CN109638304A - A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material - Google Patents
A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material Download PDFInfo
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to electrochemical fields, provide the preparation method and purposes of a kind of M-MOF-74/ graphene composite cathode material.A kind of porous M-MOF-74/ graphene (M=Co, Mn, Zn, Mg, Fe) cathode composite preparation method for material with high-specific surface area for lithium-air battery, while additionally providing a kind of lithium-air battery cathode made of the composite material.When porous M-MOF-74/ graphene composite material of the present invention is used as lithium-air battery porous electrode.Due to that will have the graphene of the active site of more and high degree of dispersion, bigger serface, abundant pore structure metal-organic framework material and ultra-high conductivity compound, be conducive to the diffusion of oxygen in the catalyst in air, there is good catalytic activity and stability.Therefore when the composite material cathode is used for lithium-air battery porous electrode, there is high charge/discharge capacity.
Description
Technical field
The invention belongs to electrochemical field, especially a kind of preparation method of M-MOF-74/ graphene composite cathode material
And purposes.
Background technique
The every year of world car ownership is with ten million growth rate, and opposite tellurian petroleum of having verified stores up
Amount will be depleted in 50 years；At the same time, a large amount of toxic, pernicious gases caused by automobile burning oil plant are also to big compression ring
Border causes great destruction.Therefore, cleanliness without any pollution, energy efficiency be high and the diversified new-energy automobile in energy source at
Have become international concern focus and scientific research hot spot.And for new-energy automobile, cleanliness without any pollution is used and developed, can be again
Novel energy storage apparatus raw, that energy density is high is the task of top priority.Lithium-air battery is a kind of extrahigh energy widely paid close attention in recent years
The novel battery system of metric density.Lithium ion embedded electrode is abandoned compared with conventional lithium ion battery, in lithium-air battery,
And it is directly reacted with oxygen in porous electrode using lithium ion to realize conversion of the chemical energy to electric energy.It is super that this has it
High theoretical energy density (11140Wh kg-1).Wherein, the performance of porous electrode is for the most important of lithium-air battery.Mesh
Preceding porous electrode and catalyst mostly use porous carbon, graphene, noble metal (such as platinum and platinum alloy, silver) and transition metal oxide
Deng, but since the catalytic activity of porous carbon, graphene is smaller, transition metal oxide specific surface area is too small, catalytic activity is limited；
Noble metal catalyst has good catalytic activity and stability, but is difficult to be commercialized due to expensive.Therefore exploitation Gao Bibiao
Face, high catalytic performance " difunctional " lithium-air battery cathode material be the hot spot of current research.
Summary of the invention
For existing some problems in porous electrode in current lithium-air battery and catalyst, the present invention provides a kind of use
In porous M-MOF-74/ graphene (M=Fe, Co, Mn, Mg, the Zn) composite cathode with high-specific surface area of lithium-air battery
The preparation method of material.A kind of lithium air made of the porous M-MOF-74/ graphene composite material is additionally provided simultaneously
Cell cathode.
The porous M-MOF-74/ graphene cathode material of high-ratio surface, which is characterized in that using graphene as carrier, metal has
Machine frame M-MOF-74 is load, is built into graphene/M-MOF-74 composite material；M-MOF-74 be transition metal iron, cobalt,
The compound that manganese, magnesium, zinc and 2,5-Dihydroxyterephthalic acid are formed, general molecular formula M2(dobdc) (M=Fe, Co, Mn,
Mg,Zn；dobdc4-=2,5-Dihydroxyterephthalic acid root), there is honey comb structure, and have exposed metal free coordination site,
Therefore, have well-regulated porous structure, big specific surface area, also there is orderly active site.M-MOF-74 particle by
Graphene connection, constitutes continuous conductive network.Therefore, which not only has well-regulated porous structure, big specific surface area,
Also there is orderly active site and higher electric conductivity.
A kind of preparation method of M-MOF-74/ graphene composite cathode material, comprising the following steps:
(1) graphene, the graphene solution that 0.5~2h of ultrasound is configured to are added in solvent A；
(2) transition metal salt and 2,5-Dihydroxyterephthalic acid ligand are put into autoclave or in bottle,
Then graphene solution made from step (1) is added in reaction kettle or bottle, is vigorously stirred, dissolves, mixed solution B is made；
(3) by reaction kettle or bottle ultrasound 0.2~for 24 hours equipped with mixed solution B, then place 1~for 24 hours；Then 25
10~72h of solvent thermal reaction after reaction washs product at~200 DEG C, and vacuum drying obtains M-MOF-74/ graphene
Composite cathode material.
In step (1), the graphene is a kind of or more in graphene oxide, reduced graphene or nitrogen-doped graphene
Kind, form is two dimension or three-dimensional；The concentration of the graphene solution is 1~50mg/mL.
In step (1), solvent A is one of water, methanol, ethyl alcohol, isopropanol, n,N dimethylformamide, two kinds or more
The mixed solvent of kind according to a certain percentage.
In step (2), in the mixed solution B, mole of transition metal salt and 2,5-Dihydroxyterephthalic acid ligand
Than (1~10): 1, the concentration of transition metal salt is 0.01~1mmol/mL.
It further include surfactant in the mixed solution B in step (2), the surfactant is cetyl three
One of methyl bromide ammonium, polyethylene glycol, polyvinylpyrrolidone.
In step (2), the transition metal salt, be the nitrate of Zn, Mn, Co, Fe, Mg, chlorate, acetate and it
One of crystalline hydrate or a variety of；
In step (2), the heating method of the solvent thermal reaction is one in physical heating, ultraviolet heating or microwave heating
Kind is a variety of.
In step (2), vacuum drying temperature is 80~250 DEG C.
M-MOF-74/ graphene composite cathode material prepared by the present invention is used for the purposes of the cathode of lithium-air battery,
Application method are as follows: by M-MOF-74/ graphene composite cathode material, conductive agent, binder according to a certain mass ratio through uniformly mixed
Close coating and form film on a current collector, the film with a thickness of 50~300 μm；.
The M-MOF-74/ graphene composite cathode material, conductive agent, binder mass ratio be (9~6): (0.5~
4): (0.5~4)；The binder is one in Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber and sodium carboxymethylcellulose
Kind；The conductive agent is acetylene black, conductive black super P, porous, electrically conductive carbon black Ketjenblack EC600JD, micropore
One or more of superconducting carbon black BP2000, carbon nano-fiber, ordered mesopore carbon, porous carbon, graphene oxide, graphene；
The collector is carbon paper.
The invention has the benefit that
(1) M-MOF/ graphene composite cathode material of the present invention, MOF even particle distribution, partial size are small, with graphite
Alkene is matrix, to be load with the M-MOF-74 of good cellular structure, constructs MOFs/ graphene composite material composite material,
The high conductivity having.
(2) porous M-MOF-74/ graphene composite cathode material of the present invention is used as lithium-air battery porous electrode
When.Since the metal for planning with more and high degree of dispersion active sites, bigger serface, abundant pore structure is organic
Frame (MOFs) material and the graphene of ultra-high conductivity are compound, are conducive to the diffusion of oxygen in the catalyst in air, tool
There are good catalytic activity and stability.Therefore when the composite material cathode is used for lithium-air battery porous electrode, have high
Charge/discharge capacity.
(3) method of the present invention is simple and convenient, easily controllable, homogeneous heating, at low cost.
Detailed description of the invention
Fig. 1 is for the first time discharge performance of the Co-MOF-74/ graphene composite material under 200mA/g current density；
Fig. 2 is following under 600mAh/g depth of discharge under Co-MOF-74/ graphene composite material 200mA/g current density
Ring performance map.
Fig. 3 is for the first time discharge performance of the Mn-MOF-74/ graphene composite material under 200mA/g current density；
Fig. 4 is for the first time discharge performance of the Zn-MOF-74/ graphene composite material under 200mA/g current density；
Fig. 5 is for the first time discharge performance of the Mg-MOF-74/ graphene composite material under 200mA/g current density；
Fig. 6 is for the first time discharge performance of the Fe-MOF-74/ graphene composite material under 200mA/g current density；
Specific embodiment
Present invention will be further explained with reference to the attached drawings and specific examples, but protection scope of the present invention is simultaneously
It is without being limited thereto.
Embodiment 1:
In volume ratio (10~20): graphene, ultrasonic 10min~2h being added in the mixed solvent of the DMF/ ethanol/water of 1:1
The graphene solution being configured to, the concentration of graphene are 1~20mg/mL.
In molar ratio (1~3): 1 weighs cabaltous nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and graphene is added
The mixed solvent of DMF/ ethanol/water, ultrasound 6~for 24 hours.It is put into autoclave, stirring, dissolution obtain the concentration of cobalt nitrate
For the solution of 0.05~0.6mmol/mL, 150 DEG C of 10~72h of heating, natural cooling obtains Co-MOF-74/GO compound, DMF
Washing 3 times, methanol wash 3~5 times, and impregnate 1~2 week, 120~250 DEG C of dryings of vacuum.
After Co-MOF-74/GO grinding prepared by embodiment 1 with micropore superconducting carbon black BP2000, Kynoar
(PVDF) binder is (9~6) by mass percentage: (0.5~4): the ratio mixing of (0.5~4), by its ultrasonic disperse in N-
It in methyl pyrrolidone (NMP), is coated on carbon paper after being stirred until homogeneous, and dries 10~72h at 70~120 DEG C, thus
Porous lithium-air battery cathode is made.Battery model is that Swagelok pattern has battery, with the bis- trifluoromethanesulfonimide lithiums of l M
(LiTFSI) tetraethyleneglycol dimethyl ether (TEGDME) solution is electrolyte, and polytetrafluoroethylene (PTFE) (PTFE) film is diaphragm, lithium metal
Piece is cathode.In the glove box (O for being full of high-purity argon gas2<1ppm,H2O < 1ppm) inner it is assembled into air cell.In order to exclude air
Middle vapor and CO2It influences, charge and discharge process carries out (RH < 5%) under the environment for leading to pure oxygen, drying, slightly holding positive pressure.It adopts
With blue electric cell tester, constant current charge-discharge performance test is carried out to simulated air battery.Charging process is constant-current charge, limitation
Voltage is 4.3V (vs.Li/Li+).Discharge process is constant-current discharge, and blanking voltage is 2.0V (vs.Li/Li+).Gained test knot
Fruit Fig. 1 shows that, when current density is 200mA/g, discharge capacity can reach 10250mAh/g to Co-MOF-74/GO for the first time.By charge and discharge
Capacitance depth limit is in 600mAh/g, we can see that circulation is after 50 weeks, capacity is not decayed, and charge and discharge platform voltage
Do not decline, charging voltage and discharge voltage plateau remain within 4.2V and 2.5V or so, as shown in Figure 2.
Therefore, by the active site with more and high degree of dispersion, bigger serface, abundant pore structure metal
Organic frame (MOFs) material and the graphene of ultra-high conductivity are compound, are conducive to the expansion of oxygen in the catalyst in air
It dissipates, there is good catalytic activity and stability.When for lithium-air battery porous electrode, there is very high charge and discharge capacitor
Amount, is very potential lithium-air battery cathode material.
Embodiment 2:
Cabaltous nitrate hexahydrate in embodiment 1 is replaced with into manganese nitrate, other obtain Mn-MOF-74/GO such as embodiment 1
Composite air electrode material, under 200 milliampere/gram current densities, discharge capacity is that 6186mAh/g is as shown in Figure 3 for the first time.
Embodiment 3:
In volume ratio (10~20): graphene being added in the mixed solvent of 1 DMF/ water, ultrasonic 10min~6h is configured to
Graphene solution, the concentration of graphene is 1~20mg/mL.In molar ratio (2~5): 1 weighs zinc nitrate hexahydrate and 2,5-
Dihydric para-phthalic acid, is added above-mentioned 100~300mL of mixed solvent containing graphene, and the concentration for obtaining metal ion is
The solution of 0.01mmol/mL~0.1mmol/mL, ultrasound 6~for 24 hours.It is then placed in 500mL reaction kettle, 100~150 DEG C of heating
10~72h, natural cooling obtain Zn-MOF-74/GO composite air electrode material, and DMF is washed 3 times, and methanol washs 3~5 times,
And it impregnates 1~2 week, 120~250 DEG C of dryings of vacuum.
Composite air electrode material will be changed and carry out charge-discharge test under 200 milliampere/gram current densities, for the first time discharge capacity
It is as shown in Figure 4 for 3536mAh/g.
Embodiment 4:
In volume ratio (10~20): graphene, ultrasonic 10min~6h being added in the mixed solvent of the DMF/ ethanol/water of 1:1
The graphene solution being configured to, the concentration of graphene are 1~20mg/mL.In molar ratio (2~5): 1 weighs magnesium nitrate hexahydrate
And 2,5-Dihydroxyterephthalic acid, above-mentioned 30~100mL of mixed solvent containing graphene is added, obtains the dense of metal ion
Degree is the solution of 0.01mmol/mL~0.1mmol/mL, ultrasonic 6~for 24 hours.Then it is dispensed into vial, it is molten in bottle
Liquid is no more than 5mL, 100~180 DEG C of 10~72h of heating, and natural cooling obtains Mg-MOF-74/GO composite air electrode material,
DMF is washed 3 times, and methanol washs 3~5 times, and is impregnated 1~2 week, 120~250 DEG C of dryings of vacuum.
The composite air electrode material is subjected to charge-discharge test under 200 milliampere/gram current densities, for the first time discharge capacity
It is as shown in Figure 5 for 3166mAh/g.
Embodiment 5:
In volume ratio (10~20): it is added graphene in the mixed solvent of the DMF/ isopropanol/water of 1:1, ultrasonic 10min~
The graphene solution that 6h is configured to, the concentration of graphene are 1~10mg/mL.In molar ratio (1~3): 1 weighs anhydrous protochloride
Iron and 2,5-Dihydroxyterephthalic acid, the mixing that above-mentioned graphene is added is molten, and the concentration of metal ion in solution is
0.05mmol/mL~0.6mmol/mL, ultrasound 6~for 24 hours.It is put into bottle, stirring, dissolution, 100~120 DEG C of heating 10~
72h, natural cooling obtain Fe-MOF-74/GO composite air electrode material, DMF washing, and methanol washs 3~5 times, impregnate 1~2
Week, 120~250 DEG C of dryings of vacuum.
The composite air electrode material is subjected to charge-discharge test under 200 milliampere/gram current densities, for the first time discharge capacity
It is as shown in Figure 6 for 2658mAh/g.
The embodiment is a preferred embodiment of the present invention, but present invention is not limited to the embodiments described above, not
In the case where substantive content of the invention, any conspicuous improvement that those skilled in the art can make, replacement
Or modification all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of M-MOF-74/ graphene composite cathode material, which comprises the following steps:
(1) graphene, the graphene solution that 0.5~2h of ultrasound is configured to are added in solvent A；
(2) transition metal salt and 2,5-Dihydroxyterephthalic acid ligand are put into autoclave or in bottle, then
Graphene solution made from step (1) is added in reaction kettle or bottle, is vigorously stirred, dissolves, mixed solution B is made；
(3) by reaction kettle or bottle ultrasound 0.2~for 24 hours equipped with mixed solution B, then place 1~for 24 hours；Then 25~200
10~72h of solvent thermal reaction at DEG C after reaction washs product, and it is compound to obtain M-MOF-74/ graphene for vacuum drying
Cathode material.
2. the preparation method of M-MOF-74/ graphene composite cathode material as described in claim 1, which is characterized in that step
(1) in, the graphene is one or more, form two in graphene oxide, reduced graphene or nitrogen-doped graphene
Dimension is three-dimensional；The concentration of the graphene solution is 1~50mg/mL.
3. the preparation method of M-MOF-74/ graphene composite cathode material as described in claim 1, which is characterized in that step
(1) in, solvent A is one of water, methanol, ethyl alcohol, isopropanol, n,N dimethylformamide, two or more are according to certain ratio
The mixed solvent of example.
4. the preparation method of M-MOF-74/ graphene composite cathode material as described in claim 1, which is characterized in that step
(2) in, in the mixed solution B, the molar ratio (1~10) of transition metal salt and 2,5-Dihydroxyterephthalic acid ligand: 1,
The concentration of transition metal salt is 0.01~1mmol/mL.
5. the preparation method of M-MOF-74/ graphene composite cathode material as described in claim 1, which is characterized in that step
(2) further include surfactant in the mixed solution B in, the surfactant be cetyl trimethylammonium bromide,
One of polyethylene glycol, polyvinylpyrrolidone.
6. the preparation method of M-MOF-74/ graphene composite cathode material as described in claim 1, which is characterized in that step
(2) in, the transition metal salt is nitrate, chlorate, acetate and their crystalline hydrate of Zn, Mn, Co, Fe, Mg
One of object is a variety of.
7. the preparation method of M-MOF-74/ graphene composite cathode material as described in claim 1, which is characterized in that step
(2) in, the heating method of the solvent thermal reaction is one of physical heating, ultraviolet heating or microwave heating or a variety of, very
The dry temperature of sky is 80~250 DEG C.
8. M-MOF-74/ graphene composite cathode material made from any one of claim 1~7 preparation method is used for
The purposes of the cathode of lithium-air battery.
9. purposes as claimed in claim 8, which is characterized in that application method are as follows: by M-MOF-74/ graphene composite cathode material
Material, conductive agent, binder form film through uniformly mixing coating according to a certain mass ratio on a current collector, the film with a thickness of 50
~300 μm；.
10. purposes as claimed in claim 9, which is characterized in that the M-MOF-74/ graphene composite cathode material, conduction
Agent, binder mass ratio be (9~6): (0.5~4): (0.5~4)；The binder is Kynoar, polytetrafluoroethyl-ne
One of alkene, butadiene-styrene rubber and sodium carboxymethylcellulose；The conductive agent is acetylene black, conductive black super P, porous
Conductive carbon black Ketjenblack EC600JD, micropore superconducting carbon black BP2000, carbon nano-fiber, ordered mesopore carbon, porous carbon,
One or more of graphene oxide, graphene；The collector is carbon paper.
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| CN110212181A (en) * | 2019-05-22 | 2019-09-06 | 南京理工大学 | Graphene/cobalt-based complex lithium cell negative pole material and preparation method thereof |
| CN111272840A (en) * | 2020-02-21 | 2020-06-12 | 衡阳师范学院 | Cu-MOFs loaded nitrogen-doped graphene composite material and preparation method and application thereof |
| CN111704732A (en) * | 2020-06-28 | 2020-09-25 | 南京工业大学 | Metal organic framework loaded graphene microspheres and preparation method and application thereof |
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