CN106252663A - Metal-organic framework materials CuBDC nanometer sheet and its preparation method and application - Google Patents

Metal-organic framework materials CuBDC nanometer sheet and its preparation method and application Download PDF

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CN106252663A
CN106252663A CN201610637309.0A CN201610637309A CN106252663A CN 106252663 A CN106252663 A CN 106252663A CN 201610637309 A CN201610637309 A CN 201610637309A CN 106252663 A CN106252663 A CN 106252663A
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cubdc
metal
nanometer sheet
organic framework
framework materials
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CN106252663B (en
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安琴友
谢少妹
张磊
赵康宁
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Wuhan University of Technology WUT
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/26—1,4 - Benzenedicarboxylic acid
    • C07C63/28—Salts thereof
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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 invention belongs to nano material and technical field of electrochemistry, it is specifically related to a kind of metal-organic framework materials CuBDC (wherein BDC=1,4 dicarboxylic acid radical benzene) nanometer sheet and preparation method thereof, it can be as anode material of lithium-ion battery, it is formed by multi-layer C uBDC nanometer sheet stacking, and monolithic nanometer sheet thickness is 15～25 nanometers, and lateral width is 3～7 microns, having loose structure, its BET specific surface area is 530～550m2/ g, the aperture of loose structure is less than 2nm, belongs to microcellular structure.The invention has the beneficial effects as follows: metal-organic framework materials CuBDC nanometer sheet pattern based on preparation is homogeneous and has excellent conductive performance, when this electrode is as the negative material of sodium-ion battery, show multiplying power, higher specific capacity and the good cyclical stability of excellence.Present invention process is simple, and economical and practical, meets the requirement of Green Chemistry, is beneficial to the marketization and promotes.

Description

Metal-organic framework materials CuBDC nanometer sheet and its preparation method and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of metal-organic framework materials CuBDC (wherein BDC=1,4-dicarboxylic acid radical benzene) nanometer sheet and preparation method thereof, it can be as anode material of lithium-ion battery.
Background technology
Nowadays, along with the fast development in the fields such as pure electric automobile, hybrid vehicle, extensive energy storage device, Lithium ions etc. possess high-energy-density, high power density, the energy storage device of long circulation life obtain the wide of vast researcher General concern.It is excellent that lithium ion battery is high with its specific energy, power density high, have extended cycle life, self discharge is little, the ratio of performance to price is high etc. Point has become as the main selection object of the rechargeable formula power supply of current portable type electronic product.But due to lithium resource shortage system The about key factor of its development, therefore, needs the energy-storage battery system of development excellent combination property of future generation badly.And sodium and lithium have Similar physics and chemical property, and sodium aboundresources, with low cost, therefore sodium-ion battery is the electricity having very much development potentiality Cell body system.But owing to sodium atom radius is relatively big, cause the commercialization negative material graphite cannot be as in lithium ion battery Embed and deviate from.Search suitable anode material of lithium-ion battery and become one of problem demanding prompt solution.
Research shows, the specific surface area of nano material (such as nano wire, nanometer rods, nano-particle, nanometer sheet etc.) relatively big and Size is less, can shorten the evolving path of lithium ion, improves the ionic conductivity of material, and the most effectively reducing material internal should Power, finally prevents electrode material structural breakdown in charge and discharge process.But, owing to nano material is formed instability SEI quantity is more, makes the irreversible capacity of electrode material increase and coulombic efficiency reduces.Construct by dividing that nano-particle is formed The mesoporous laminated structure of level micro-meter scale or submicron-scale is considered as the effective way solving these problems.
Summary of the invention
It is an object of the invention to provide that a kind of technique is simple, meet the requirement of Green Chemistry, have good electric chemical Metal-organic framework materials CuBDC nanometer sheet of energy and its preparation method and application.
The present invention solves above-mentioned technical problem the technical scheme is that metal-organic framework materials CuBDC nanometer sheet, It is formed by multi-layer C uBDC nanometer sheet stacking, and monolithic nanometer sheet thickness is 15～25 nanometers, and lateral width is 3～7 microns, tool Having loose structure, its BET specific surface area is 530～550m2/ g, the aperture of loose structure is less than 2nm, belongs to microcellular structure.
The preparation method of described metal-organic framework materials CuBDC nanometer sheet, includes following steps:
1) weigh copper nitrate solid 0.25～0.3g, to dibenzoic acid solid 1.2～1.5g, dissolve with organic solvent；
2) by step 1) gained solution water-bath heated and stirred；
3) by step 2) gained solution put in baking oven dry, obtain metal-organic framework materials CuBDC nanometer sheet.
By such scheme, described drying temperature is 80 DEG C, drying time 18-24 hour.
By such scheme, described organic solvent is 20mL acetonitrile and 40mLN, the mixing of dinethylformamide.
By such scheme, described water bath heating temperature 60～80 DEG C, stir 6～8 hours.
Described metal-organic framework materials CuBDC nanometer sheet is as the application of the negative active core-shell material of sodium-ion battery.
By such scheme, the positive pole being sode cell half-cell with metal-organic framework materials CuBDC nanometer sheet, sodium sheet is sodium The negative pole of battery half cell assembles.
The present invention is by the CuBDC of strategy synthesis from top to down, and its liquid medium is divided into three layers, and top is copper nitrate solution, Bottom be to dibenzoic acid solution, and it is by the separation of intermediate flux layer, copper ion and sending out dibenzoic acid at zone line The growth of raw BDC crystal, synthesized CuBDC porous, surface area is big, has good chemical property.
The invention has the beneficial effects as follows: based on preparation metal-organic framework materials CuBDC nanometer sheet pattern homogeneous and There is excellent conductive performance, when this electrode is as the negative material of sodium-ion battery, show the multiplying power of excellence, higher specific volume Amount and good cyclical stability.Present invention process is simple, and economical and practical, meets the requirement of Green Chemistry, beneficially market Change and promote.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the metal-organic framework materials CuBDC nanometer sheet of embodiment 1；
Fig. 2 is the metal-organic framework materials CuBDC nanometer sheet SEM figure of embodiment 1；
Fig. 3 is the metal-organic framework materials CuBDC rice sheet XPS figure of embodiment 1；
Fig. 4 is the metal-organic framework materials CuBDC nanometer sheet FT-IR figure of embodiment 1；
Fig. 5 is the CV figure of the metal-organic framework materials CuBDC nanometer sheet of embodiment 1；
Fig. 6 is the cycle performance figure of the metal-organic framework materials CuBDC nanometer sheet of embodiment 1；
Fig. 7 is the metal-organic framework materials CuBDC nanometer sheet high rate performance figure of embodiment 1.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention Content is not limited solely to the following examples.
Embodiment 1:
The preparation method of metal-organic framework materials CuBDC nanometer sheet, includes following steps:
1) copper nitrate solid 0.3g is weighed, to dibenzoic acid solid 1.313g, with acetonitrile and the 40ml N of 20ml, N-diformazan The dissolving of base formamide solution；
2) by step 1) 60 DEG C of heating in water bath of gained solution stir 6 hours；
3) by step 2) gained solution put in 80 DEG C of baking ovens dry 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet；
As it is shown in figure 1, it is the highest to prepare metal-organic framework materials CuBDC nanometer sheet purity, there is no other impurity and exist；As Shown in Fig. 2, observing nanometer sheet thickness in scanning electron microscope (SEM) clearly is 15～25 nanometers, lateral width be 3～ 7 microns；As it is shown on figure 3, XPS figure shows when electric discharge 0.01v, Cu2+It is reduced into Cu0, when charging to 3v, it is oxidizing to again Cu2+.As shown in Figure 4, there is the symmetrical and asymmetric vibration of BDC, show that BDC is not destroyed.As it is shown in figure 5, tested by CV It can be seen that tested by CV it can be seen that the CV curve co-insides degree of its former circles is the highest, the reversibility that sodium ion reacts is described Excellent.
The preparation method of sodium-ion battery negative pole of the present invention is as follows, uses metal-organic framework materials CuBDC nanometer sheet to make For active material, acetylene black is as conductive agent, and politef is as binding agent, active material, acetylene black, the mass ratio of CMC For 60:30:10；After they being sufficiently mixed in proportion, add a small amount of isopropanol, grind uniformly, by active substance and acetylene black After being sufficiently mixed in proportion, add the CMC aqueous solution of respective amount, grind uniformly, gained mixed solution is applied to about 10 microns of thickness Copper Foil on.The oven drying that electrode slice after coating is placed in 80 DEG C took out after 24 hours, was made into a diameter of 14 microns Electrode slice standby.NaPF with 1M6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) as electrolyte, sodium Sheet is negative pole, and Celgard2325 is barrier film, and CR2016 type rustless steel is that battery case is assembled into button sode cell half-cell.Sodium Remaining step of the preparation method of battery half cell is identical with common preparation method.
The metal-organic framework materials CuBDC nanometer sheet that as shown in Figure 6 prepared by the present invention, through carrying out electricity in glove box Charge-discharge test is carried out after the assembling in pond.Cyclic voltammetry shows, metal-organic framework materials CuBDC nanometer sheet exists Under the electric current density of 5000mA/g, after circulation 100 circle, capacity still has 120mAh/g.As it is shown in fig. 7, prepared by the present invention The test of metal-organic framework materials CuBDC nanometer sheet high rate performance shows, the multiplying power of metal-organic framework materials CuBDC nanometer sheet Performance highlights, and under the electric current density of 100mA/g to 10000mA/g, has the highest capacity, close at the electric current of 10000mA/g Under degree, with CMC as binding agent, its capacity still has 75mAh/g.And when electric current density returns to 100mh/g, still possess very Good capacity restoration performance.
Comparative example 2:
The preparation method of metal-organic framework materials CuBDC nanometer sheet, includes following steps:
1) copper nitrate solid 0.3g is weighed, to dibenzoic acid solid 1.313g, with 60ml DMF solution Dissolve；
2) by step 1) 60 DEG C of heating in water bath of gained solution stir 6 hours；
3) by step 2) gained solution put in 80 DEG C of baking ovens dry 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet, the material pattern heterogeneity of gained.
The metal-organic framework materials CuBDC nanometer sheet active material obtained by this example assembles half-cell, uses button Formula battery is tested.Constant current charge-discharge test shows, metal-organic framework materials CuBDC nanometer sheet electrode is 5000mA/g's Under electric current density, after circulation 100 circle, capacity is 20mAh/g, poor performance compared with example 1.
Embodiment 3:
1) copper nitrate solid 0.3g is weighed, to dibenzoic acid solid 1.313g, with acetonitrile and the 40ml N of 20ml, N-diformazan Base formamide solution dissolves；
2) by step 1) 60 DEG C of heating in water bath of gained solution stir 8 hours；
3) by step 2) gained solution put in 80 DEG C of baking ovens dry 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet.
The metal-organic framework materials CuBDC nanometer sheet active material obtained by this example assembles half-cell, uses button Formula battery is tested.Constant current charge-discharge test shows, metal-organic framework materials CuBDC nanometer sheet electrode is 5000mA/g's Under electric current density, after circulation 100 circle, capacity is 114mAh/g.
Embodiment 4:
1) copper nitrate solid 0.3g is weighed, to dibenzoic acid solid 1.313g, with acetonitrile and the 40ml N of 20ml, N-diformazan Base formamide solution dissolves；
2) by step 1) 80 DEG C of heating in water bath of gained solution stirring stirring 8 hours；
3) by step 2) gained solution put in 80 DEG C of baking ovens dry 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet.
The metal-organic framework materials CuBDC nanometer sheet active material obtained by this example assembles half-cell, uses button Formula battery is tested.Constant current charge-discharge test shows, metal-organic framework materials CuBDC nanometer sheet electrode is 5000mA/g's Under electric current density, after circulation 50 circle, capacity is 117mAh/g.
Comparative example 5:
1) copper nitrate solid 0.1208g is weighed, to dibenzoic acid solid 2.0g, with acetonitrile and the 40ml N of 20ml, N-bis- Methylformamide solution dissolves；
2) by step 1) 60 DEG C of heating in water bath of gained solution stirring stirring 6 hours；
3) by step 2) gained solution put in 80 DEG C of baking ovens dry 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet, gained material pattern heterogeneity.
The metal-organic framework materials CuBDC nanometer sheet active material obtained by this example assembles half-cell, uses button Formula battery is tested.Constant current charge-discharge test shows, metal-organic framework materials CuBDC nanometer sheet electrode is 5000mA/g's Under electric current density, after circulation 100 circle, capacity is 24mAh/g, poor performance compared with example 1.

Claims (7)

1. metal-organic framework materials CuBDC nanometer sheet, its by multi-layer C uBDC nanometer sheet stacking form, monolithic nanometer sheet thickness Being 15～25 nanometers, lateral width is 3～7 microns, has loose structure, and its BET specific surface area is 540～550m2/ g, porous The aperture of structure is less than 2nm, belongs to microcellular structure.
2. the preparation method of the metal-organic framework materials CuBDC described in claim 1, includes following steps:
1) weigh copper nitrate solid 0.25～0.3g, dibenzoic acid solid 1.2～1.5g organic solvent is dissolved；
2) by step 1) gained solution water-bath heated and stirred；
3) by step 2) gained solution put in baking oven dry, obtain metal-organic framework materials CuBDC nanometer sheet.
3. the preparation method of the metal-organic framework materials CuBDC as described in claim 1, it is characterised in that described drying temperature Degree is 80 DEG C, drying time 18-24 hour.
4. the preparation method of the metal-organic framework materials CuBDC as described in claim 1, it is characterised in that described is organic molten Agent is 20mL acetonitrile and 40mLN, the mixing of dinethylformamide.
5. the preparation method of the metal-organic framework materials CuBDC as described in claim 1, it is characterised in that described water-bath adds Hot temperature 60～80 DEG C, stir 6～8 hours.
6. the metal-organic framework materials CuBDC nanometer sheet described in claim 1 is as the negative active core-shell material of sodium-ion battery Application.
7. the application as described in claim 6, it is characterised in that with metal-organic framework materials CuBDC nanometer sheet for sode cell half The positive pole of battery, sodium sheet is that the negative pole of sode cell half-cell assembles.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573519A (en) * 2017-09-30 2018-01-12 华南理工大学 A kind of method of the mesoporous Cu BDC materials of Fast back-projection algorithm
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.
WO2019158932A1 (en) * 2018-02-15 2019-08-22 The Chancellor, Masters And Scholars Of The University Of Cambridge Constant shear continuous reactor device
CN112002938A (en) * 2020-08-28 2020-11-27 南京大学 Composite solid electrolyte membrane based on Cu (BDC) MOF (Metal organic framework) multilevel structure and preparation method thereof
CN112657352A (en) * 2020-11-30 2021-04-16 同济大学 Polyamide thin film layer composite reverse osmosis film and preparation method and application thereof
CN114875429A (en) * 2022-02-17 2022-08-09 上海应用技术大学 Flexible thin film electrode and preparation method and application thereof
TWI779977B (en) * 2021-12-29 2022-10-01 芯量科技股份有限公司 Anode slurry and preparation method thereof and battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101516894A (en) * 2006-07-27 2009-08-26 巴斯夫欧洲公司 Method for producing copper-containing organometallic framework material
CN103456961A (en) * 2013-09-12 2013-12-18 电子科技大学 Organic cathode material for sodium ion battery
CN104362310A (en) * 2014-09-23 2015-02-18 四川省有色冶金研究院有限公司 Organic anode material for lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101516894A (en) * 2006-07-27 2009-08-26 巴斯夫欧洲公司 Method for producing copper-containing organometallic framework material
CN103456961A (en) * 2013-09-12 2013-12-18 电子科技大学 Organic cathode material for sodium ion battery
CN104362310A (en) * 2014-09-23 2015-02-18 四川省有色冶金研究院有限公司 Organic anode material for lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ELAHE AHMADI FEIJANI ET AL.: ""Poly(vinylidene fluoride) based mixed matrix membranes comprising metal organic frameworks for gas separation applications"", 《CHEMICAL ENGINEERING RESEARCH AND DESIGN》 *
ZHIFENG XIN ET AL.: ""Hierarchically Micro-and Mesoporous Coordination Polymer Nanostructures with High Adsorption Performance"", 《CRYSTAL GROWTH & DESIGN》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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.
CN107573519A (en) * 2017-09-30 2018-01-12 华南理工大学 A kind of method of the mesoporous Cu BDC materials of Fast back-projection algorithm
CN111902207B (en) * 2018-02-15 2022-08-05 剑桥企业有限公司 Continuous reactor device with constant shear
WO2019158932A1 (en) * 2018-02-15 2019-08-22 The Chancellor, Masters And Scholars Of The University Of Cambridge Constant shear continuous reactor device
CN111902207A (en) * 2018-02-15 2020-11-06 剑桥企业有限公司 Continuous reactor device with constant shear
US11724241B2 (en) 2018-02-15 2023-08-15 Cambridge Enterprise Limited Constant shear continuous reactor device
CN112002938A (en) * 2020-08-28 2020-11-27 南京大学 Composite solid electrolyte membrane based on Cu (BDC) MOF (Metal organic framework) multilevel structure and preparation method thereof
CN112002938B (en) * 2020-08-28 2022-03-15 南京大学 Composite solid electrolyte membrane based on Cu (BDC) MOF (Metal organic framework) multilevel structure and preparation method thereof
CN112657352B (en) * 2020-11-30 2021-11-12 同济大学 Polyamide thin film layer composite reverse osmosis film and preparation method and application thereof
CN112657352A (en) * 2020-11-30 2021-04-16 同济大学 Polyamide thin film layer composite reverse osmosis film and preparation method and application thereof
TWI779977B (en) * 2021-12-29 2022-10-01 芯量科技股份有限公司 Anode slurry and preparation method thereof and battery
CN114875429A (en) * 2022-02-17 2022-08-09 上海应用技术大学 Flexible thin film electrode and preparation method and application thereof
CN114875429B (en) * 2022-02-17 2023-08-04 上海应用技术大学 Flexible thin film electrode and preparation method and application thereof

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