CN114649560A - Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof - Google Patents
Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof Download PDFInfo
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- 229910007566 Zn-MOF Inorganic materials 0.000 title claims abstract description 86
- 239000013094 zinc-based metal-organic framework Substances 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 146
- 239000002135 nanosheet Substances 0.000 claims abstract description 32
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- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000002344 surface layer Substances 0.000 abstract description 5
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- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 150000002641 lithium Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 2
- -1 Polyethylene Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a Zn-MOF/PAN @ PAN composite diaphragm material, a preparation method and application thereof, and relates to the technical field of lithium batteries. Dissolving the prepared two-dimensional ultrathin Zn-MOF nanosheet in an organic solvent, adding PAN (polyacrylonitrile) for mixing to obtain a third mixed solution; dissolving PAN in an organic solvent to serve as spinning solution, and preparing a PAN fiber membrane through electrostatic spinning; and spraying the third mixed solution onto the PAN fiber membrane through electrostatic spraying to prepare the Zn-MOF/PAN @ PAN composite membrane material. The Zn-MOF/PAN @ PAN composite membrane material prepared by the invention introduces two-dimensional ultrathin Zn-MOF nanosheets and PAN surface layer structures, so that the pore size distribution is more uniform, and Li adjustment is facilitated+Has a high ion conductivityAnd good electrochemical performance. The preparation method is simple, green and safe, and can realize large-area continuous rapid production.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a Zn-MOF/PAN @ PAN composite diaphragm material and a preparation method and application thereof.
Background
Among various novel energy storage technologies, lithium batteries are widely used in the aspects of electric tools, power cars, electronic equipment, large-scale energy storage batteries and the like due to the advantages of high energy density, long service life, no pollution and the like. The diaphragm is a key internal storage component in the lithium battery, and has the functions of isolating the positive electrode and the negative electrode, preventing short circuit, absorbing electrolyte, allowing lithium ions to be transferred and blocking electrons. Most commercial separators in lithium batteries are microporous polymeric membranes prepared from Polyethylene (PE), polypropylene (PP) and other polyolefins and their blends or copolymers by dry and wet processes. These microporous polymer membranes have good chemical stability, high mechanical strength, and uniform thickness, but have low thermal stability and porosity, and poor wettability with an electrolyte, resulting in high battery resistance and reduced energy density.
The development of a novel composite polymer separator material is expected to solve the above problems. One effective approach is to incorporate various functional materials into the polymer-based separator, such as ceramic nanoparticles, Liukuqing topic group (Zhu F, Liu J, Zhuao H, et Al2O3Preparation for enhanced lithium batteries, ChemElectrochem,2019,6(11): 2883-2890) by using non-solvent induced phase separation technique2O3Ceramic nanoparticles and Polyetherimide (PEI)) The composite diaphragm has excellent cycle performance, thermal stability and ionic conductivity. The concentration of the added nanoparticles is limited to a relatively low level because the aggregation of the nanoparticles under high loading may lead to a risk of poor cycling performance of the battery.
Compared with the traditional nano ceramic particles, the MOF material has attracted extensive attention due to the characteristics of high specific surface area, adjustable chemical properties, uniform morphology and the like. Direct use in lithium batteries has proven feasible due to their particular physical and chemical properties. The Manual Stephan project group (Suiyakumar S, Kanagaraj M, Kathiesan M, et al, Metal-organic frame based membrane as a permselective separator for lithium-sulfur batteries. Electrochimica Acta,2018,265: 151-. Similarly, the Sun King task group (Wu X, Fan L, Qiu Y, et al, ion-Selective practical Blue-Modified cell Separator for High-Performance Lithium-Sulfur Battery. ChemSumschem, 2018,11(18):3345-3351.) proposed the modification of PB MOF into a Celgard membrane that exhibits remarkable properties of High reversibility and long cycling stability.
However, the MOFs used for modifying the membranes described above are all three-dimensional structures with low conductivity.
Compared with three-dimensional MOF, the two-dimensional MOF nanosheet has higher atom utilization rate, low ion transmission resistance and uniform pore channels. Two-dimensional MOF nanosheets with high specific surface area and high selectivity are adopted as lithium battery separators to enable Li to be uniform+Flux, and thus Li+The deposition behavior of (a) improves the cycle stability of the lithium negative electrode. In consideration of the advantages of the two-dimensional MOF nanosheet, the two-dimensional ultrathin Zn-MOF nanosheet is adopted as a modification material of the lithium battery diaphragm, and the technology is not reported in a public way.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a Zn-MOF/PAN @ PAN composite diaphragm material, a preparation method and application thereof, wherein the Zn-MOF/PAN @ PAN composite diaphragm material is used for preparing a lithium battery diaphragm, and L can be uniformi+Flux and improves the comprehensive performance of the lithium battery.
The invention provides a preparation method of a Zn-MOF/PAN @ PAN composite membrane material, which comprises the following steps:
(1) dissolving terephthalic acid in a first mixed solution of an organic solvent and an alcohol solution in a volume ratio of 8: 1, adding zinc salt for dissolving, adding triethylamine or ammonia water for uniformly mixing to obtain a second mixed solution, mechanically stripping the second mixed solution to obtain a two-dimensional ultrathin Zn-MOF nanosheet,
dissolving the prepared two-dimensional ultrathin Zn-MOF nanosheet in an organic solvent, adding PAN (polyacrylonitrile) for mixing to obtain a third mixed solution;
(2) dissolving PAN in an organic solvent to serve as spinning solution, and preparing a PAN fiber membrane through electrostatic spinning;
(3) spraying the third mixed solution in the step (1) onto the PAN fiber membrane in the step (2) through electrostatic spraying to prepare the Zn-MOF/PAN @ PAN composite membrane material;
wherein, the organic solvent in the step (1) is N, N-dimethylformamide, N-dimethylacetamide, formamide, trifluoroacetic acid or dimethyl sulfoxide; the alcohol solution is 50% ethanol solution or methanol solution by volume percentage.
The mechanical stripping method in the step (1) can be a high-power probe ultrasonic stripping method.
Preferably, the zinc salt is zinc chloride, zinc nitrate, zinc sulfate or zinc acetate.
Preferably, triethylamine or ammonia water is added and uniformly mixed to obtain a second mixed solution, the temperature of the second mixed solution is 0-10 ℃ during ultrasonic treatment, the temperature is raised due to heat release of the ultrasonic treatment, and the temperature is kept at a lower temperature.
Specifically, in the step (2), the electrostatic spinning voltage is 25-30kV, the perfusion speed of the spinning solution is 1.2-1.5mL/h, the spinning temperature is 25 +/-2 ℃ and the humidity is 45 +/-5%.
Preferably, the mass ratio of the PAN to the two-dimensional ultrathin Zn-MOF nanosheets in the third mixed solution prepared in step (1) is 1: 0.5-2.
More preferably, the mass ratio of PAN to two-dimensional ultrathin Zn-MOF nanosheets in the third mixed solution prepared in step (1) is 1: 2.
Due to the high specific surface area and porosity of the two-dimensional ultrathin Zn-MOF nanosheet, the aperture of the composite membrane is reduced, the aperture distribution is more uniform, and the adjustment of Li is facilitated+The flux of the composite diaphragm is improved, so that the battery assembled by the composite diaphragm has excellent cycle performance, and the specific discharge capacity of the battery is kept.
Preferably, the Zn-MOF/PAN @ PAN composite membrane material has a thickness of 45-65 μm. The mechanical strength and the electrochemical property synchronously meet the requirements of the lithium battery diaphragm under the thickness.
The invention also provides a Zn-MOF/PAN @ PAN composite membrane material prepared by the preparation method.
The invention also provides application of the Zn-MOF/PAN @ PAN composite diaphragm material in preparation of a lithium battery diaphragm.
The invention has the beneficial effects that:
(1) the method for preparing the two-dimensional Zn-MOF is simple and easy to repeat, is easy for industrial production, is green and environment-friendly, and has high research significance and economic value.
(2) The Zn-MOF/PAN @ PAN composite membrane material prepared by the invention introduces two-dimensional ultrathin Zn-MOF nanosheets to the PAN surface layer structure, so that the pore size distribution is more uniform, and Li adjustment is facilitated+Has high ion conductivity and good electrochemical performance.
(3) According to the invention, the two-dimensional ultrathin Zn-MOF nanosheet is prepared and then mixed with PAN to prepare the composite diaphragm in one step by utilizing the electrostatic spinning and electrostatic spraying technologies, the preparation method is simple, convenient, green and safe, and large-area continuous and rapid production can be realized.
(4) The preparation method can efficiently prepare the battery diaphragm with good cycle performance and specific capacity, namely the method is very suitable for producing batteries with high capacity and high power.
Drawings
Fig. 1 is an SEM image of two-dimensional ultrathin Zn-MOF nanoplates prepared in example 1.
Fig. 2 is a TEM image of two-dimensional ultrathin Zn-MOF nanoplates prepared in example 1.
FIG. 3 is a schematic process diagram of the preparation of a two-dimensional ultrathin Zn-MOF nanosheet modified lithium battery separator; wherein Zn-MOF/PAN @ PAN fiber membrane means that the PAN fiber membrane is coated with Zn-MOF/PAN.
FIG. 4 is a graph of pore size distribution for Zn-MOF/PAN @ PAN composite membranes prepared in examples 5 and 6.
FIG. 5 is an SEM image of the Zn-MOF/PAN (1/2) @ PAN membrane prepared in example 5.
FIG. 6 is an SEM image of Zn-MOF/PAN (2/1) @ PAN membrane prepared in example 6.
Fig. 7 is a discharge curve of lithium batteries assembled by different separators under different rates.
Fig. 8 is a cycle curve at 1C rate for lithium batteries assembled with different separators.
Detailed Description
Example 1
Preparing a two-dimensional ultrathin Zn-MOF nanosheet:
dissolving 0.498g of terephthalic acid in a mixed solution of 128mL of N, N-Dimethylformamide (DMF) and 16mL of 50% ethanol solution (v/v) by ultrasonic, adding 0.409g of zinc chloride, performing ultrasonic treatment until the zinc chloride is completely dissolved, quickly adding 3.2mL of triethylamine, stirring for 5min to obtain a uniform mixed solution, and performing ultrasonic treatment on the mixed solution at 0-10 ℃ for 9 h. And finally, centrifuging the mixed solution, washing the product with ethanol for three times, and drying in a vacuum oven at 100 ℃ for 12 hours to obtain the two-dimensional ultrathin Zn-MOF nanosheet. An SEM image of the prepared two-dimensional ultrathin Zn-MOF nanosheet is shown in figure 1, the size is uniform, the morphology is controllable, and the two-dimensional sheet reaches a continuous large sheet of 5-10 mu m after being stacked through intermolecular force. TEM image is shown in FIG. 2, the two-dimensional MOF has transverse dimension of about 200nm and thickness of 5-10 nm.
Example 2
Preparing a two-dimensional ultrathin Zn-MOF nanosheet:
dissolving 0.498g of terephthalic acid in a mixed solution of 128mL of dimethyl sulfoxide (DMSO) and 16mL of 50% ethanol solution (v/v) by ultrasonic, adding 0.5g of zinc nitrate by ultrasonic until the zinc nitrate is completely dissolved, quickly adding 3.2mL of triethylamine, stirring for 5min to obtain a uniform mixed solution, and performing ultrasonic treatment on the mixed solution for 9h at the temperature of 0-10 ℃. And finally, centrifuging the mixed solution, washing the product with ethanol for three times, and drying in a vacuum oven at 100 ℃ for 12 hours to obtain the two-dimensional ultrathin Zn-MOF nanosheet.
Example 3
Preparation of PAN fiber membrane:
73.6g of DMF is taken in a stirring tank, 6.4g of Polyacrylonitrile (PAN) powder is slowly added into the stirring tank while stirring, and then stirring is carried out for 24 hours at normal temperature to prepare a clear 8 wt% PAN spinning solution. The PAN fiber membrane is prepared by utilizing an electrostatic spinning technology under the high-voltage electric field force, the electrostatic spinning voltage is 25kV, the spinning solution perfusion speed is 1.2mL/h, and the spinning temperature and the spinning humidity are respectively 25 +/-2 ℃ and 45 +/-5%.
Example 4
Preparation of PAN fiber membrane:
73.6g of DMF was taken in a stirred tank, 8.2g of PAN powder was slowly added to the stirred tank while stirring, and then stirred at room temperature for 24 hours to obtain a clear 10 wt% PAN spinning solution. The PAN fiber membrane is prepared by utilizing an electrostatic spinning technology under the high-voltage electric field force, the electrostatic spinning voltage is 30kV, the filling speed of a spinning solution is 1.5mL/h, and the spinning temperature and the spinning humidity are respectively 25 +/-2 ℃ and 45 +/-5%.
Example 5
Preparing a Zn-MOF/PAN @ PAN composite membrane material:
dissolving 0.5g of the two-dimensional ultrathin Zn-MOF nanosheet prepared in the example 1 in 18.5g of DMF, slowly adding 1g of PAN powder while stirring, stirring at normal temperature for 24 hours to dissolve the two-dimensional ultrathin Zn-MOF nanosheet to obtain a Zn-MOF-PAN spinning solution, spraying the Zn-MOF-PAN spinning solution onto the PAN fiber membrane prepared in the example 3 through an electrostatic spraying technology to obtain a Zn-MOF/PAN @ PAN composite membrane material, and drying in a vacuum oven at 50 ℃ for 12 hours. Wherein the electrostatic spraying voltage is 30kV, the perfusion speed of the spinning solution is 1.5mL/h, and the spinning temperature and the spinning humidity are respectively 25 +/-2 ℃ and 45 +/-5%.
FIG. 3 is a schematic diagram of a process for preparing a two-dimensional ultrathin Zn-MOF nanosheet modified lithium battery diaphragm (named as Zn-MOF/PAN @ PAN composite diaphragm), wherein a Zn-MOF/PAN (the mass ratio of Zn-MOF/PAN is 1/2) surface layer structure (the thickness of the surface layer structure finally accounts for only about 10% of the whole diaphragm) is introduced to a PAN fiber membrane prepared by electrostatic spinning through an electrostatic spraying method to obtain the Zn-MOF/PAN @ PAN composite diaphragm, which is named as Zn-MOF/PAN (1/2) @ PAN. Fig. 4 is a pore size distribution diagram of a Zn-MOF/PAN @ PAN composite membrane, fig. 5 is an SEM diagram of the Zn-MOF/PAN (1/2) @ PAN composite membrane prepared by the example, and it can be seen from fig. 4 and 5 that two-dimensional ultrathin Zn-MOF nanosheets are mainly embedded in the fiber and exposed on the surface of the fiber, forming some nano protrusions and folds, so that the fiber becomes rough, which is beneficial to reducing the pore size and adjusting the pore size distribution of the Zn-MOF/PAN @ PAN composite membrane.
Example 6
Dissolving 2g of the two-dimensional ultrathin Zn-MOF nanosheet prepared in the embodiment 2 in 17g of DMF, slowly adding 1g of PAN powder while stirring, stirring at normal temperature for 24 hours to dissolve the two-dimensional ultrathin Zn-MOF nanosheet to obtain Zn-MOF-PAN spinning solution, spraying the Zn-MOF-PAN spinning solution onto the PAN fiber membrane prepared in the embodiment 4 through an electrostatic spraying technology to obtain a Zn-MOF/PAN @ PAN composite membrane material, and drying in a vacuum oven at 50 ℃ for 12 hours. Wherein the electrostatic spraying voltage is 30kV, the perfusion speed of the spinning solution is 1.5mL/h, and the spinning temperature and the spinning humidity are respectively 25 +/-2 ℃ and 45 +/-5%.
FIG. 3 is a schematic diagram of a process for preparing a two-dimensional ultrathin Zn-MOF nanosheet modified lithium battery diaphragm (named as Zn-MOF/PAN @ PAN composite diaphragm), wherein a Zn-MOF-PAN (the mass ratio of Zn-MOF/PAN is 2/1) surface layer structure is introduced to a PAN fiber membrane prepared by electrostatic spinning through an electrostatic spraying method to obtain the Zn-MOF/PAN @ PAN composite diaphragm, named as Zn-MOF/PAN (2/1) @ PAN. FIG. 4 is a graph of pore size distribution for a Zn-MOF/PAN @ PAN composite membrane with an increased Zn-MOF ratio and a decreased average pore size of the composite membrane. FIG. 6 is SEM image of Zn-MOF/PAN (2/1) @ PAN membrane prepared in example, from which it can be seen that the content of two-dimensional ultrathin Zn-MOF nanosheets is increased, and some nano-projections and wrinkles formed in the fiber interior and exposed on the fiber surface are increased, so that the fiber becomes rougher.
Detection example 1
Electrochemical performance tests were performed on lithium batteries prepared with Zn-MOF/PAN (1/2) @ PAN composite separator, Zn-MOF/PAN (2/1) @ PAN composite separator, PAN separator (spectra, P1316) and commercial Celgard separator (CELGARD, 2320).
Fig. 7 and 8 show a pairThe performance comparison curves and the cycle performance curves at different multiplying factors (0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C) of the lithium batteries assembled by Zn-MOF/PAN (1/2) @ PAN composite diaphragm (prepared in example 3), Zn-MOF/PAN (2/1) @ PAN composite diaphragm (prepared in example 4), PAN diaphragm and Celgard diaphragm at different multiplying factors (0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C) are shown in figure 7, when the discharge current density is increased from 0.2C to 10C, the specific discharge capacity of the batteries assembled by the Zn-MOF/PAN @ PAN composite diaphragm, the PAN diaphragm and the Celgard diaphragm is reduced, the test curves are stepped, and the reasons for generating the phenomena are all related to the polarization of the batteries. Moreover, when the charging rate returns to 0.1C again, the reversible specific discharge capacity of all the batteries is close to the initial specific discharge capacity of 0.1C, which indicates that the structure of the diaphragm is not affected by the large current density. The specific discharge capacity of the battery assembled by commercial Celgard diaphragm, PAN diaphragm and Zn-MOF/PAN (1/2) @ PAN, Zn-MOF/PAN (2/1) @ PAN composite diaphragm at 35 cycles (10C) is 93.1mAh/g, 84.4mAh/g, 97.6mAh/g and 103.3mAh/g respectively, and the capacity retention rates are 62.54%, 59.25%, 64.31% and 63.71% respectively. The Zn-MOF/PAN @ PAN composite separator assembled battery showed higher discharge capacity and lower capacity loss. In addition, the specific discharge capacity is increased along with the increase of the Zn-MOF ratio, and particularly, the difference between the specific discharge capacities is further increased under the high charge-discharge rate of 2C-5C. As can be seen from FIG. 8, the batteries assembled by Zn-MOF/PAN (1/2) @ PAN and Zn-MOF/PAN (2/1) @ PAN composite membranes show more stable cycle performance, and the specific discharge capacities after 300 cycles are respectively 140mAh/g and 129.1mAh/g under the condition of 1C, which are higher than those of Celgard membranes (117.8mAh/g) and PAN membranes (127.3 mAh/g). This is because the two-dimensional ultrathin Zn-MOF nanosheets, due to their high specific surface area and porosity, reduce the pore size of the composite membrane and make the pore size distribution more uniform, which is beneficial to adjusting Li+The flux of the battery improves the ionic conductivity, so that the battery assembled by the Zn-MOF/PAN @ PAN composite diaphragm obtains excellent cycle performance, and the specific discharge capacity of the battery is kept.
Claims (8)
1. A preparation method of a Zn-MOF/PAN @ PAN composite membrane material is characterized by comprising the following steps:
(1) dissolving terephthalic acid in a first mixed solution of an organic solvent and an alcohol solution in a volume ratio of 8: 1, adding zinc salt for dissolving, adding triethylamine or ammonia water for uniformly mixing to obtain a second mixed solution, mechanically stripping the second mixed solution to obtain a two-dimensional ultrathin Zn-MOF nanosheet,
dissolving the prepared two-dimensional ultrathin Zn-MOF nanosheet in an organic solvent, adding PAN (polyacrylonitrile) for mixing to obtain a third mixed solution;
(2) dissolving PAN in an organic solvent to serve as spinning solution, and preparing a PAN fiber membrane through electrostatic spinning;
(3) spraying the third mixed solution in the step (1) onto the PAN fiber membrane in the step (2) through electrostatic spraying to prepare the Zn-MOF/PAN @ PAN composite membrane material;
wherein, the organic solvent in the step (1) is N, N-dimethylformamide, N-dimethylacetamide, formamide, trifluoroacetic acid or dimethyl sulfoxide; the alcohol solution is 50% ethanol solution or methanol solution by volume percentage.
2. The method of claim 1, wherein the zinc salt is zinc chloride, zinc nitrate, zinc sulfate, or zinc acetate.
3. The preparation method according to claim 1, wherein the electrospinning voltage in the step (2) is 25 to 30kV, the dope pouring speed is 1.2 to 1.5mL/h, the spinning temperature is 25 ± 2 ℃ and the humidity is 45 ± 5%.
4. The preparation method of claim 1, wherein the mass ratio of PAN to two-dimensional ultrathin Zn-MOF nanosheets in the third mixed solution prepared in step (1) is 1: 0.5-2.
5. The preparation method of claim 4, wherein the mass ratio of PAN to two-dimensional ultrathin Zn-MOF nanosheets in the third mixed solution prepared in step (1) is 1: 2.
6. The method of claim 1, wherein in step (3), the Zn-MOF/PAN @ PAN composite membrane material has a thickness of 45 to 65 μm.
7. A Zn-MOF/PAN @ PAN composite membrane material prepared by the preparation method of claims 1-6.
8. Use of the Zn-MOF/PAN @ PAN composite separator material of claim 7 in the preparation of a lithium metal battery separator.
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