CN117712319A - MOF-based lithium-sulfur battery interlayer material and preparation method thereof - Google Patents
MOF-based lithium-sulfur battery interlayer material and preparation method thereof Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011229 interlayer Substances 0.000 title claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 20
- 239000013207 UiO-66 Substances 0.000 claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 23
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 20
- -1 carboxyl carbon nano tube Chemical compound 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002262 Schiff base Substances 0.000 abstract description 2
- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229960000583 acetic acid Drugs 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- PAEZRCINULFAGO-OAQYLSRUSA-N (R)-homocamptothecin Chemical compound CC[C@@]1(O)CC(=O)OCC(C2=O)=C1C=C1N2CC2=CC3=CC=CC=C3N=C21 PAEZRCINULFAGO-OAQYLSRUSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium-sulfur battery interlayer material based on MOF and a preparation method thereof. The composition of the material comprises NH 2 -UIO-66-FC and carbon nanotube CNT in a mass ratio of 2-3:1; in the preparation, the Schiff base reaction is utilized to branch ferrocene formaldehyde to NH 2 on-UIO-66, NH with smaller pore size is synthesized 2 -UIO-66-FC, and carbon nanotube CNT and NH are prepared by in-situ growth method and physical mixing method 2 Composite CNT@NH of-UIO-66-FC 2 -UIO-66-FC. The invention has good electron conductivity and ion conductivity, and can effectively inhibit shuttle effect as the lithium sulfur battery interlayer material due to the special pore size distribution,improving the cycle performance of the lithium sulfur battery. The material provided by the invention is simple to prepare, and the raw materials are cheap and easy to obtain, so that the material is beneficial to large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery interlayer material based on MOF and a preparation method thereof.
Background
The development and utilization of traditional fossil energy are accompanied by serious energy crisis and environmental problems, which seriously threatens the long-term survival of human beings. Finding renewable energy sources has become a significant challenge for human survival. Over the last 30 years, lithium ion batteries have been used in various aspects of our lives. However, with further development of electronic products and rapid increase in demand for people, inherent disadvantages of lithium ion batteries, such as low energy density and low power density, have begun to develop. Therefore, energy storage devices that are required to have high energy density and long cycle life are becoming a hotspot for researchers.
Lithium sulfur (Li-S) battery is 1675mA h g -1 Theoretical specific capacity of 2600Wh Kg -1 Is one of the most potential energy storage elements at present. In addition, sulfur has the characteristics of no toxicity, low cost, environmental friendliness, high natural abundance and the like, so that the lithium-sulfur battery has the possibility of infinite development. However, the existing lithium-sulfur battery has the problems of fast capacity decay, low coulombic efficiency, poor cycle stability and the like, so that the lithium-sulfur battery is limited in practical application. Among them, the shuttle effect of polysulfide in the electrolyte is a main cause of defects in battery performance, and intensive studies have been made to solve this problem. Among them, metal Organic Frameworks (MOFs) are widely used in the field of batteries because of their high specific surface area, high porosity, abundant active sites and adjustable structure. CN 111320761A discloses a metal organic framework nanocomposite, a preparation method and application thereof, which comprises the steps of firstly carrying out bromobutyl modification on a synthesized polypyrrole nanotube, then carrying out chemical modification on 2-amino-1, 4-terephthalic acid molecules on the surface of the polypyrrole nanotube, then complexing metal ions, and finally assembling with terephthalic acid molecules into a UIO-66 crystal, thereby obtaining ppynts@uio-66. The material has extremely strong polarity and good conductive performance, and can inhibit the shuttle of polysulfide. However, this process is complicated in preparation steps and long in preparation time. CN 113410575B discloses a metal organic framework material based on aperture division strategy and uses it for lithium sulfur battery separator modification by HCPT, coCl 2 ·6H 2 O and Tripp dissolved in DMA-H 2 O-HBF 4 And heating and reacting the mixed solution to synthesize FJU-90 material. FJU-90 material can well inhibit the shuttle of polysulfide and catalyze the conversion of polysulfide, but still has poor conductivityIs a problem of (a).
Disclosure of Invention
The invention overcomes the defects of the technology and provides a lithium-sulfur battery interlayer material based on MOF and a preparation method thereof. The invention utilizes Schiff base reaction to branch ferrocenyl formaldehyde (cas: 12093-10-6) to NH 2 on-UIO-66, NH with smaller pore size is synthesized 2 -UIO-66-FC, and carbon nanotube CNT and NH are prepared by in-situ growth method and physical mixing method 2 Composite CNT@NH of-UIO-66-FC 2 -UIO-66-FC. Composite CNT@NH 2 The UIO-66-FC has good electronic conductivity and ion conductivity, and meanwhile, due to the special pore size distribution, the material can be used as a lithium sulfur battery interlayer material to effectively inhibit the shuttle effect and improve the cycle performance of the lithium sulfur battery. The material provided by the invention is simple to prepare, and the raw materials are cheap and easy to obtain, so that the material is beneficial to large-scale preparation.
In order to achieve the above purpose, the invention adopts the following technical scheme:
MOF-based lithium-sulfur battery interlayer material comprising NH 2 -UIO-66-FC and carbon nanotube CNT in a mass ratio of 3-2:1;
wherein NH is 2 The structural formula of the UIO-66-FC is as follows:
the preparation method of the MOF-based lithium-sulfur battery interlayer material is any one of the following two modes:
a first method; preparation of CNT@NH by physical milling 2 -UIO-66-FC comprising the steps of:
zirconium tetrachloride (ZrCl) 4 ) Mixing with N, N-Dimethylformamide (DMF), stirring, and adding 2-amino terephthalic acid (NH) 2 BDC) and acetic acid, stirring to obtain a mixed solution; carrying out microwave reaction on the mixed solution for 30-45 minutes at the temperature of 120-150 ℃; cooling to room temperature, washing, drying to obtain NH 2 -UIO-66; NH is then added 2 -UIO-66 and ferrocenecarboxaldehyde are dissolved in absolute ethanol and heated at 80-100 ℃ under refluxAfter 12-24 hours, cooling to room temperature, washing and drying to obtain sample NH 2 -UIO-66-FC; finally, carboxyl carbon nano tube and NH 2 Fully grinding the-UIO-66-FC to obtain the CNT@NH 2 -UIO-66-FC；
Wherein zirconium tetrachloride (ZrCl) 4 ) 2-amino terephthalic acid (NH) 2 -BDC) and ferrocenecarboxaldehyde in a molar ratio of 1:1:1; the volume ratio of N, N-Dimethylformamide (DMF) to acetic acid is 8-16:1; carboxyl carbon nanotubes and NH used 2 The mass ratio of the-UIO-66-FC is 1:2-3; adding 0.1-0.5 mmol of zirconium tetrachloride into each 10mL of N, N-dimethylformamide;
alternatively, method two, in-situ growth to prepare CNT@NH 2 -UIO-66-FC comprising the steps of:
zirconium tetrachloride (ZrCl) 4 ) Mixing carboxyl carbon nano tube and N, N-Dimethylformamide (DMF), stirring, and adding 2-amino terephthalic acid (NH) 2 BDC) and acetic acid, stirring to obtain a mixed solution; the mixed solution is subjected to microwave reaction for 30 to 45 minutes at the temperature of 120 to 150 ℃, and is cooled to room temperature, washed and dried to obtain CNT@NH 2 -UIO-66; cnt@nh 2 Dissolving UIO-66 and ferrocene formaldehyde in absolute ethyl alcohol, refluxing and heating for 12-24 hours at 80-100 ℃, cooling to room temperature, washing and drying to obtain a sample CNT@NH 2 -UIO-66-FC；
Wherein zirconium tetrachloride (ZrCl) 4 ) 2-amino terephthalic acid (NH) 2 -BDC) and ferrocenecarboxaldehyde in a molar ratio of 1:1:1; the volume ratio of N, N-Dimethylformamide (DMF) to acetic acid is 8-16:1; the mass ratio of the carboxyl carbon nano tube to the zirconium tetrachloride is 1:2-3; 0.1 to 0.5mmol of zirconium tetrachloride is added per 10mL of N, N-dimethylformamide.
The application of the MOF-based lithium-sulfur battery interlayer material is used for preparing a diaphragm of a lithium-sulfur battery.
The anode of the application of the MOF-based lithium-sulfur battery interlayer material is a carbon nano tube-sulfur composite material; the negative electrode is aluminum foil; the diaphragm is CNT@NH 2 -UIO-66-FC modified separator; the electrolyte is 1, 3-dioxolane containing 1.0M lithium bistrifluoromethane sulfonate (LiTFSI)A mixed solvent of cyclic (DOL) and dimethyl ether (DME) (volume ratio of 1:1);
the preparation method of the positive electrode comprises the following steps: mixing sulfur powder and carbon nano tube in the mass ratio of 3-4:1, and adding CS 2 The solution is preserved for 12 to 14 hours at the temperature of 155 to 160 ℃ and dried to obtain the carbon nano tube-sulfur composite material;
fully mixing the carbon nano tube-sulfur composite material, conductive carbon black and polyvinylidene fluoride (PVDF) as a binder (the mass ratio is 8:1:1), dripping N-methyl pyrrolidone (NMP) into the mixture to prepare slurry, coating the slurry on an aluminum foil, drying the slurry, and cutting the slurry to obtain a positive plate of the lithium-sulfur battery;
the preparation method of the CNT@NH2-UIO-66-FC modified membrane comprises the following steps: CNT@NH 2 Adding an N-methyl pyrrolidone solvent into UIO-66-FC and a binder polyvinylidene fluoride (PVDF), performing ultrasonic dispersion, performing suction filtration on the membrane, and performing drying and cutting to obtain the membrane of the lithium-sulfur battery:
wherein, the mass ratio is CNT@NH 2 -UIO-66-FC: binder = 8:2-1; the membrane is made of polypropylene microporous membrane and CNT@NH 2 -UIO-66-FC loading of 0.2-0.3 mg cm -2 。
The beneficial effects of the invention are as follows:
(1) CNT@NH prepared by the method 2 -UIO-66-FC shows 1490mA h g as a sandwich material for lithium sulphur cells -1 High specific capacity, and 1186mAh g is still maintained after 200 circles of circulation under 0.1 coulomb -1 The high specific capacity can obviously inhibit the shuttle effect and promote the commercial application of the lithium-sulfur battery.
(2) Preparation of CNT@NH according to the invention 2 The raw materials required by the UIO-66-FC are cheap and easy to obtain (the unit price of 2-amino terephthalic acid is less than 500 yuan/Kg, the unit price of ferrocene formaldehyde is less than 3000 yuan/Kg, and the unit price of zirconium tetrachloride is less than 400 yuan/Kg), and the preparation method is simple and easy for large-scale production.
Drawings
FIG. 1 is a graph of CNT@NH prepared in example 1 2 -UIO-66 and cnt@nh 2 -fourier transform infrared spectrogram of UIO-66-FC.
FIG. 2 is a graph of CNT@N prepared in example 1H 2 -scanning electron microscope image and digital photo image of UIO-66-FC membrane;
FIG. 3 is the CNT@NH prepared in example 1 and example 2 2 Cycling performance profile at 0.1C of a lithium sulfur cell with UIO-66-FC as separator sandwich.
Detailed description of the preferred embodiments
The invention is further described below with reference to examples and figures. The method and the equipment adopted by the invention are conventional methods and equipment in the technical field, and all reagents and materials are commercially available.
Example 1
(1) Preparation of CNT@NH by physical milling 2 -UIO-66-FC：
47 mg (i.e., 0.2 mmol) of zirconium tetrachloride (ZrCl) 4 ) And 8 ml of N, N-Dimethylformamide (DMF) were mixed and stirred to dissolve them sufficiently, and 36.2 mg (i.e., 0.2 mmol) of 2-aminoterephthalic acid (NH) 2 BDC) and 0.5 ml glacial acetic acid are added to the mixture and stirred to dissolve it thoroughly; and (3) putting the uniformly dispersed mixed solution into a microwave synthesizer, heating to 120 ℃, and keeping the constant temperature for 30 minutes. Cooling to room temperature, washing, drying to obtain NH 2 -UIO-66. NH to be obtained later 2 -UIO-66 and 44 mg (i.e. 0.2 mmol) ferrocene formaldehyde are dissolved in 50 ml absolute ethanol, heated at 80 ℃ under reflux for 12 hours, cooled to room temperature, washed and dried to obtain sample NH 2 -UIO-66-FC. Finally 30 mg of carboxyl carbon nanotubes (cas: 308068-56-6 available from Shenzhen ear scale technology Co., ltd.) and 60 mg of NH 2 Fully grinding the-UIO-66-FC to obtain the CNT@NH 2 -UIO-66-FC。
CNT@NH 2 -UIO-66 and cnt@nh 2 The IR spectrum of-UIO-66-FC is shown in FIG. 1.
(2) Preparation of the separator:
25 mg of CNT@NH 2 Adding the UIO-66-FC and 7 mg of binder polyvinylidene fluoride (PVDF) into 50 ml of N-methyl pyrrolidone solvent, uniformly dispersing by ultrasonic, taking 5 ml of mixed solution, filtering on a polypropylene pp membrane, drying and cutting into a membrane with the diameter of 18mm, and obtaining the membrane of the lithium-sulfur battery. The scanning electron microscope image and the digital photo image are shown in fig. 2.
(3) Preparation of carbon nanotube-sulfur composite:
150 mg of sulfur powder and 50 mg of carbon nanotubes were mixed and 5 ml of CS was added dropwise 2 And (3) preserving the temperature of the solvent at 155 ℃ for 12 hours, and drying to obtain the carbon nano tube-sulfur composite material. And then, fully mixing 160 mg of carbon nano tube-sulfur composite material, 20 mg of conductive carbon black and 20 mg of polyvinylidene fluoride, dripping 3 ml of N-methyl pyrrolidone (NMP) to prepare slurry, coating the slurry on aluminum foil, coating the slurry with the thickness of 100 mu m, drying, and cutting the slurry into the diameter of 14mm to obtain the positive plate of the lithium sulfur battery.
(4) Assembling a battery:
the anode is made of a carbon nano tube-sulfur composite material; the negative electrode is aluminum foil; the diaphragm is CNT@NH 2 -UIO-66-FC modified PP separator; the electrolyte is a mixed solution of 1, 3-Dioxolane (DOL) and dimethyl ether (DME) (volume ratio is 1:1) containing 1.0M lithium bistrifluoromethyl sulfonate imide (LiTFSI), and the button-type lithium sulfur battery is assembled in a glove box filled with argon. The battery cycle performance is shown in fig. 3, and has excellent cycle stability at a current density of 0.1C.
FIG. 1 shows that CNT@NH 2 -UIO-66 and cnt@nh 2 Fourier transform infrared Spectrum of-UIO-66-FC at 1265cm -1 The C-N bond was found to have a stretching vibration absorption peak at 1429cm -1 The C-C bond was found to have a peak of absorption of stretching vibration at 1587cm -1 The stretching vibration absorption peak of the c=o bond was found, indicating NH 2 Successful synthesis of UIO-66. With CNT@NH 2 CNT@NH as compared to UIO-66 2 -UIO-66-FC at 3400cm -1 The symmetrical and asymmetrical stretching vibration absorption peaks of N-H bond at the left and right broadband are obviously weakened and are in 1685cm -1 The occurrence of the C=N bond stretching vibration absorption peak proves that the structure is-NH 2 Consumed, ferrocene has been successfully grafted to cnt@nh by covalent bonds 2 on-UIO-66, CNT@NH was successfully synthesized 2 -UIO-66-FC。
FIG. 2 shows that CNT@NH is obtained by suction filtration 2 The UIO-66-FC is uniformly coated on the surface of the PP to form a uniform black coating, which indicates the existence of the carbon nano tube, and the carbon nano tube can increase the conductivity of the material, so that the material can be better used for lithium-sulfur batteriesIs a kind of medium.
Example 2
Other procedures were as in example 1 except that 30 mg of the carboxylated carbon nanotubes were mixed with zirconium tetrachloride and N, N-dimethylformamide and stirred to dissolve them sufficiently, not with NH 2 -UIO-66-FC mixing, i.e. in situ growth preparation.
FIG. 3 shows that in situ grown CNT@NH 2 After activation of the UIO-66-FC with New Wired cell cabinets at 0.05C, 1305mAh g was presented at 0.1C -1 Initial discharge capacity, capacity after 200 cycles was maintained at 1186mAh g -1 The average capacity decay rate per cycle was 0.045% with coulombic efficiency approaching 100%. In contrast, physically mixed cnt@nh 2 -UIO-66-FC, after activation at 0.05C, was started 1275mAh g from the initial -1 Decay to 1141mAh g -1 The average capacity decay rate per cycle was 0.052% and the coulombic efficiency was 100%. The interlayer material of the invention improves the discharge specific capacity and the cycle stability of the lithium sulfur battery.
Example 3
The other steps were the same as in example 1 except that the amount of acetic acid was 1 ml.
Example 4
The other steps were the same as in example 1 except that the mixed solution was heated to 150℃in a microwave synthesizer.
Example 5
The other steps are the same as in example 1, except that they are kept at constant temperature for 45 minutes.
Example 6
The other steps are the same as in example 1, except that the heating is performed at 100℃under reflux.
Example 7
The other steps are the same as in example 1 except that the heating reflux is conducted for 24 hours.
Example 8
The other steps are the same as in example 1, except that the temperature is kept at 160 ℃.
Example 9
The other steps are the same as in example 1, except that the temperature is kept for 14 hours.
Example 10
The other steps are the same as in example 1, except that 3.125 mg of binder is used.
Example 11
The other steps were the same as in example 1 except that 175 mg of sulfur powder was used.
Example 12
The other steps were the same as in example 2 except that the amount of acetic acid was 1 ml.
Example 13
The other steps were the same as in example 2 except that the mixture was heated to 150℃in a microwave synthesizer.
Example 14
The other steps are the same as in example 2, except that they are kept at constant temperature for 45 minutes.
Example 15
The other steps are the same as in example 2, except that the heating is performed at 100℃under reflux.
Example 16
The other steps are the same as in example 2 except that the heating reflux is conducted for 24 hours.
Example 17
The other steps are the same as in example 2, except that the temperature is kept at 160 ℃.
Example 18
The other steps are the same as in example 2, except that the temperature is kept for 14 hours.
Example 19
The other steps are the same as in example 2, except that 3.125 mg of binder is used.
Example 20
The other steps were the same as in example 2 except that 175 mg of sulfur powder was used. The invention is not a matter of the known technology.
Claims (4)
1. A lithium-sulfur battery interlayer material based on MOF is characterized in that the composition of the material comprises NH 2 -UIO-66-FC and carbon nanotube CNT in a mass ratio of 3-2:1;
wherein NH is 2 The structural formula of the UIO-66-FC is as follows:
2. the method for preparing the MOF-based lithium-sulfur battery interlayer material according to claim 1, wherein the method is characterized by either of the following two ways:
a first method; preparation of CNT@NH by physical milling 2 -UIO-66-FC comprising the steps of:
mixing zirconium tetrachloride and N, N-dimethylformamide, stirring, adding 2-amino terephthalic acid and acetic acid, and stirring to obtain a mixed solution; carrying out microwave reaction on the mixed solution for 30-45 minutes at the temperature of 120-150 ℃; cooling to room temperature, washing, drying to obtain NH 2 -UIO-66; NH is then added 2 Dissolving UIO-66 and ferrocene formaldehyde in absolute ethyl alcohol, refluxing and heating for 12-24 hours at 80-100 ℃, cooling to room temperature, washing and drying to obtain NH 2 -UIO-66-FC; finally, carboxyl carbon nano tube and NH 2 grinding-UIO-66-FC to obtain CNT@NH 2 -UIO-66-FC；
Wherein zirconium tetrachloride (ZrCl) 4 ) 2-amino terephthalic acid (NH) 2 -BDC) and ferrocenecarboxaldehyde in a molar ratio of 1:1:1; the volume ratio of N, N-Dimethylformamide (DMF) to acetic acid is 8-16:1; carboxyl carbon nanotubes and NH used 2 The mass ratio of the-UIO-66-FC is 1:2-3; adding 0.1-0.5 mmol of zirconium tetrachloride into each 10mL of N, N-dimethylformamide;
alternatively, method two, in-situ growth to prepare CNT@NH 2 -UIO-66-FC comprising the steps of:
mixing zirconium tetrachloride, carboxyl carbon nano tube and N, N-dimethylformamide, stirring, adding 2-amino terephthalic acid and acetic acid, and stirring to obtain a mixed solution; the mixed solution is subjected to microwave reaction for 30 to 45 minutes at the temperature of 120 to 150 ℃, and is cooled to room temperature, washed and dried to obtain CNT@NH 2 -UIO-66; cnt@nh 2 Dissolving UIO-66 and ferrocene formaldehyde in absolute ethyl alcohol, refluxing and heating for 12-24 hours at 80-100 ℃, cooling to room temperatureWashing and drying to obtain CNT@NH 2 -UIO-66-FC；
Wherein, the mol ratio of zirconium tetrachloride, 2-amino terephthalic acid and ferrocenyl formaldehyde is 1:1:1; the volume ratio of the N, N-dimethylformamide to the acetic acid is 8-16:1; the mass ratio of the carboxyl carbon nano tube to the zirconium tetrachloride is 1:2-3; 0.1 to 0.5mmol of zirconium tetrachloride is added per 10mL of N, N-dimethylformamide.
3. Use of the MOF-based lithium sulfur battery interlayer material according to claim 1 for the preparation of a separator for a lithium sulfur battery.
4. The use of the MOF-based lithium sulfur battery interlayer material of claim 3, wherein in the lithium sulfur battery, the positive electrode is a carbon nanotube-sulfur composite material; the negative electrode is aluminum foil; the diaphragm is CNT@NH 2 -UIO-66-FC modified separator; the electrolyte is a lithium bistrifluoromethane sulfonate (LiTFSI) solution containing 1.0M, and the solvent is a mixed solvent of 1, 3-Dioxolane (DOL) and dimethyl ether (DME) in a volume ratio of 1:1;
the preparation method of the positive electrode comprises the following steps: mixing sulfur powder and carbon nano tube in the mass ratio of 3-4:1, and adding CS 2 The solution is preserved for 12 to 14 hours at the temperature of 155 to 160 ℃ and dried to obtain the carbon nano tube-sulfur composite material;
fully mixing the carbon nano tube-sulfur composite material, conductive carbon black and a binder (the mass ratio is 8:1:1), dripping N-methyl pyrrolidone (NMP) into the mixture to prepare slurry, coating the slurry on an aluminum foil, drying the slurry, and cutting the slurry to obtain a positive plate of the lithium-sulfur battery;
the preparation method of the CNT@NH2-UIO-66-FC modified membrane comprises the following steps: CNT@NH 2 Adding an N-methyl pyrrolidone solvent into UIO-66-FC and a binder polyvinylidene fluoride (PVDF), performing ultrasonic dispersion, performing suction filtration on the membrane, and performing drying and cutting to obtain the membrane of the lithium-sulfur battery;
wherein, the mass ratio is CNT@NH 2 -UIO-66-FC: binder = 8:2-1; the membrane is made of polypropylene microporous membrane.
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