CN110112382A - Cu-MOF/GO compound and its preparation method and application based on green organic ligand - Google Patents
Cu-MOF/GO compound and its preparation method and application based on green organic ligand Download PDFInfo
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- CN110112382A CN110112382A CN201910285018.3A CN201910285018A CN110112382A CN 110112382 A CN110112382 A CN 110112382A CN 201910285018 A CN201910285018 A CN 201910285018A CN 110112382 A CN110112382 A CN 110112382A
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a kind of preparation methods of Cu-MOF/GO compound based on green organic ligand, comprising the following steps: is dispersed in water conductive paste material, transition metal salt is added, dissolution obtains solution one；Green organic ligand is soluble in water, obtain solution two；The solution one and solution two are mixed, 5~30h of hydro-thermal reaction at 60~200 DEG C, obtained solids is Cu-MOF/GO compound；Wherein, the conductive paste material is graphene oxide, and the transition metal salt is Cu (NO3)2Or its hydrate, the green organic ligand is citric acid or its hydrate.The invention also discloses the Cu-MOF/GO compound prepared by the above method and its applications.The preparation method of Cu-MOF/GO compound of the invention can substantially reduce cost, and environmental pollution is effectively reduced using citric acid green ligand.
Description
Technical field
The present invention relates to metal-organic framework material technical fields, and in particular to a kind of Cu- based on green organic ligand
MOF/GO compound and its preparation method and application.
Background technique
With the continuous development of society, demand of the mankind to resource is increasing.Since being widely used for fossil fuel is made
At lack of energy, the problems such as greenhouse effects and environmental pollution.Therefore seem extremely urgent to the development and utilization of new energy.In recent years
Come, the clean energy resourcies such as solar energy, wind energy, tide energy, water energy and nuclear energy are since its is renewable and the characteristics such as low pollution cause entirely
Worldwide extensive concern.But most of clean energy resource, all have discontinuous, unstable and is difficult to direct benefit
The characteristics of using.Thus how to realize efficient, cheap and environmentally friendly energy stores and conversion in the 21 century for pursuing sustainable development
Today seem and be even more important.In order to overcome the use bring energy and environmental crisis of fossil fuel, develop high-efficiency environment friendly
Energy storage technology is particularly important.And lithium ion battery is because it is big with energy density, operating voltage is high, has extended cycle life, certainly
It discharges many advantages, such as low, maintenance cost is few and environmental-friendly, is occupied an important position in energy storage field.In recent years electronic market and
The fields such as electric car rapidly develop, higher and higher to the performance requirement of lithium ion battery.Therefore research and development have high-performance, it is low at
This lithium ion battery has a very important significance.
Lithium ion battery is mainly made of anode, cathode, diaphragm and four part of electrolyte, during the work time by chemical energy
It is converted to electric energy.And important component of the cathode as lithium ion battery, it is largely fixed the performance of battery.Mesh
Before, negative electrode material is mainly graphite, and theoretical capacity only has 372mA h g-1, be no longer satisfied at present to high power density and
The requirement of energy density.Therefore, it is badly in need of developing a kind of with low cost, the novel cathode material of high capacity and more preferable durability
Material.However, some electrode materials with superior function developed at present, such as metal alloy, silicon, transition metal oxide
With sulfide etc., but the preparation step of these negative electrode materials is various, and program is complicated and needs expensive equipment, so that it is difficult
To replace graphite cathode material, to hinder their commercialized development.
However, metal organic frame (MOFs) causes each as versus young and the porous material of fast development
The huge interest of area research person.MOFs material has been widely used in gas trapping and storage at present, and proton conduction is urged
The fields such as the storage and conversion of change, drug delivery and energy.In recent years using MOFs as the electrode material of lithium ion battery
Receive the extensive concern of researchers.
MOFs is a series of interesting porosu solids, has specific crystal structure and great surface area, they are usually
It is synthesized by the complexation reaction between metal cluster/ion and organic ligand appropriate.In late 1990s by Yaghi and Li
It was found that.Synthesizing the common metal cluster/ion of MOFs is transition metal and some lanthanide series, and organic ligand usually contains pyridyl group
And cyano, crown ether, polyamines, phosphonate or carboxylate, play the function served as bridge of metal ion in connection MOF.It is various each due to having
The difference of the main member unit of sample can effectively can be made by solvent-thermal method, microwave heating method, electrochemical process and Mechanical Method
The MOF structure of standby 0D, 1D, 2D, 3D out.Up to the present having reported more than 20000 kinds has controlled dimensions, shape and characteristic
MOFs.Therefore, according to the demand of different application, by adjusting the type of metal center ion and the type and ruler of organic ligand
It is very little, can by MOFs design of material at specific structure snd size to meet the needs of practical application.
Since the preparation process of MOFs is simple, energy consumption is low, and the cathode of MOFs and its derivative as lithium ion battery
Material has many significant advantages, such as: 1) it can be by designing various MOF and combining specific heat treatment, it is easy to ground
Adjust their chemical component；2) MOFs has controllable porosity and huge surface area, enters electrode and true convenient for electrolyte
Protect big electrolyte/electrode contact surface product；3) have well-regulated duct, can significantly shorten electronics and ion diffusion path, this
It is very beneficial for improving the high rate performance of MOFs electrode material；4) preparation process is simple, at low cost, there is very big commercialized development
Potentiality.So that MOFs shows huge potentiality in energy storage and conversion aspect.In recent years, researcher there are many and
Its seminar is dedicated to studying novel multi-functional MOFs, and the electrode material as lithium ion battery is simultaneously shown excellent
Chemical property.
Currently, pure MOFs has been considered to be a kind of very promising electrode material.MOFs in addition to can directly other than use,
Presoma template is also used as by different heat treatment or chemically treated method to obtain various porous materials, including carbon
Sill, metal oxide, metal carbides and multicomponent composite materials etc..With traditional inorganic material and polymers function material
Material is compared, and MOFs can inherit the advantage of both they, has proven to very promising secondary cell and super capacitor
The electrode material of device.
R.Senthil Kumar etc. utilizes Cu2+[Cu is prepared for by electrochemical synthesis with terephthalic acid (TPA)2
(C8H4O4)4] n metal organic framework.As the negative electrode material of lithium ion battery, it is found that this porous crystalline material has
Reversible Li+ storage capacity.It provides 227mA h g in first circulation-1Capacity, about the 95% of theoretical capacity.
Studies have found that Cu-BTC is in certain Li+It can be stabilized in concentration.And Cu3(BTC)2Due to having big
Surface area, high pore volume, high chemical stability and its have in conjunction with small molecule ability.So Maiti etc. utilizes Cu
(NO3)2·2.5H2O and trimesic acid (H3BTC) pass through solvent structure regular octahedron Cu3(BTC)2, and for the first time as
The negative electrode material of lithium ion battery.Cu3(BTC)2Negative electrode material is in 96mA g-1Current density under, 740mA h g can be kept-1Reversible capacity.In 383mA g-1Current density under specific capacity be 474mA h g-1, circulation 50 circle after capacity almost without
Decaying.This is the result shows that MOFs is the electrode material of promising next-generation lithium ion battery.
However, pure MOFs is due to itself poorly conductive, so that its chemical property is difficult to achieve the desired results.So
Researchers pass through the electric conductivity with the compound improvement MOFs of conductive paste material.Li et al. uses Cu (NO first3)2·3H2O and to benzene two
Formic acid and redox graphene (RGO) prepare Cu-MOF/RGO composite material by hydro-thermal method, then as preceding
It drives body and calcines 2h at 350 DEG C in air, be prepared for porous C uO/RGO composite material.The material is as the negative of lithium ion battery
Pole material is in 100mA g-1Current density under circulation 50 circle after its capacity be 466.6mA h g-1。
Gao etc. utilizes Cu (NO3)2·6H2O is metal center ion, and aspartic acid is organic ligand, with oxygen reduction fossil
Black alkene (rGO) is compound to be prepared for Cu-MOF/rGO composite material.When being made the negative electrode material of lithium ion battery, in 50mA g-1
Current density under, circulation 50 circle after material specific discharge capacity up to 520mA h g-1.Therefore by multiple with conductive paste material
The electric conductivity that can effectively improve MOFs is closed, high performance lithium ion battery is prepared.But its energy density and power density
Existing market is far from satisfying to the performance requirement of lithium ion battery.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Cu-MOF/GO compounds based on green organic ligand, lead to
Cross MOFs and the material oxidation graphene with superior electrical conductivity and containing abundant functional group is compound, MOFs and graphene oxide
(GO) with chemical bonds between, the electric conductivity and stability of MOFs both can be improved, and can produce synergistic effect, by two kinds
The chemical property of material is overlapped, to prepare the negative electrode material haveing excellent performance.
In order to solve the above-mentioned technical problems, the present invention provides a kind of Cu-MOF/GO based on green organic ligand is compound
The preparation method of object, comprising the following steps:
Conductive paste material is dispersed in water, transition metal salt is added, dissolution obtains solution one；
Green organic ligand is soluble in water, obtain solution two；
The solution one and solution two are mixed, 5~30h of hydro-thermal reaction at 60~200 DEG C, obtained solids is
Cu-MOF/GO compound；
Wherein, the conductive paste material is graphene oxide, and the transition metal salt is Cu (NO3)2Or its hydrate, institute
Stating green organic ligand is citric acid or its hydrate.
Further, the mass ratio of the conductive paste material and Cu-MOF are 1~50wt%, and wherein Cu-MOF is transition gold
Belong to salt and the product that hydro-thermal reaction obtains occurs for green organic ligand.
Further, Cu (NO3)2Hydrate is Cu (NO3)2·3H2O, citric acid hydrate are monohydrate potassium.
Further, the molar ratio of the transition metal salt and green organic ligand is preferably 1~3:1, and more preferably 2:
1。
Further, the temperature of the hydro-thermal reaction is 140 DEG C, time 20h.
Further, include the steps that obtained Cu-MOF/GO composite solids are filtered, cleaned and dried.
Further, the temperature of the drying is 100~120 DEG C, and drying time is 2~8h.
Another aspect of the present invention additionally provides the Cu-MOF/GO compound being prepared according to the method.
In addition, the application the present invention also provides the Cu-MOF/GO compound as lithium ion battery negative material.
Beneficial effects of the present invention:
1, the present invention is used as " green " ligand using citric acid, with Cu2+It prepares together and meets negative electrode of lithium ion battery material
Expect desired Cu-MOF material, on the one hand reduces the harm in synthesis process to human body, on the other hand, the valence of citrate ligand
Lattice organic ligand more complicated than common terephthalic acid (TPA) or trimesic acid etc. is cheaper, can substantially reduce cost, and effectively drop
Low environment pollution.
2, the present invention is compound by MOFs and the material oxidation graphene with superior electrical conductivity and containing abundant functional group,
With chemical bonds between MOFs and GO, the electric conductivity and stability of MOFs both can be improved, and can produce synergistic effect, it will
The chemical property of two kinds of materials is overlapped, to prepare the lithium cell cathode material haveing excellent performance.
Detailed description of the invention
Fig. 1 is the XRD powder diagram of the compound of the embodiment of the present invention 1~3, the compound of comparative example 1 and GO；
Fig. 2 is the transmission electron microscope picture (TEM) of Cu-MOF/GO compound of the invention；
Fig. 3 is the electrochemical impedance spectroscopy of the compound of the embodiment of the present invention 1~3；
Fig. 4 is the high rate performance schematic diagram of the compound of the embodiment of the present invention 1~3.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with
It more fully understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1-3: preparation Cu-MOF/GO compound
(1) it calculates, claims according to the ratio that the mass ratio of GO and Cu-CA-MOF is respectively 1.75wt%, 2wt%, 3.5wt%
GO, ultrasonic 20min is taken to be dispersed in the deionized water of 15mL；
(2) Cu (NO of 4mmol (0.966g) is weighed3)2·3H2O is dissolved in the deionized water for being dispersed with graphene oxide,
Magnetic agitation is to being completely dissolved；
(3) monohydrate potassium for weighing 2mmol (0.420g), is dissolved in the deionized water of 5mL, and magnetic agitation is to complete
Dissolution, is added in the solution of (2), magnetic agitation 30min；
(4) mixed solution that (3) obtain being transferred in the reaction kettle of 50mL, setting oven temperature is 140 DEG C, 20h is reacted,
Obtain blue solid；
(5) obtained crystal is filtered, and be washed with deionized water 3-5 times；
(6) solid powder being prepared is dried to 5h at 110 DEG C, to remove the water in Free water and crystal structure,
Obtained compound is denoted as Cu-MOF/GO1, Cu-MOF/GO2 and Cu-MOF/GO3 respectively, and (mass ratio of GO is respectively
1.75wt%, 2wt% and 3.5wt%).
Comparative example 1: preparation Cu-MOF compound
(1) Cu (NO of 4mmol (0.966g) is weighed3)2·3H2O is dissolved in deionized water, magnetic agitation to completely it is molten
Solution；
(2) monohydrate potassium for weighing 2mmol (0.420g), is dissolved in the deionized water of 5mL, and magnetic agitation is to complete
Dissolution, is added in the solution of (1), magnetic agitation 30min；
(3) mixed solution that (2) obtain being transferred in the reaction kettle of 50mL, setting oven temperature is 140 DEG C, 20h is reacted,
Obtain blue solid；
(4) obtained crystal is filtered, and be washed with deionized water 3-5 times；
(5) solid powder being prepared is dried to 5h at 110 DEG C, to remove the water in Free water and crystal structure.
Detection and characterization
Referring to Fig. 1, by XRD spectrum it was found that the position of the characteristic peak of Cu-MOF is respectively at 19.7 °, 17.02 °,
19.6 °, 22.3-25.2 °.For Cu-MOF/GO composite material, diffracting spectrum is substantially similar with Cu-MOF, shows Cu-MOF
Crystal property retained in the composite, the intensity of all diffraction maximums of Cu-MOF/GO composite material all significantly drops
It is low and almost disappear at 30 ° of later peaks, show that GO is appropriate during synthetic composite material and hinders the knot of Cu-MOF
Crystalline substance causes Cu-MOF structure that slight deformation has occurred.
By Fig. 2 it can be found that the material forms sandwich, one layer of 5nm or so is uniformly scattered in GO piece interlayer
Cu-MOF particle.Such sandwich can effectively promote the chemical property of material.
As shown in figure 3, straight line two parts of semicircle and low frequency range that electrochemical impedance map is gone by high frequency form, high frequency
The semicircle in area represents charge transfer resistance, and the slope of the straight line of low frequency range represents ion transmission resistance.We have found that with GO
The increase of content, Cu-MOF/GO composite material gradually become smaller in half circular diameter of high frequency region, illustrate its electronic conductivity with GO
The increase of content becomes more excellent, and the increase of the content with GO, and the straight line of low frequency range tends to parallel Y-axis, so with
The increase of GO content, the ionic conductivity of material also become more excellent.So can effectively be improved by the compound of GO
The electrochemical impedance of Cu-MOF material.
As shown in figure 4, working as current density 100mA g-1Progressively increase to 200,500mA g-1Afterwards, 100mA g is returned-1
When, the discharge capacity when capacity of the Cu-MOF/GO composite material can still restore to about third circle.Also, with
100mA g-1Current density under continue cycling through, Cu-MOF/GO composite material shows apparent capacity rise phenomenon, this
It may be due to the volume progress with circulation, contact of the electrode material with electrolyte is more abundant, has activated electrode material and table
Reveal the phenomenon that capacity rises.
Therefore, Cu-MOF/GO composite materials prepared by the present invention, preparation method is simple, environmentally protective, and can mention
The electric conductivity and stability of high MOFs is a kind of ideal lithium cell cathode material.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (10)
1. a kind of preparation method of the Cu-MOF/GO compound based on green organic ligand, which is characterized in that including following step
It is rapid:
Conductive paste material is dispersed in water, transition metal salt is added, dissolution obtains solution one；
Green organic ligand is soluble in water, obtain solution two；
The solution one and solution two are mixed, 5~30h of hydro-thermal reaction at 60~200 DEG C, obtained solids is Cu-
MOF/GO compound；
Wherein, the conductive paste material is graphene oxide, and the transition metal salt is Cu (NO3)2Or its hydrate, it is described green
Color organic ligand is citric acid or its hydrate.
2. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as described in claim 1
In the mass ratio of the conductive paste material and Cu-MOF are 1~50wt%.
3. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as described in claim 1
In Cu (NO3)2Hydrate is Cu (NO3)2·3H2O, citric acid hydrate are monohydrate potassium.
4. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as described in claim 1
In the molar ratio of the transition metal salt and green organic ligand is 1~3:1.
5. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as claimed in claim 4
In the molar ratio of the transition metal salt and green organic ligand is 2:1.
6. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as described in claim 1
In the temperature of the hydro-thermal reaction is 140 DEG C, time 20h.
7. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as described in claim 1
In include thing steps that obtained solid is filtered, cleans and is dried.
8. the preparation method of the Cu-MOF/GO compound based on green organic ligand, feature exist as claimed in claim 7
In the temperature of the drying is 100~120 DEG C, and drying time is 2~8h.
9. the Cu-MOF/GO compound that described in any item methods are prepared according to claim 1~8.
10. application of the Cu-MOF/GO compound as claimed in claim 9 as lithium ion battery negative material.
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| CN112691704A (en) * | 2020-08-27 | 2021-04-23 | 王睿哲 | Flower-ball-shaped Cu-MOF-74/GO visible light catalyst and preparation method thereof |
| CN114989444A (en) * | 2022-07-06 | 2022-09-02 | 杭州师范大学 | Preparation method and nitrogen fixation application of citric acid-based metal organic framework material |
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