CN106252663B - 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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CN106252663B
CN106252663B CN201610637309.0A CN201610637309A CN106252663B CN 106252663 B CN106252663 B CN 106252663B CN 201610637309 A CN201610637309 A CN 201610637309A CN 106252663 B CN106252663 B CN 106252663B
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nanometer sheet
metal
organic framework
framework materials
cubdc
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CN106252663A (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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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/60Selection of substances as active materials, active masses, active liquids of organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41Preparation of salts of carboxylic acids
    • C07C51/418Preparation of metal complexes containing carboxylic acid moieties
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14Monocyclic dicarboxylic acids
    • C07C63/15Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/261,4 - Benzenedicarboxylic acid
    • C07C63/28Salts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to nanometer material and electrochemical technology fields, more particularly 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 used as anode material of lithium-ion battery, it is stacked by multi-layer C uBDC nanometer sheet, and monolithic nanometer sheet thickness is 15~25 nanometers, and lateral width is 3~7 microns, with porous structure, BET specific surface area is 530~550m2The aperture of/g, porous structure are less than 2nm, belong to microcellular structure.The beneficial effects of the present invention are: the metal-organic framework materials CuBDC nanometer sheet pattern based on preparation is uniform and has excellent conductive performance, when negative electrode material of the electrode as sodium-ion battery, excellent multiplying power, higher specific capacity and good cyclical stability are shown.Present invention process is simple, and economical and practical, meets the requirement of Green Chemistry, is conducive 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 nanometer material and electrochemical technology fields, and in particular to a kind of metal-organic framework materials CuBDC (wherein BDC=1,4- dicarboxylic acid radical benzene) nanometer sheet and preparation method thereof, can be used as anode material of lithium-ion battery.
Background technique
Nowadays, with the fast development in the fields such as pure electric automobile, hybrid vehicle, extensive energy storage device, Lithium ion etc. have high-energy density, high power density, long circulation life energy storage device obtain the wide of numerous researchers General concern.It is excellent that lithium ion battery is high with its specific energy, power density is high, have extended cycle life, self discharge is small, the ratio of performance to price is high etc. Point has become the main selecting object of the rechargeable formula power supply of current portable electronic product.But due to lithium resource shortage system An important factor for about it develops, therefore, needs the energy-storage battery system for developing next-generation excellent combination property.And sodium and lithium have Similar physics and chemical property, and sodium is resourceful, it is low in cost, therefore sodium-ion battery is the electricity for having very much development potentiality Pond body system.But since sodium atom radius is larger, cause commercialization negative electrode material graphite can not be as in lithium ion battery It is embedded in and is deviate from.Searching suitable anode material of lithium-ion battery becomes one of urgent problem to be solved.
Studies have shown that the specific surface area of nano material (such as nano wire, nanometer rods, nano particle, nanometer sheet) it is larger and Size is smaller, can shorten the diffusion path of lithium ion, improves the ionic conductivity of material, while effectively reducing material internal and answering Power finally prevents structural breakdown of the electrode material in charge and discharge process.However, by nano material formed it is unstable SEI quantity is more, makes the irreversible capacity increase of electrode material and coulombic efficiency reduces.It constructs and is formed by point by nano particle The mesoporous laminated structure of grade micro-meter scale or submicron-scale is considered as the effective way solved these problems.
Summary of the invention
The purpose of the present invention is to provide a kind of simple process, the requirement that meets Green Chemistry, there is excellent electrochemistry The metal-organic framework materials CuBDC nanometer sheet and its preparation method and application of energy.
The technical proposal adopted by the invention to solve the above technical problems is that: metal-organic framework materials CuBDC nanometer sheet, It is stacked by multi-layer C uBDC nanometer sheet, and monolithic nanometer sheet thickness is 15~25 nanometers, and lateral width is 3~7 microns, tool There is porous structure, BET specific surface area is 530~550m2The aperture of/g, porous structure are less than 2nm, belong to microcellular structure.
The preparation method of the metal-organic framework materials CuBDC nanometer sheet, includes following steps:
1) copper nitrate 0.25~0.3g of solid is weighed, to dibenzoic acid 1.2~1.5g of solid, is dissolved with organic solvent;
2) step 1) acquired solution heating water bath is stirred;
3) step 2) acquired solution is put into baking oven and is dried, obtain metal-organic framework materials CuBDC nanometer sheet.
According to the above scheme, the drying temperature is 80 DEG C, drying time 18-24 hours.
According to the above scheme, the organic solvent is 20mL acetonitrile and 40mLN, the mixing of dinethylformamide.
According to the above scheme, 60~80 DEG C of the water bath heating temperature stirs 6~8 hours.
The application of negative electrode active material of the metal-organic framework materials CuBDC nanometer sheet as sodium-ion battery.
According to the above scheme, using metal-organic framework materials CuBDC nanometer sheet as the anode of sode cell half-cell, sodium piece is sodium The cathode of battery half cell is assembled.
The present invention is divided into three layers by the CuBDC of strategy synthesis from top to down, liquid medium, and top is copper nitrate solution, Bottom is to be sent out in intermediate region by an intermediate flux layer separation, copper ion and to dibenzoic acid dibenzoic acid solution The growth of raw BDC crystal, synthesized CuBDC is porous, and surface area is big, has good chemical property.
The beneficial effects of the present invention are: the metal-organic framework materials CuBDC nanometer sheet pattern based on preparation it is uniform and With excellent conductive performance, when negative electrode material of the electrode as sodium-ion battery, excellent multiplying power, higher specific volume are shown Amount and good cyclical stability.Present invention process is simple, and economical and practical, meets the requirement of Green Chemistry, is conducive to market Change and promotes.
Detailed description of the invention
Fig. 1 is the XRD diagram 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 CuBDC meters of piece XPS figures of metal-organic framework materials 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.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the 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 the acetonitrile and 40ml N, N- diformazan of 20ml The dissolution of base formamide solution;
2) 60 DEG C of heating water baths of step 1) acquired solution are stirred 6 hours;
3) step 2) acquired solution is put into 80 DEG C of baking ovens and is dried 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet;
As shown in Figure 1, it is very high to prepare metal-organic framework materials CuBDC nanometer sheet purity, other impurities presence is had no;Such as Shown in Fig. 2, clearly observed in scanning electron microscope (SEM) nanometer sheet thickness be 15~25 nanometers, lateral width be 3~ 7 microns;As shown in figure 3, XPS chart is bright in electric discharge 0.01v, Cu2+It is reduced into Cu0, when charging to 3v, and it is oxidizing to Cu2+.As shown in figure 4, there are BDC symmetrically to vibrate with asymmetry, show that BDC is not destroyed.As shown in figure 5, being tested by CV As can be seen that it is very high by the CV curve co-insides degree that CV test can be seen that its former circle, illustrate the invertibity of sodium ion reaction It is excellent.
The preparation method of sodium-ion battery cathode of the present invention is as follows, is made using metal-organic framework materials CuBDC nanometer sheet For active material, acetylene black as conductive agent, polytetrafluoroethylene (PTFE) as binder, active material, acetylene black, CMC mass ratio For 60:30:10;After they are sufficiently mixed in proportion, a small amount of isopropanol is added, grinding is uniform, by active material and acetylene black After being sufficiently mixed in proportion, the CMC aqueous solution of corresponding amount is added, gained mixed solution uniformly, is applied to about 10 microns of thickness by grinding Copper foil on.It is taken out after electrode slice after coating to be placed in oven drying 24 hours of 80 DEG C, being made into diameter is 14 microns Electrode slice it is spare.With the NaPF of 1M6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) as electrolyte, sodium Piece is cathode, and Celgard2325 is diaphragm, and CR2016 type stainless 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 as common preparation method.
Metal-organic framework materials CuBDC nanometer sheet prepared by the present invention as shown in Figure 6, by carrying out electricity in glove box Charge-discharge test is carried out after the assembling in pond.Cyclic voltammetry shows that metal-organic framework materials CuBDC nanometer sheet exists Under the current density of 5000mA/g, after 100 circle of circulation, capacity still has 120mAh/g.As shown in fig. 7, prepared by the present invention Metal-organic framework materials CuBDC nanometer sheet high rate performance tests the multiplying power for showing metal-organic framework materials CuBDC nanometer sheet Performance is prominent, under the current density of 100mA/g to 10000mA/g, has very high capacity, close in the electric current of 10000mA/g Under degree, using CMC as binder, capacity still has 75mAh/g.And when current density is restored to 100mh/g, still have 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 n,N-Dimethylformamide solution Dissolution;
2) 60 DEG C of heating water baths of step 1) acquired solution are stirred 6 hours;
3) step 2) acquired solution is put into 80 DEG C of baking ovens and is dried 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet, resulting substance pattern are inhomogenous.
This example metal-organic framework materials CuBDC nanometer sheet active material obtained is assembled into half-cell, using button Formula battery is tested.Constant current charge-discharge test shows CuBDC nanometers of plate electrodes of metal-organic framework materials 5000mA/g's Under current density, after 100 circle of circulation, capacity 20mAh/g, the poor performance compared with example 1.
Embodiment 3:
1) copper nitrate solid 0.3g is weighed, to dibenzoic acid solid 1.313g, with the acetonitrile and 40ml N, N- diformazan of 20ml The dissolution of base formamide solution;
2) 60 DEG C of heating water baths of step 1) acquired solution are stirred 8 hours;
3) step 2) acquired solution is put into 80 DEG C of baking ovens and is dried 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet.
This example metal-organic framework materials CuBDC nanometer sheet active material obtained is assembled into half-cell, using button Formula battery is tested.Constant current charge-discharge test shows CuBDC nanometers of plate electrodes of metal-organic framework materials 5000mA/g's Under current density, after 100 circle of circulation, capacity 114mAh/g.
Embodiment 4:
1) copper nitrate solid 0.3g is weighed, to dibenzoic acid solid 1.313g, with the acetonitrile and 40ml N, N- diformazan of 20ml The dissolution of base formamide solution;
2) by heating water bath stirring stirring 8 hours of 80 DEG C of step 1) acquired solution;
3) step 2) acquired solution is put into 80 DEG C of baking ovens and is dried 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet.
This example metal-organic framework materials CuBDC nanometer sheet active material obtained is assembled into half-cell, using button Formula battery is tested.Constant current charge-discharge test shows CuBDC nanometers of plate electrodes of metal-organic framework materials 5000mA/g's Under current density, after 50 circle of circulation, capacity 117mAh/g.
Comparative example 5:
1) copper nitrate solid 0.1208g is weighed, to dibenzoic acid solid 2.0g, with the acetonitrile and 40ml N, N- bis- of 20ml The dissolution of methylformamide solution;
2) by heating water bath stirring stirring 6 hours of 60 DEG C of step 1) acquired solution;
3) step 2) acquired solution is put into 80 DEG C of baking ovens and is dried 24 hours, obtain metal-organic framework materials CuBDC Nanometer sheet, obtained material pattern are inhomogenous.
This example metal-organic framework materials CuBDC nanometer sheet active material obtained is assembled into half-cell, using button Formula battery is tested.Constant current charge-discharge test shows CuBDC nanometers of plate electrodes of metal-organic framework materials 5000mA/g's Under current density, after 100 circle of circulation, capacity 24mAh/g, the poor performance compared with example 1.

Claims (3)

1. the preparation method of metal-organic framework materials CuBDC, the metal-organic framework materials CuBDC nanometer sheet is by multilayer CuBDC nanometer sheet stacks, and monolithic nanometer sheet thickness is 15~25 nanometers, and lateral width is 3~7 microns, has porous knot Structure, BET specific surface area are 540~550m2The aperture of/g, porous structure are less than 2nm, belong to microcellular structure, include following Step:
1) copper nitrate 0.25~0.3g of solid is weighed, 1.2~1.5g of dibenzoic acid solid is dissolved with organic solvent;Described has Solvent is 20mL acetonitrile and 40mLN, the mixing of dinethylformamide;
2) step 1) acquired solution heating water bath is stirred;60~80 DEG C of the water bath heating temperature stirs 6~8 hours;
3) step 2) acquired solution is put into baking oven and is dried, obtain metal-organic framework materials CuBDC nanometer sheet;The baking Dry temperature is 80 DEG C, drying time 18-24 hours.
2. nanometer sheet obtained by the preparation method of metal-organic framework materials CuBDC described in claim 1 is as sodium-ion battery Negative electrode active material application.
3. application as described in claim 2, it is characterised in that using metal-organic framework materials CuBDC nanometer sheet as sode cell half The anode of battery, sodium piece are that the cathode of sode cell half-cell is assembled.
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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
CN111902207A (en) * 2018-02-15 2020-11-06 剑桥企业有限公司 Continuous reactor device with constant shear
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

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