.
4. the ionic liquid described in claim 1 is characterized in that anionicsite is that titanium replaces Keggin type polyoxometallic acid salt anionic PTi 2W 10O 40 7-, concrete formula composed as follows: [(n-C 8H 17) 4N] 7PTi 2W 10O 40
5. the ionic liquid described in claim 1 is characterized in that anionicsite replaces Keggin type polyoxometallic acid salt anionic SiW for containing the peroxy niobium 9Nb 3O 43 7-, concrete formula composed as follows: [(n-C 8H 17) 4N] 7SiW 9Nb 3O 43
6. preparation method of ionic liquid described in claim 1 is characterized in that specifically may further comprise the steps:
The first step: press the synthetic required Keggin type polyoxometallate of literature method, be mixed with the certain density aqueous solution;
Second step: just taking by weighing-four octyl group brometo de amonios by certain stoichiometric ratio and be mixed with dichloromethane solution, the dichloromethane solution of octyl group brometo de amonio just-four is added drop-wise in the aqueous solution of Keggin polyoxometallate, stir under the room temperature, ion exchange reaction takes place, and tells organic phase and also obtains except that desolvating.
CN2010101741347A 2010-05-14 2010-05-14 Keggin polyoxometallate-based ion liquid and synthesis method thereof Expired - Fee Related CN101870658B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101741347A CN101870658B (en) 2010-05-14 2010-05-14 Keggin polyoxometallate-based ion liquid and synthesis method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010101741347A CN101870658B (en) 2010-05-14 2010-05-14 Keggin polyoxometallate-based ion liquid and synthesis method thereof

Publications (2)

Publication Number Publication Date
CN101870658A true CN101870658A (en) 2010-10-27
CN101870658B CN101870658B (en) 2013-02-13

Family

ID=42995761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101741347A Expired - Fee Related CN101870658B (en) 2010-05-14 2010-05-14 Keggin polyoxometallate-based ion liquid and synthesis method thereof

Country Status (1)

Country Link
CN (1) CN101870658B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584708A (en) * 2012-01-06 2012-07-18 中国科学院过程工程研究所 Heteropoly-based ionic liquid electrolyte and preparation method thereof
CN103125483A (en) * 2012-09-18 2013-06-05 齐齐哈尔大学 Green double active center antibacterial agent and preparation method thereof
CN106622364A (en) * 2016-12-21 2017-05-10 新疆大学 Solid phase preparation method of ionic liquid polyoxometallate nano electrocatalyst
CN106902873B (en) * 2017-03-24 2020-12-22 河南大学 Arsenic vanadium oxygen cluster based polyacid ionic liquid and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101205221A (en) * 2006-12-22 2008-06-25 中国科学院大连化学物理研究所 Method for preparing p-vinyl epoxy cyclohexane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101205221A (en) * 2006-12-22 2008-06-25 中国科学院大连化学物理研究所 Method for preparing p-vinyl epoxy cyclohexane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《Journal of Electroanalytical Chemistry》 20040220 Ming-Hsi Chiang,et al Redox chemistry of the Keggin heteropolyoxotungstate anion in ionic liquids. 第77页第1段至第80页表格 1-6 第567卷, *
《Journal of Molecular Catalysis A:Chemical》 20021231 Ji Hu，et al Homogeneous-phase catalytic H2O2 oxidation of isobutyraldehyde using Keggin, Dawson and transition metal-substituted lacunary heteropolyanions 第452页至453页实验部分，表格1 1、2、6 第184卷, *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584708A (en) * 2012-01-06 2012-07-18 中国科学院过程工程研究所 Heteropoly-based ionic liquid electrolyte and preparation method thereof
CN103125483A (en) * 2012-09-18 2013-06-05 齐齐哈尔大学 Green double active center antibacterial agent and preparation method thereof
CN106622364A (en) * 2016-12-21 2017-05-10 新疆大学 Solid phase preparation method of ionic liquid polyoxometallate nano electrocatalyst
CN106902873B (en) * 2017-03-24 2020-12-22 河南大学 Arsenic vanadium oxygen cluster based polyacid ionic liquid and preparation method and application thereof

Also Published As

Publication number Publication date
CN101870658B (en) 2013-02-13

Similar Documents

Publication Publication Date Title
Chotard et al. Discovery of a sodium-ordered form of Na3V2 (PO4) 3 below ambient temperature
Reale et al. Synthesis and thermal behavior of crystalline hydrated iron (III) phosphates of interest as positive electrodes in Li batteries
CN104261472B (en) A kind of vanadic anhydride nanobelt and normal temperature synthesis method and application
CN102593441B (en) The synthetic method of modified columbic anhydride for lithium ion battery
CN101870658B (en) Keggin polyoxometallate-based ion liquid and synthesis method thereof
CN105261784B (en) A kind of aluminum secondary battery
CN107154493A (en) A kind of fluorophosphoric acid vanadium sodium salt and its production and use
CN102530906A (en) Microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries
CN104201340B (en) A kind of preparation method of lithium ion battery material lithium vanadate
CN101891181B (en) Preparation method of pure-phase high-crystallinity lithium iron phosphate
CN109761276B (en) Layered ammonium vanadate electrode material and preparation method and application thereof
CN101869851A (en) Supported polyoxometallate crystalline catalyst and preparation method thereof
CN106252592A (en) The carbon in lithium ion battery of a kind of micro-nano structure is combined the preparation method of niobium pentaoxide material
CN102225899A (en) Ionic liquid based on Dawson-type polyoxometalate and synthesis method thereof
Pralong et al. Transition metal hydrogenophosphates: a potential source of new protonic and lithium conductors
CN106025178A (en) Method for preparing metal oxide employing MOF as template and application of metal oxide in negative electrode material of lithium battery
CN103872324A (en) Preparation method of petaloid lithium ion battery negative electrode material VPO4
CN107720718B (en) A kind of high voltage N ASICON structure water system sodium-ion battery negative electrode material and its synthetic method
CN108963242A (en) A kind of unformed sodium-ion battery positive material and preparation method thereof and sodium-ion battery
CN103904343A (en) Preparation method of electrolyte for all-vanadium redox flow battery
CN102479944B (en) Preparation method and application of lithium iron phosphate composite material
CN110511237A (en) Lindqvist type vanadium heteropoly tungstic acid alcoxyl derivative and preparation method thereof
CN114361437A (en) NASICON type structure sodium ion positive electrode material and preparation method and application thereof
Schmidt et al. Lithium iron methylenediphosphonate: a model material for new organic–inorganic hybrid positive electrode materials for Li ion batteries
CN103050696B (en) Nanometer lithium iron phosphate as well as preparation method and application 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
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130213

Termination date: 20130514