CN106935825A - A kind of graphene oxide/metal organic frame composite and its preparation method and application - Google Patents
A kind of graphene oxide/metal organic frame composite and its preparation method and application Download PDFInfo
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- CN106935825A CN106935825A CN201710169134.XA CN201710169134A CN106935825A CN 106935825 A CN106935825 A CN 106935825A CN 201710169134 A CN201710169134 A CN 201710169134A CN 106935825 A CN106935825 A CN 106935825A
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Abstract
The present invention provides a kind of graphene oxide/metal organic frame composite, by graphene oxide, cobalt acetate tetrahydrate and 2, after 5 dihydric para-phthalic acids mix by a certain percentage, is prepared through solvent-thermal method reaction.Its preparation method includes：（1）Graphene oxide is disperseed in a solvent to obtain graphene oxide solution；（2）Cobalt acetate tetrahydrate and 2,5 dihydric para-phthalic acids are added in deionized water and form mixed liquor；（3）Reactor is put into after gained mixed liquor and gained graphene oxide solution are mixed；（4）In an oven after heated at constant temperature, product is taken out, washed, after drying, be obtained.Application as lithium ion battery negative material of the invention, through electrochemical property test, when current density is 100 mA g‑1When, specific capacity value is 520 600mAh g‑1.Material circulation stability of the present invention is high, and discharge and recharge long lifespan has broad application prospects in field of lithium ion battery.
Description
Technical field
The present invention relates to inorganic material preparation process technical field, and in particular to a kind of graphene oxide/metal has machine frame
Frame composite and its preparation method and application.
Background technology
Lithium ion battery is a kind of novel energy storage cell, there is that specific capacity is big, have extended cycle life, operating voltage is high, work
Wide temperature range, environmental pollution are small, nuisanceless, the low clear superiority of self-discharge rate.Lithium ion battery is in daily life and life
Application in product is more and more extensive, and more application is in the digital products such as mobile phone, camera, laptop computer and electric automobile, boat
My god, the field such as aviation.At present in lithium ion battery, commercialized negative material is graphite.
Metal organic framework compound（Metal-Organic Frameworks, MOFs）Being will be organic by coordination
Part and metal ion self assembly are got up, so as to the material with periodicity network structure constructed out.MOFs is by organic ligand
With metal ion composition, the diversity of part and metal-complexing can be made full use of, make its structure that there is the Modulatory character of height；
As porous material, with specific surface area high, multifarious pore space structure, size, multifunction is made it have；Synthetic method
It is fairly simple, low cost.MOFs shows in fields such as gas storage, Selective Separation, catalysis, sensing and electrochemical applications
Great potential.But electric conductivity is poor in itself for most of MOFs, mechanical strength is poor, so as to limit its it is large-scale it is actual should
With.
In terms of new MOFs design of material, in order to improve the chemical property and mechanical performance of MOFs materials, base is built
The extensive concern of researcher is caused in the composite of MOF.Wherein, graphene oxide is because its intensity is high, pliability strong, electricity
The advantages of chemical property is good, becomes the focus of research.It is reported that MIL-101 (Cr)/GO is negative as lithium ion battery
During the material of pole, relative to MIL-101 (Cr), by adulterating, graphene oxide substantially increases chemical property.But MIL-101
(Cr)/GO is in 50 mA g-1Current density under, second specific discharge capacity is only 107.2 mAhg-1, specific capacity is relatively low, still
Demand [the Inorg. Chem. Commun, 2016,64 of practical application are not reached: 63-66].By graphene oxide and cobalt-based
MOFs is compound can to utilize both synergies to further enhance stability, improve electrical conductivity, be applied to lithium ion battery and bear
Pole material.
The content of the invention
It is an object of the invention to provide a kind of graphene oxide/metal organic frame composite and preparation method thereof and should
With, the cyclical stability of electrode material is improved, extend its charge and discharge electric life.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
The quality for pressing graphene oxide by graphene oxide, cobalt acetate tetrahydrate and 2,5- dihydric para-phthalic acids is acetic acid
The 5-10% of cobalt tetrahydrate quality, and the mol ratio of cobalt acetate tetrahydrate and 2,5-Dihydroxyterephthalic acid is（1-
1.5）：After 1 mixing, it is prepared through solvent-thermal method reaction.
The preparation method of graphene oxide/metal organic frame composite, comprises the following steps：
（1）Add graphene oxide into tetrahydrofuran and deionized water is by volume（1-1.5）：Solvent obtained by 1 mixing
In, sonic oscillation 20-40 min form dispersed graphene oxide solution；
（2）At room temperature, it is by certain mol proportion by cobalt acetate tetrahydrate and 2,5-Dihydroxyterephthalic acid（1-1.5）：1 adds
Enter in 10-20 mL deionized waters, ultrasonic vibration, form mixed liquor；
（3）By step（2）Gained mixed liquor and step（1）Mix by a certain percentage in gained graphene oxide solution, ultrasound shake
10-15 min are swung, after being well mixed, reactor is put into, the ratio is cobalt acetate tetrahydrate for the quality of graphene oxide
The 5-10% of quality；
（4）Reactor is put into baking oven, heated at constant temperature to 100-120 DEG C, initiation reaction, the reaction system such as after reaction 36-96 h
It is slowly cooled to room temperature, after product is taken out, with absolute ethyl alcohol and the repeated multiple times washing of deionized water, in 80-100 DEG C of condition
After lower drying, graphene oxide/metal organic frame composite is obtained.
Graphene oxide/metal organic frame composite as lithium ion battery negative material application, through electrochemistry
Test detection understands, is 100 mA g in current density-1When, reversible specific capacity is 520-600mAh g-1。
Graphene oxide of the invention/metal organic frame composite carries out chemical property survey after being made button cell
Examination, step is as follows：
（1）The preparation of working electrode
By active material, conductive carbon（Super P）In mass ratio it is 7 with binding agent Kynoar：2：1 ratio mixing, so
Polypyrrole alkanone is added afterwards（NMP）Solvent, is uniformly mixed, and obtains slurry, and slurry is equably coated into copper using scraper
On paper tinsel, the uniform Copper Foil of coating is held in vacuum drying oven and is incubated 12 h at 60 DEG C, the negative electrode sheet material dried
Material, the cathode pole piece material of drying is cut into the disk of a diameter of 14 mm, obtains negative electricity pole piece, deduction blank copper of weighing
The quality of the graphene oxide/metal organic frame composite on cathode pole piece is obtained after paper tinsel, finally by negative electricity pole piece
It is held in glove box standby to treat；
（2）The assembling of battery
In the glove box full of argon gas, with step（2）The cathode pole piece of gained is the negative pole of battery, and lithium piece is positive pole, barrier film
Celgard2400 is used, electrolyte is the LiPF6-EC+DEC+EMC of the mol/L of concentration 1（Volume ratio is 1:1:1）It is mixed
Solution is closed, CR2016 type button cells is assembled into, in case electro-chemical test；
(3) electrochemical property test
Electrochemical property test uses LAND test systems, its model LandCT2001A types（Wuhan City's gold promise electronics is limited
Company）, it is 25 DEG C that test process temperature is constant, and its discharge and recharge blanking voltage is 3.0-0.01 V.It is 100 mA in current density
g-1When, the reversible specific capacity of graphene oxide/metal organic frame composite is 520-600mAh g-1, while showing good
Good cyclical stability.
The present invention relative to prior art, with advantages below：
1. binding site is formed using oxy radicals such as surface of graphene oxide carboxyls in the present invention, by a large amount of between two components
Hydrogen bond action and pi-pi accumulation effect so that graphene oxide is combined together with metal organic frame, formation graphite oxide
Synergy between alkene/metal organic frame composite, component causes that the chemical property of combination electrode material is greatly improved；
2. the charge and discharge circulation life of combination electrode material is improved using graphene oxide.Metal-organic framework material is by 40
After individual circulation, specific capacity starts in rapid decrease trend, and in the 100th circulation of discharge and recharge, specific capacity is 492 mAh g-1.Phase
For, the capacity attenuation of graphene oxide/metal organic frame composite is slower, after 100 charge and discharge cycles,
Specific capacity is maintained at 540 mAh g-1, the addition of graphene oxide improves the charge and discharge circulation life of combination electrode material；
3. when the graphene oxide prepared by the present invention/metal organic frame composite is as lithium ion battery negative material,
It is 100 mA g in current density-1When, reversible specific capacity is 520-600mAh g-1, while showing good stable circulation
Property.
Therefore, the present invention has broad application prospects in field of lithium ion battery.
Brief description of the drawings：
Fig. 1 is that metal organic frame prepared by specific embodiment and the graphene oxide/metal containing 5%, 10% graphene oxide have
The X-ray diffractogram of machine frame composite；
Fig. 2 is metal organic frame and the graphene oxide/metal containing 5%, 10% graphene oxide prepared by specific embodiment
The cyclic curve of organic frame composite；
Fig. 3 is metal organic frame and the graphene oxide/metal containing 5%, 10% graphene oxide prepared by specific embodiment
The high rate performance curve of organic frame composite.
Specific embodiment
The present invention is described in further detail, but be not right with reference to Figure of description by embodiment to present invention
Limitation of the invention.
Embodiment
The preparation side of the graphene oxide containing 5% graphene oxide/metal organic frame composite MOF-74-THF-5GO
Method, concrete operation step is as follows：
Step（1）, weigh the mixed solution that 12.454 mg graphene oxides are added to tetrahydrofuran and deionized water（Volume ratio
It is 1:1, totally 20 mL）In, the min of sonic oscillation 30 forms dispersed graphene oxide solution；
Step（2）, weigh 0.24908 g（0.001 mol）Cobalt acetate tetrahydrate and 0.19813 g（0.001 mol）'s
2,5-Dihydroxyterephthalic acid is added in 10 mL deionized waters, ultrasonic vibration, forms mixed liquor；
Step（3）, by step（3）The 10 mL mixed liquors and step of gained（2）Mixed in the 20mL graphene oxide solutions of gained
Close, the min of ultrasonic vibration 10, after being well mixed, be put into reactor, the ratio is cobalt acetate four for the quality of graphene oxide
The 5% of hydration amount of substance；
Step（4）, reactor is put into baking oven, heated at constant temperature to 120 DEG C, initiation reaction, reaction system is delayed after 72 h of reaction etc.
Slow cool down after product is taken out, with absolute ethyl alcohol and the repeated multiple times washing of deionized water, is dried to room temperature under the conditions of 85 DEG C
Afterwards, the graphene oxide/metal organic frame composite containing 5% graphene oxide is obtained.
The preparation of the graphene oxide containing 10% graphene oxide/metal organic frame composite MOF-74-THF-10GO
Method, concrete operation step is as follows：
Not specified step and the graphene oxide/metal organic frame composite MOF-74- containing 5% graphene oxide
The preparation method of THF-5GO is identical, and difference is：Step（1）The quality for weighing graphene oxide is 24.908 mg.
In order to contrast the influence without graphene oxide to material property.Metal organic frame material without graphene oxide
Expect the preparation method of MOF-74-THF, concrete operation step is as follows：
Not specified step and the graphene oxide/metal organic frame composite MOF-74- containing 5% graphene oxide
The preparation method of THF-5GO is identical, and difference is：Not comprising step（1）.
Graphene oxide of the invention/metal organic frame composite carries out chemical property survey after being made button cell
Examination, step is as follows：
（1）The preparation of working electrode
By active material, conductive carbon（Super P）In mass ratio it is 7 with binding agent Kynoar：2：1 ratio mixing, so
Polypyrrole alkanone is added afterwards（NMP）Solvent, is uniformly mixed, and obtains slurry, and slurry is equably coated into copper using scraper
On paper tinsel, the uniform Copper Foil of coating is held in vacuum drying oven and is incubated 12 h at 60 DEG C, the negative electrode sheet material dried
Material, the cathode pole piece material of drying is cut into the disk of a diameter of 14 mm, obtains negative electricity pole piece, deduction blank copper of weighing
The quality of the graphene oxide/metal organic frame composite on cathode pole piece is obtained after paper tinsel, finally by negative electricity pole piece
It is held in glove box standby to treat；
（2）The assembling of battery
In the glove box full of argon gas, with step（2）The cathode pole piece of gained is the negative pole of battery, and lithium piece is positive pole, barrier film
Celgard2400 is used, electrolyte is the LiPF6-EC+DEC+EMC of the mol/L of concentration 1（Volume ratio is 1:1:1）It is mixed
Solution is closed, CR2016 type button cells is assembled into, in case electro-chemical test；
(3) electrochemical property test
Electrochemical property test uses LAND test systems, its model LandCT2001A types（Wuhan City's gold promise electronics is limited
Company）, it is 25 DEG C that test process temperature is constant, and its discharge and recharge blanking voltage is 3.0-0.01 V.
Test result is as follows：
As shown in figure 1, three kinds of materials are in 2 θ=6.5-7 °, place occurs in that the characteristic peak of MOF-74 in 11.5-12 °, illustrates multiple
There is MOF-74 crystal in condensation material.Additionally, with the increase of graphene oxide content, the peak intensity of X-ray spectrogram has weakened,
During the diffraction maximum of GO itself does not appear in the XRD spectrum of composite simultaneously.Analysis reason has at following 2 points：1）GO's is low strong
Degree diffraction maximum compared with the MOF-74 with perfect crystal sharp high intensity diffraction peak intensity, it is difficult to significantly it was observed that, and
GO contents in the composite are relatively low（5%、10%）；2）By ultrasonic disperse into graphene oxide individual layer, this can make GO
The XRD diffraction maximums that carbon-coating spacing is produced disappear.
As shown in Fig. 2 in 100 mA g-1Current density under, metal-organic framework material by 40 circulate after, specific volume
Amount starts in rapid decrease trend, and in the 100th circulation of discharge and recharge, specific capacity is 492 mAh g-1.Comparatively, stone is aoxidized
The capacity attenuation of black alkene/metal organic frame composite is slower, and after 100 charge and discharge cycles, specific capacity is maintained at
540 mAh g-1, the addition of graphene oxide improves the charge and discharge circulation life of combination electrode material.
As shown in Figure 3, it can be seen that current density is from 100 mA g-1Increase to 1A g-1, 100 mA are then returned to again
g-1During, the specific capacity of MOF-74-THF-10GO is gradually successively decreased with the increase of current density first, last specific capacity
It is 585mAhg-1, it is indicated above graphene oxide/metal organic frame composite material exhibits and goes out good multiplying power property.
Claims (10)
1. a kind of graphene oxide/metal organic frame composite, it is characterised in that：By graphene oxide, the water of cobalt acetate four
After compound and 2,5-Dihydroxyterephthalic acid mix by a certain percentage, it is prepared through solvent-thermal method reaction.
2. graphene oxide according to claim 1/metal organic frame composite, it is characterised in that：The ratio
The quality for being graphene oxide is the 5-10% of cobalt acetate tetrahydrate quality, and cobalt acetate tetrahydrate and 2,5- dihydroxy
The mol ratio of terephthalic acid (TPA) is（1-1.5）：1.
3. the preparation method of graphene oxide/metal organic frame composite according to claim 1, it is characterised in that bag
Include following steps：
（1）Dispersion in solvent is added graphene oxide into, through sonic oscillation, dispersed graphene oxide solution is formed；
（2）At room temperature, cobalt acetate tetrahydrate and 2,5-Dihydroxyterephthalic acid are added to deionization by certain mol proportion
In water, ultrasonic vibration forms mixed liquor；
（3）By step（2）Gained mixed liquor and step（1）Mix by a certain percentage in gained graphene oxide solution, ultrasound shake
After swinging uniformly, reactor is put into；
（4）Reactor is put into baking oven, heated at constant temperature initiation reaction, then etc. reaction system be slowly cooled to room temperature, by product
After taking-up, with absolute ethyl alcohol and the repeated multiple times washing of deionized water, after drying, graphene oxide/metal organic frame is obtained multiple
Condensation material.
4. preparation method according to claim 3, it is characterised in that：The step（1）Solvent tetrahydrofuran and to go
Ionized water is by volume（1-1.5）：1 mixing gained, ultrasonic time is 20-40 min.
5. preparation method according to claim 3, it is characterised in that：The step（2）Cobalt acetate tetrahydrate and 2,
The mol ratio of 5- dihydric para-phthalic acids is（1-1.5）：1, deionized water volume is 10-20 mL.
6. preparation method according to claim 3, it is characterised in that：The step（3）Mixed liquor and graphene oxide are molten
The ratio of liquid is the 5-10% of cobalt acetate tetrahydrate quality for the quality of graphene oxide.
7. preparation method according to claim 3, it is characterised in that：The step（3）Ultrasonic time be 10-15
min。
8. preparation method according to claim 3, it is characterised in that：The step（4）The condition of reaction be, reaction temperature
It is 100-120 DEG C to spend, and the reaction time is 36-96 h.
9. preparation method according to claim 3, it is characterised in that：The step（4）Dry temperature is 80-100
℃。
10. according to claim 1 graphene oxide/metal organic frame composite as lithium ion battery negative material
Application, it is characterised in that：When current density is 100 mA g-1When, specific capacity value is 520-600mAh g-1。
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