CN112421133A - Graphene/functionalized metal-organic framework material composite intercalation and preparation method and application thereof - Google Patents
Graphene/functionalized metal-organic framework material composite intercalation and preparation method and application thereof 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/052—Li-accumulators
-
- 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 discloses a graphene/functionalized metal-organic framework material composite intercalation, a preparation method and application thereof.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a graphene/functionalized metal-organic framework material composite intercalation and a preparation method and application thereof.
Background
The lithium-sulfur battery has ultrahigh energy density and theoretical capacity, and is rich in raw materials, low in price and environment-friendly. However, lithium sulfur batteries also have some inherent disadvantages, and soluble polysulfides have severe shuttling behavior, easily cause loss of active materials, and seriously affect the cycle performance and service life of the battery. In order to realize commercialization thereof, these problems need to be solved effectively.
The separator material is applied to a lithium-sulfur battery, and has adsorption and barrier effects on lithium polysulfide so as to prevent the lithium polysulfide from shuttling. The research at the present stage shows that after the intercalation material is added between the positive electrode and the diaphragm, the shuttle effect of polysulfide can be further inhibited, and the electrode electrochemical reaction kinetics are improved, so that the performance of the lithium-sulfur battery is improved. In recent years, carbon materials have been widely used for intercalation in lithium-sulfur batteries, but the interaction between nonpolar carbon materials and polar polysulfides is weak, limiting their further applications. Therefore, the reasonable design of the composite intercalation material is very critical. Chinese patent CN111554936A (published Japanese 2020.5.18) discloses a conductive MOF modified carbon fiber paper intercalation material for lithium-sulfur battery, which utilizes metal-organic framework material Co3(HITP)2The carbon fiber paper material modified by the conductive MOF is prepared by being attached to the surface of carbon fiber in hydrophilic carbon fiber paper and is used as an intercalation material of a lithium-sulfur battery to solve the problems of low conductivity of the intercalation material and low shuttle inhibition efficiency of lithium polysulfide, but the problem of insufficient cycle stability still exists.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defect and the defect of insufficient cycling stability of the existing intercalation material, and provide a graphene/functionalized metal-organic framework material composite intercalation which is arranged on the cathode side of a non-polar diaphragm of a lithium-sulfur battery, not only can absorb polysulfide to limit the diffusion of the polysulfide and inhibit the shuttle effect of the polysulfide, but also can promote the absorption of electrolyte and the diffusion of lithium ions, effectively reduce the interface impedance, reduce the loss of active substances, and enable the battery to show good rate capability and excellent cycling stability.
The invention further aims to provide a preparation method of the graphene/functionalized metal-organic framework material composite intercalation.
The invention also aims to provide application of the graphene/functionalized metal-organic framework material composite intercalation.
The above purpose of the invention is realized by the following technical scheme:
the graphene/functionalized metal-organic framework material composite intercalation comprises graphene and a functionalized metal-organic framework material, wherein the functionalized metal-organic framework material is distributed on the surface of the graphene, the mass ratio of the graphene to the functionalized metal-organic framework material is 5-1: 1, and the functionalized metal-organic framework material is UIO-66, UIO-66-COOH, UIO-66-2OH, UiO-66-2NH2One or more of them.
The invention relates to a composite intercalation prepared from a functional metal-organic framework material and graphene in a certain proportion, which belongs to an inorganic composite intercalation, wherein the graphene with high conductivity in the composite intercalation can effectively improve the conductivity of the intercalation material, improve the electron and ion transmission in the electrochemical reaction process and improve the kinetic rate of the electrochemical reaction, and the functional metal-organic framework material uniformly and densely distributed on the surface of the graphene can prevent the diffusion and shuttling of lithium polysulfide through physical barrier and chemical adsorption and improve the cycle stability of a lithium-sulfur battery.
Preferably, the mass ratio of the graphene to the functionalized metal-organic framework material is 3-1: 1.
Preferably, the functionalized metal-organic framework material is UIO-66-COOH, UIO-66-2OH, UiO-66-2NH2One or more of them.
The invention protects the preparation method of the graphene/functionalized metal-organic framework material composite intercalation, which comprises the following steps:
s1, uniformly mixing graphene and a functionalized metal-organic framework material to obtain a graphene/functionalized metal-organic framework material dispersion liquid;
s2, depositing the graphene/functionalized metal-organic framework material dispersion liquid obtained in the step S1 on a lithium-sulfur battery nonpolar membrane, and drying to obtain the graphene/functionalized metal-organic framework material composite intercalation.
Preferably, the concentration of the functionalized metal-organic framework material in the graphene/functionalized metal-organic framework material dispersion liquid in the step S1 is 0.2-4 mg/mL.
Preferably, the concentration of graphene in the graphene/functionalized metal-organic framework material dispersion liquid in the step S1 is 0.1-2 mg/mL.
Preferably, the solvent in step S1 is one of water, ethanol and methanol.
Preferably, the step S1 is to mix uniformly by using ultrasonic dispersion.
Preferably, the time of ultrasonic dispersion is 0.5-4 h.
Preferably, the non-polar separator in step S2 is a polypropylene separator and/or a glass fiber separator.
Preferably, the areal density of the graphene/functionalized metal-organic framework material deposited on the nonpolar membrane of the lithium-sulfur battery in the step S2 is 0.1-0.5 mg/cm2。
Preferably, the preparation method of the functionalized metal-organic framework material comprises the following steps:
dissolving metal salt and an organic ligand in a solvent, reacting at 80-120 ℃ for 12-36 h, washing with absolute ethyl alcohol, centrifuging, and drying to obtain the functionalized metal-organic framework material.
Preferably, the organic ligand is one or more of terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1,2, 4-benzene tricarboxylic acid and 2-amino terephthalic acid.
Preferably, the metal salt is a zirconium salt.
Preferably, the solvent is one of water, ethanol and methanol.
The invention also protects the application of the graphene/functionalized metal-organic framework material composite intercalation in a lithium-sulfur battery.
Preferably, the method comprises the following steps:
the composite of the carbon nano tube and the sulfur is used as a positive electrode material, the lithium sheet is used as a negative electrode material, and the composite is intercalated and assembled with the graphene/functional metal-organic framework material to form the button type lithium-sulfur battery.
Preferably, the mass ratio of the carbon nanotubes to the sulfur in the carbon nanotube-sulfur composite is 1: 2-5.
Compared with the prior art, the invention has the beneficial effects that:
the graphene/functionalized metal-organic framework material composite intercalation prepared by taking the metal-organic framework material and the graphene as main bodies is placed on the cathode side of a nonpolar diaphragm of a lithium sulfur battery, so that electrolyte absorption and lithium ion diffusion can be promoted, interface impedance is effectively reduced, polysulfide is adsorbed to limit the diffusion, the shuttle effect of the polysulfide is inhibited, the loss of active substances is reduced, the assembled lithium sulfur battery has high capacity and slow attenuation under high rate, and excellent cycle stability and rate capability are shown.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene/functionalized metal-organic framework material composite intercalation prepared in example 1 of the present invention.
Fig. 2 is a graph of rate performance of discharge of lithium-sulfur batteries assembled by graphene/functionalized metal-organic framework composite intercalation according to example 1 of the present invention and intercalation material according to comparative example 1.
Fig. 3 is a graph of the cycling performance at 1C rate of separately assembled lithium-sulfur batteries of example 1 graphene/functionalized metal-organic framework composite intercalation according to the present invention and comparative example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-66-2NH2Wherein UiO-66-2NH2Distributed on the surface of graphene, the graphene and UiO-66-2NH2The mass ratio of (A) to (B) is 3: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation comprises the following steps:
s1, weighing 0.23g of zirconium chloride and 0.18g of 2-amino terephthalic acid, uniformly dissolving in 5mL of N, N-Dimethylformamide (DMF) mixed solution, placing the solution in a 25mL stainless steel reaction kettle with polytetrafluoroethylene lining, keeping the temperature at 100 ℃ for 24h, after the reaction is cooled, washing and centrifuging by using DMF and methanol, and then carrying out vacuum drying at 60 ℃ to obtain the functionalized metal-organic framework material UiO-66-NH2；
S2, mixing 0.03gUiO-66-NH2Mixing with 0.01g of graphene in 60mL of ethanol, performing ultrasonic treatment for 4 hours, and uniformly dispersing to obtain graphene/UiO-66-NH2The suspension is deposited on a glass fiber membrane by vacuum filtration and dried at 60 ℃ overnight before use to obtain graphene/UiO-66-2 NH2And (4) compounding and intercalating.
Example 2
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-662Wherein the UiO-66 is distributed on the surface of the graphene, and the mass ratio of the graphene to the UiO-66 is 3: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation layer of the present embodiment is the same as that of embodiment 1, except that 2-aminoterephthalic acid is replaced by terephthalic acid in step (1).
Example 3
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-66-2OH, wherein the UiO-66-2OH is distributed on the surface of the graphene, and the mass ratio of the graphene to the UiO-66-2OH is 3: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation layer of the embodiment is the same as that of the embodiment 1, except that the 2-aminoterephthalic acid is replaced by 2, 5-dihydroxyterephthalic acid in the step (1).
Example 4
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-66-COOH, wherein the UiO-66-COOH is distributed on the surface of the graphene, and the mass ratio of the graphene to the UiO-66-COOH is 3: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation in this example is the same as that in example 1, except that 2-aminoterephthalic acid is replaced by 1,2, 4-benzenetricarboxylic acid in step (1).
Example 5
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-66-2NH2Wherein UiO-66-2NH2Distributed on the surface of graphene, the graphene and UiO-66-2NH2The mass ratio of (A) to (B) is 2: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation layer of the embodiment is the same as that of the embodiment 1.
Example 6
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-66-2NH2Wherein UiO-66-2NH2Distributed on the surface of graphene, the graphene and UiO-66-2NH2The mass ratio of (A) to (B) is 1: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation layer of the embodiment is the same as that of the embodiment 1.
Example 7
A graphene/functionalized metal-organic framework material composite intercalation comprises graphene and UiO-66-2NH2Wherein UiO-66-2NH2Distributed on the surface of graphene, the graphene and UiO-66-2NH2The mass ratio of (A) to (B) is 5: 1.
The preparation method of the graphene/functionalized metal-organic framework material composite intercalation layer of the embodiment is the same as that of the embodiment 1.
Comparative example 1
This comparative example is a pure glass fiber membrane.
Comparative example 2
The graphene/functionalized metal-organic framework material composite intercalation of the present comparative example and the preparation method thereof are the same as those of example 1,with the difference that graphene is mixed with UiO-66-2NH2Replacing the mass ratio by 1: 5.
comparative example 3
The graphene/functionalized metal-organic framework material composite intercalation of the present comparative example and the preparation method thereof are the same as example 1 except that UiO-66-2NH is added2Substitution with Metal-organic framework Material Co3(HITP)2。
Performance testing
1. Test method
The composite intercalation materials prepared in the examples and the intercalation materials prepared in the comparative examples are respectively assembled into: the button type lithium-sulfur battery takes a compound with the mass ratio of the carbon nano tube to the sulfur being 1:3 as a positive electrode and a lithium sheet as a negative electrode. And respectively carrying out rate performance test and cycle performance test in a Xinwei test cabinet. The rate performance test was performed by sequentially charging and discharging at rates of 0.2C, 0.5C, 1C, 2C, 3C, and 1C (1C — 1675 mAh/g). The cycle performance test is carried out by constant current charging and discharging under the multiplying power of 1C.
2. Test results
As can be seen from the scanning electron micrograph of FIG. 1, the graphene/UiO-66-2 NH prepared in example 12Ordered structure of composite intercalation, UiO-66-NH2The particles are uniformly, tightly and orderly distributed on the graphene sheet, no agglomeration is caused, a tightly packed structure is realized, and the graphene/functionalized metal-organic framework material composite intercalation structure prepared in the embodiment 2-7 is the same as that prepared in the embodiment 1 and is a tightly and orderly packed structure. Such a structure is advantageous for extending the diffusion path of polysulfides that will be captured by the highly adsorptive functionalized metal-organic framework material during diffusion, inhibiting the shuttling effect of the polysulfides. In contrast to the tightly ordered distribution of UiO-66-NH in example 12UiO-66-NH in comparative example 22Because the mass ratio is too high, a large amount of polysulfide agglomerates and is unevenly distributed, the shuttle of polysulfide is not limited. graphene/UiO-66-2 NH compared to example 12Composite intercalation, Co in comparative example 33(HITP)2The adsorption to polysulfide is poor, and the diffusion of polysulfide cannot be effectively limited.
The data in fig. 2 show that the lithium-sulfur battery assembled in example 1 has specific discharge capacities of 1675mAh/g, 1100mAh/g, 900mAh/g, 725mAh/g, 705mAh/g and 900mAh/g when 0.2C, 0.5C, 1C, 2C and 3C are returned to 1C for charging and discharging, and it can be seen that the lithium-sulfur battery has high capacity, and the capacity returned to 1C is the same as the initial 1C, showing excellent rate capability, and both capacity and rate capability are significantly better than those of the lithium-sulfur battery assembled in comparative example 1. The rate performance test result of the graphene/functionalized metal-organic framework material composite intercalation prepared in the embodiments 2-7 is equivalent to the experiment result of the embodiment 1.
From the data in fig. 3, it can be found that the lithium-sulfur battery assembled in example 1 can reach 859mAh/g after being charged and discharged at a rate of 1C and being cycled for 500 cycles at a high rate of 1C, the single-cycle decay rate is only 0.06%, the capacity is high, the decay is slow, and the assembled battery is proved to have good cycling stability, and the cycling stability is obviously superior to that of the lithium-sulfur battery assembled in comparative example 1. The cycle stability test result of the graphene/functionalized metal-organic framework material composite intercalation prepared in the embodiments 2-7 is equivalent to the experiment result of the embodiment 1. UiO-66-NH in comparative example 22And Co having poor adsorption to polysulfide in comparative example 33(HITP)2Leading to a large amount of dissolution and shuttling of polysulfides, so that the capacity of the assembled lithium-sulfur battery is quickly attenuated, and the rate performance and the cycling stability are poor.
The results show that the composite intercalation prepared by the graphene composite functionalized metal-organic framework material can promote the absorption of electrolyte and the diffusion of lithium ions, effectively reduce the interface impedance, adsorb polysulfide to limit the diffusion of the polysulfide, reduce the loss of active substances, and enable the battery to show good rate capability and excellent cycle stability.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The graphene/functionalized metal-organic framework material composite intercalation is characterized by comprising graphene and a functionalized metal-organic framework material, wherein the functionalized metal-organic framework material is distributed on the surface of the graphene, the mass ratio of the graphene to the functionalized metal-organic framework material is 5-1: 1, and the functionalized metal-organic framework material is UIO-66, UIO-66-COOH, UIO-66-2OH, UiO-66-2NH2One or more of them.
2. The graphene/functionalized metal-organic framework material composite intercalation according to claim 1, wherein the mass ratio of the graphene to the functionalized metal-organic framework material is 3-1: 1.
3. The graphene/functionalized metal-organic framework material composite intercalation layer according to claim 1 or 2, wherein the functionalized metal-organic framework material is UIO-66-COOH, UIO-66-2OH, UiO-66-2NH2One or more of them.
4. The preparation method of the graphene/functionalized metal-organic framework material composite intercalation according to any one of claims 1 to 3, characterized by comprising the following steps:
s1, uniformly mixing graphene and a functionalized metal-organic framework material to obtain a graphene/functionalized metal-organic framework material dispersion liquid;
s2, depositing the graphene/functionalized metal-organic framework material dispersion liquid obtained in the step S1 on a lithium-sulfur battery nonpolar membrane, and drying to obtain the graphene/functionalized metal-organic framework material composite intercalation.
5. The preparation method according to claim 4, wherein the concentration of the functionalized metal-organic framework material in the graphene/functionalized metal-organic framework material dispersion liquid in the step S1 is 0.2-4 mg/mL.
6. The preparation method according to claim 4, wherein the concentration of graphene in the graphene/functionalized metal-organic framework material dispersion liquid in the step S1 is 0.1-2 mg/mL.
7. The method according to claim 4, wherein the non-polar separator of step S2 is a polypropylene separator and/or a glass fiber separator.
8. The method according to claim 4, wherein the graphene/functionalized metal-organic framework material deposited on the nonpolar separator of the lithium-sulfur battery in the step S2 has an areal density of 0.1-0.5 mg/cm2。
9. The method according to claim 4, wherein the solvent in step S1 is one of water, ethanol and methanol.
10. The use of the graphene/functionalized metal-organic framework material composite intercalation according to any one of claims 1 to 3 in a lithium-sulfur battery.
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