CN114824194B - Supermolecule crown ether polyacid/sulfur composite positive electrode material, preparation method and application thereof - Google Patents
Supermolecule crown ether polyacid/sulfur composite positive electrode material, preparation method and application thereof Download PDFInfo
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- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 88
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011593 sulfur Substances 0.000 title claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 62
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 18
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 4
- 229920001021 polysulfide Polymers 0.000 abstract description 10
- 239000005077 polysulfide Substances 0.000 abstract description 10
- 150000008117 polysulfides Polymers 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 31
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The invention discloses a supermolecule crown ether polyacid/sulfur composite positive electrode material, a preparation method and application thereof. The invention takes supermolecule first generation macrocyclic crown ether 18-crown ether-6 as a main body, keggin type polyoxometallate as a guest, forms supermolecule crown ether polyacid crystals by self-assembly through intermolecular forces in acetonitrile, and then obtains the supermolecule crown ether polyacid/sulfur composite anode material by ball milling and mixing the crystals with sublimated sulfur. According to the invention, the supermolecular crown ether polyacid composite material is used as a host material of the positive electrode of the lithium-sulfur battery, so that the mutual transformation of polysulfides in the lithium-sulfur battery can be promoted, the reaction kinetics can be improved, and meanwhile, the supermolecular crown ether polyacid composite material has the capability of coordinating with lithium ions, so that the ion conductivity and the adsorption capability on the polysulfides are increased, and the battery performance is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and relates to a supermolecular crown ether polyacid/sulfur composite positive electrode material, a preparation method and application thereof.
Background
With the rapid development of portable electronic devices and electric automobiles and the rapid development of current lithium ion batteries, high-energy-density and long-life batteries are receiving more and more attention, however, lithium ion batteries have been further developed due to low energy density. Lithium sulfur (Li-S) battery systems, which have much higher energy densities than the lithium ion battery systems currently commercialized, are considered to be the most promising next generation high energy density secondary battery systems. However, for lithium sulfur batteries, the insulating properties of elemental sulfur result in low sulfur utilization. The "shuttle effect" is the most critical problem limiting the practical application of Li-S batteries, because the "shuttle effect" of polysulfides causes continuous flow of active materials and surface passivation of lithium negative electrodes, which in turn causes serious problems of battery capacity decay, coulombic efficiency reduction, poor cycle stability and the like, and also increases excessive consumption of electrolyte.
The Polyoxometallate (POM) is a sulfur host material with double-function catalytic performance, has the characteristics of metal oxide, limits polysulfide dissolution through chemical oxidation reduction, can participate in the whole charge-discharge cycle in the form of a molecular catalyst in the charge-discharge process of a battery, can reversibly store and transfer a plurality of electrons, can bidirectionally catalyze the discharge reduction process of lithium polysulfide and the charge oxidation process of lithium sulfide, promotes the solid-liquid-solid phase conversion of sulfur species in the battery, and is expected to substantially alleviate the shuttle effect problem of polysulfide. However, the prior research of polyacids in lithium sulfur batteries has not improved the capacity of the batteries and the cycle stability is still poor, and the overall performance is improved only to a limited extent (W.Yao, L.Liu, X.Wu, Q.Chao, H.Xie, Z Su, ACS appl. Mater. Interfaces,2018,10,35911-35918.).
Crown ethers, as the first generation of supramolecular macrocycles, have evolved rapidly in the field of supramolecular chemistry. The supermolecular crown ether has the capability of coordinating with lithium ions, can increase the ion conductivity and can obviously improve the battery performance, so the supermolecular crown ether can be applied to lithium metal batteries (H.Wang, J.He, J.Liu, et al, adv. Function. Mate. 2020,31,2002578.).
Disclosure of Invention
The invention aims to provide a supermolecule crown ether polyacid/sulfur composite positive electrode material, a preparation method thereof and application thereof in lithium-sulfur batteries. According to the invention, the supermolecular crown ether polyacid composite material is used as a host material of the positive electrode of the lithium-sulfur battery, so that the mutual transformation of polysulfides in the lithium-sulfur battery can be promoted, the reaction kinetics can be improved, the ion conductivity and the adsorption capacity to the polysulfides of the battery can be increased, and the battery performance can be remarkably improved.
The technical solution for achieving the purpose of the invention is as follows:
the preparation method of the supermolecular crown ether polyacid/sulfur composite positive electrode material comprises the following steps:
(1) Keggin type polyoxometallate H 3 [PW 12 O 40 ]Or H 3 [PMo 12 O 40 ]Dissolving in acetonitrile, adding LiCl, heating to 60-80 ℃, adding 18-crown ether-6, stirring for reaction, filtering after the reaction is finished, volatilizing a solvent, filtering, washing, and drying to obtain supermolecule crown ether polyacid crystals;
(2) And uniformly mixing the supermolecular crown ether polyacid crystal with sublimated sulfur by ball milling to obtain the supermolecular crown ether polyacid/sulfur composite anode material.
Preferably, in step (1), H 3 [PW 12 O 40 ]Or H 3 [PMo 12 O 40 ]The concentration in acetonitrile was 1.67×10 -3 mol/L。
Preferably, in step (1), the stirring reaction time is 30 to 40 minutes.
Preferably, in step (1), H 3 [PW 12 O 40 ]Or H 3 [PMo 12 O 40 ]The molar ratio of LiCl to 18-crown-6 was 1:5:5.
preferably, in step (1), the solvent is volatilized for 7 to 10 days at room temperature.
Preferably, in step (1), the drying temperature is 60℃and the drying time is 24 hours.
Preferably, in step (2), the mass ratio of sublimed sulphur to supermolecular crown ether polyacid crystals is 7:3.
Preferably, in step (2), the ball milling mixing time is 4 hours.
The invention also provides the supermolecular crown ether polyacid/sulfur composite positive electrode material prepared by the preparation method.
Further, the invention provides application of the supermolecular crown ether polyacid/sulfur composite positive electrode material in lithium-sulfur batteries.
Compared with the prior art, the invention has the advantages that:
(1) The invention takes supermolecule first generation macrocyclic crown ether 18-crown ether-6 as a main body, keggin type polyoxometallate [ PW ] 12 O 40 ] 3- Or [ PMo ] 12 O 40 ] 3- As a guest, the supermolecule crystal material is formed by self-assembly in acetonitrile through intermolecular force, the synthesis method is simple, and the yield is high.
(2) The invention obtains supermolecular crystal through self-assembly, and prepares supermolecular crystal material with stable crystal structure by controlling the conditions of reaction time, mole ratio of each raw material, stirring time, temperature and the like.
(3) The supermolecular crown ether polyacid/sulfur composite material prepared by the invention solves the shuttle effect problem in lithium sulfur batteries, can promote polysulfide interconversion in the lithium sulfur batteries, improve reaction kinetics, increase ion conductivity and adsorption capacity to polysulfide of the batteries, and has better cycle reversibility and stability for the lithium sulfur batteries taking the supermolecular crown ether polyacid/sulfur composite material as a positive electrode material.
Drawings
FIG. 1 is a polyhedral diagram of (a) a supramolecular crown ether phosphotungstic acid crystal and (b) a supramolecular crown ether phosphomolybdic acid crystal.
FIG. 2 is a plot of the packing of (a) supramolecular crown ether phosphotungstic acid crystals and (b) supramolecular crown ether phosphomolybdic acid crystals.
FIG. 3 is a scanning electron microscope image of (a) supramolecular crown ether phosphotungstic acid crystals and (b) supramolecular crown ether phosphomolybdic acid crystals.
FIG. 4 is a graph showing the comparison of the theoretical values of X-ray powder diffraction with the experimental values of (a) supramolecular crown ether phosphotungstic acid crystals and (b) supramolecular crown ether phosphomolybdic acid crystals.
FIG. 5 is a comparison of Fourier transform infrared spectroscopy analysis of (a) supramolecular crown ether phosphotungstic acid crystals and (b) supramolecular crown ether phosphomolybdic acid crystals and their synthetic monomers.
FIG. 6 is a thermogravimetric analysis of (a) supramolecular crown ether phosphotungstic acid crystals and (b) supramolecular crown ether phosphomolybdic acid crystals and other synthetic monomers.
Fig. 7 is a graph of battery magnification of (a) supramolecular crown-ether phosphotungstic acid/sulfur composite and (b) supramolecular crown-ether phosphomolybdic acid/sulfur composite as positive electrode material for lithium-sulfur battery.
Fig. 8 is a graph of a long cycle of the battery of (a) supramolecular crown ether phosphotungstic acid/sulfur composite and (b) supramolecular crown ether phosphomolybdic acid/sulfur composite as positive electrode material for lithium sulfur battery.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1
The preparation of the supermolecular crown ether phosphotungstic acid/sulfur composite material comprises the following specific steps:
(1) Preparing supermolecule crown ether phosphotungstic acid crystal: 720mg (0.25 mmol) of Keggin-type heteropolyacid H 3 [PW 12 O 40 ]Dissolved in 150mL of CH 3 In CN, the temperature of the system is heated to 70 ℃ through a water bath, and the temperature is kept at H 3 [PW 12 O 40 ]After complete dissolution, 53mg (1.25 mmol) of LiCl and 330mg (1.25 mmol) of 18-crown-6 were added in sequence. The mixed solution is stirred and reacted for 30 minutes, then filtered while the mixed solution is hot, and the mixed solution is slowly volatilized along with the solution at room temperature to obtain yellowish green blocky crystals. Suction filtering, and fully using a large amount of acetonitrileWashing to obtain supermolecule crown ether phosphotungstic acid crystal Li 3 PW 12 O 40 (CH 3 CN) 2 (C 12 O 6 H 24 ) 3 HCl 0.833g, yield 88.0% (based on W).
The crystallographic parameters of the supramolecular crown ether phosphotungstic acid crystals are shown in table 1.
TABLE 1 crystallographic parameters of supramolecular crown ether phosphotungstic acid crystals
(2) Supermolecular crown ether phosphotungstic acid/sulfur composite material: and uniformly mixing the supermolecular crown ether phosphotungstic acid crystal with sublimated sulfur ball milling for 4 hours to obtain the supermolecular crown ether phosphotungstic acid/sulfur composite material.
Example 2
The preparation method of the supermolecular crown ether phosphomolybdic acid/sulfur composite material comprises the following specific steps:
(1) Preparation of supramolecular crown ether phosphomolybdic acid crystals: 456mg (0.25 mmol) of Keggin-type heteropoly acid H 3 [PMo 12 O 40 ]Dissolved in 150mL of CH 3 In CN, the temperature of the system is heated to 70 ℃ through a water bath, and the temperature is kept at H 3 [PMo 12 O 40 ]After complete dissolution, 11mg (2.5 mmol) of LiCl and 660mg (2.5 mmol) of 18-crown-6 were added in sequence. The mixed liquid was stirred for 30 minutes, filtered while hot, and slowly evaporated with the solution at room temperature to give yellowish green bulk crystals. Suction filtering, and fully washing with a large amount of acetonitrile to obtain supermolecule crown ether phosphomolybdic acid crystal H 3 PMo 12 O 40 (CH 3 CN) 2 (C 12 O 6 H 24 ) 3 (H 2 O) 4 HCl 0.623g with a yield of 88.9% (based on Mo).
The crystallographic parameters of the supramolecular crown ether phosphomolybdic acid crystals are shown in table 2.
TABLE 2 crystallographic parameters of supramolecular crown ether phosphomolybdic acid crystals
(2) Preparation of supramolecular crown ether phosphomolybdic acid/sulfur composite material: and uniformly mixing the supermolecular crown ether phosphomolybdic acid crystal with sublimated sulfur for ball milling for 4 hours to obtain the supermolecular crown ether phosphomolybdic acid/sulfur composite material.
Comparative example 1
This comparative example is substantially the same as example 1, except that the Keggin-type heteropoly acid H 3 [PW 12 O 40 ]The molar ratios of LiCl and 18-crown-6 were 1:10: 10. 1:4:4. crystals were not synthesized at this ratio, and solid precipitates were formed.
Comparative example 2
This comparative example is essentially the same as example 1, with the only difference that the polyoxometalate used is silicotungstic acid. Under these conditions, crystals cannot be synthesized, and only solid precipitates can be formed.
Comparative example 3
This comparative example is essentially the same as example 1, except that the lithium salt used is lithium nitrate. Under these conditions, crystals cannot be synthesized, and only solid precipitates can be formed.
Comparative example 4
This comparative example was substantially the same as example 1, except that the reaction temperatures in step (1) were 55℃and 85℃respectively. Under these conditions, crystals cannot be synthesized, and only solid precipitates can be formed.
Comparative example 5
This comparative example is substantially the same as example 1, except that the mass ratio of the crystals and sulfur in step (1) is 3: 1. 3:2. the composite positive electrode material prepared in the proportion has poor battery effect.
FIG. 1 is a polyhedral diagram of a supermolecular crown ether phosphotungstic acid crystal and a supermolecular crown ether phosphomolybdic acid crystal prepared by the invention. It can be seen that each phosphotungstic or phosphomolybdic acid molecule combines with a supramolecular crown ether through intermolecular hydrogen bonds to form a supramolecular crown ether polyacid crystal.
FIG. 2 is a diagram showing the stacking of supramolecular crown ether phosphotungstic acid crystals and supramolecular crown ether phosphomolybdic acid crystals prepared according to the invention. It can be seen that phosphotungstic acid or phosphomolybdic acid and crown ether are interlaced with each other, and are closely stacked through intermolecular hydrogen bonds, forming an ordered stacked structure.
FIG. 3 is a scanning electron microscope image of the supermolecular crown ether phosphotungstic acid crystal and supermolecular crown ether phosphomolybdic acid crystal prepared by the invention, and the diameter of the crystal is about 400 nanometers, and the crystal has a square structure.
FIG. 4 is a graph showing the comparison of the theoretical value and the experimental value of the X-ray powder diffraction of the supermolecular crown ether phosphotungstic acid crystal and the supermolecular crown ether phosphomolybdic acid crystal prepared by the invention, and the graph shows that the experimental value of the X-ray powder diffraction of the crystal material is quite identical with the peak position of the theoretical simulation value, the peak strength and the peak shape are kept identical, the graph is almost identical, the signal-to-noise of experimental data is smaller, the analysis of the crystal is completely correct, and the purity of the prepared crystal material is higher.
FIG. 5 is a chart of Fourier transform infrared spectroscopy analysis of the supramolecular crown ether phosphotungstic acid crystals and supramolecular crown ether phosphomolybdic acid crystals prepared by the invention and the synthetic monomers thereof, and it can be seen that all characteristic peaks of phosphotungstic acid or phosphomolybdic acid and crown ether exist, which indicates that the supramolecular complex crystals really contain the two basic components.
FIG. 6 is a thermogravimetric analysis chart of the supermolecular crown ether phosphotungstic acid crystal and supermolecular crown ether phosphomolybdic acid crystal and the synthetic monomer thereof, which are prepared by the invention, and the molar ratio of each component in the crystal analysis is well verified, and the accuracy of the crystal structure analysis is also again verified.
Fig. 7 is a graph of battery magnification of supermolecular crown ether phosphotungstic acid/sulfur composite material and supermolecular crown ether phosphomolybdic acid/sulfur composite material prepared by the invention as positive electrode material of lithium-sulfur battery. The discharge specific capacity of the supermolecule crown ether phosphotungstic acid/sulfur positive electrode composite material is about 1437mAh g -1 Near theory of86% of capacity (1675 mAh g -1 ). Supermolecular crown phosphotungstic acid/sulfur anodes can provide discharge capacities of 1249, 1210, 1184, 1120, 1019, 913 and 622mAh g, respectively, when cycled at 0.2, 0.3, 0.5, 1.0, 2.0, 3.0 and 5.0C current densities -1 . When the current density returns to 0.1C, the discharge capacity of the supermolecule crown ether phosphotungstic acid/sulfur anode is recovered to 1249mAh g -1 Good battery capacity and excellent reversibility are exhibited. The discharge specific capacity of the supermolecular crown ether phosphomolybdic acid/sulfur positive electrode composite material is about 1341mAh g -1 Near 80% of theoretical capacity (1675 mAh g -1 ). Supermolecular crown phosphomolybdic acid/sulfur anodes can provide discharge capacities of 1205, 1149, 1086, 1068, 893, 783, and 566mAh g, respectively, when cycled at 0.2, 0.3, 0.5, 1.0, 2.0, 3.0, and 5.0C current densities -1 . When the current density returns to 0.1C, the discharge capacity of the supermolecule crown ether phosphomolybdic acid/sulfur anode is recovered to 1127mAh g -1 Good battery capacity and excellent reversibility are exhibited.
FIG. 8 is a graph showing the long cycle of the supermolecular crown ether phosphotungstic acid/sulfur composite material prepared by the invention as a positive electrode material of a lithium sulfur battery. After 300 times of circulation, the supermolecule crown ether phosphotungstic acid/sulfur anode can still realize good circulation stability (initial capacity 1112mAh g) at a current rate of 1.0C -1 After 1000 times of circulation, the product is 348mAh g -1 ) And the capacity attenuation rate of each period is only 0.068%, and the coulomb efficiency is above 95%. After 300 times of circulation, the supermolecule crown ether phosphomolybdic acid/sulfur positive electrode can still realize good circulation stability at the current rate of 1.0C (initial capacity 923mAh g) -1 713mAh g after 300 cycles -1 ) And the capacity attenuation rate per cycle is only 0.076%, and the coulomb efficiency is above 95%.
Claims (8)
1. The preparation method of the supermolecular crown ether polyacid/sulfur composite positive electrode material is characterized by comprising the following steps of:
(1) Keggin type polyoxometallate H 3 [PW 12 O 40 ]Or H 3 [PMo 12 O 40 ]Dissolved in acetonitrileThen LiCl is added, the mixture is heated to 60-80 ℃, then 18-crown ether-6 is added, the mixture is stirred for reaction, after the reaction is finished, the mixture is filtered, the solvent is volatilized, the mixture is filtered, washed and dried to obtain supermolecular crown ether polyacid crystal, H 3 [PW 12 O 40 ]Or H 3 [PMo 12 O 40 ]The molar ratio of LiCl to 18-crown-6 was 1:5:5, a step of;
(2) And uniformly mixing the supermolecular crown ether polyacid crystal and sublimated sulfur by ball milling to obtain the supermolecular crown ether polyacid/sulfur composite positive electrode material, wherein the mass ratio of sublimated sulfur to the supermolecular crown ether polyacid crystal is 7:3.
2. The process according to claim 1, wherein in step (1), H 3 [PW 12 O 40 ]Or H 3 [PMo 12 O 40 ]The concentration in acetonitrile was 1.67×10 -3 mol/L。
3. The method according to claim 1, wherein in the step (1), the stirring reaction time is 30 to 40 minutes.
4. The preparation method according to claim 1, wherein in the step (1), the solvent is volatilized for 7 to 10 days at room temperature.
5. The method according to claim 1, wherein in the step (1), the drying temperature is 60℃and the drying time is 24 hours.
6. The method according to claim 1, wherein in the step (2), the ball-milling mixing time is 4 hours.
7. The supermolecular crown ether polyacid/sulfur composite positive electrode material prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the supramolecular crown ether polyacid/sulfur composite positive electrode material according to claim 7 in lithium-sulfur batteries.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210269823.9A CN114824194B (en) | 2022-03-18 | 2022-03-18 | Supermolecule crown ether polyacid/sulfur composite positive electrode material, preparation method and application thereof |
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| CN202210269823.9A CN114824194B (en) | 2022-03-18 | 2022-03-18 | Supermolecule crown ether polyacid/sulfur composite positive electrode material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN112940051A (en) * | 2021-03-15 | 2021-06-11 | 扬州大学 | Preparation method of supramolecular crystal material based on crown ether-Keggin type polyacid |
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| CN112436114A (en) * | 2020-11-16 | 2021-03-02 | 扬州大学 | Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof |
| CN112940051A (en) * | 2021-03-15 | 2021-06-11 | 扬州大学 | Preparation method of supramolecular crystal material based on crown ether-Keggin type polyacid |
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