CN116462223B - ZnS/MoO2Composite material and preparation method thereof, lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery - Google Patents
ZnS/MoO2Composite material and preparation method thereof, lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title description 8
- 239000000243 solution Substances 0.000 claims abstract description 83
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 70
- 238000010438 heat treatment Methods 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 43
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 35
- 239000011592 zinc chloride Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 60
- 235000015393 sodium molybdate Nutrition 0.000 claims description 30
- 239000011684 sodium molybdate Substances 0.000 claims description 30
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000006255 coating slurry Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 239000005077 polysulfide Substances 0.000 description 12
- 229920001021 polysulfide Polymers 0.000 description 12
- 150000008117 polysulfides Polymers 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 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 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- 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
- H01M50/431—Inorganic material
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a ZnS/MoO 2 composite material and a preparation method thereof, a lithium-sulfur battery diaphragm and a preparation method thereof, and a lithium-sulfur battery, and the preparation method of ZnS/MoO 2 comprises the following steps: 1) Uniformly dispersing MoO 2 into deionized water; according to the mole ratio of Mo atoms to Zn atoms of 1:1, adding zinc chloride into deionized water according to the mass ratio of zinc chloride to sodium sulfide of 1:2, weighing sodium sulfide, adding deionized water, uniformly stirring, sequentially adding a zinc chloride solution and a sodium sulfide solution into a MoO 2 solution, and ultrasonically stirring to obtain a mixed solution A; 2) Cleaning the mixed solution A, and drying the collected solid matters to obtain a product B; 3) And (3) fully grinding the product B, placing the product B in a tube furnace, pre-burning the product B in an argon atmosphere at a temperature rising rate of 5-10 ℃/min from room temperature to 300-500 ℃, then heating the product B to 700-900 ℃ at a temperature rising rate of 5-10 ℃/min, preserving heat, naturally cooling the product B to obtain ZnS/MoO 2, modifying a commercial battery diaphragm by using ZnS/MoO 2, and assembling the product B into a lithium sulfur battery with excellent cycling stability and high specific discharge capacity.
Description
Technical Field
The invention belongs to the technical field of lithium sulfur batteries, and particularly relates to a ZnS/MoO 2 composite material, a preparation method thereof, a lithium sulfur battery diaphragm, a preparation method thereof and a lithium sulfur battery.
Background
Along with the increasing demand of emerging devices such as portable devices and electric vehicles, the relevant standards of energy storage systems are also increasing in order to meet the requirements of energy supply, socioeconomic performance and other conditions. Lithium-sulfur (Li-S) batteries have a high theoretical specific capacity (1675 mAhg -1) and high energy density (2600 WhKg -1), and are rich in elemental sulfur production, low in cost, and environmentally friendly, and are considered to be one of the next generation of chemical energy storage devices with high efficiency and reliability compared to commercial lithium ion batteries. However, dissolution and deposition of sulfur on the electrode surface involve complex multiple electron transfer processes and multiphase reactions, which make lithium sulfur batteries subject to problems in the development process, which are mainly manifested as: the slow electric conversion rate of the first lithium polysulfide is easy to cause a larger concentration gradient near the positive electrode; the second lithium polysulfide and the third lithium polysulfide are easy to diffuse through the diaphragm under the action of high concentration difference to generate a shuttle effect, so that the cycle life and the stability of the battery can be greatly reduced, and further the lithium-sulfur battery is difficult to develop rapidly.
The membrane is used as one of key components of the lithium sulfur battery, plays a very important role in the performance of the battery, and the existing commercial polypropylene membrane is very easy to cause the shuttle effect due to the characteristics of porous surface and large pores, so that researchers in recent years adopt a membrane modification method for the lithium sulfur battery to slow down the shuttle effect, thereby improving the cycling stability of the battery, and the existing membrane modification method accelerates the deposition conversion process of the lithium polysulfide by coating a material with adsorption and catalytic conversion effects on the lithium polysulfide. In addition, the scholars improve the cycling stability of the battery by preparing the functional separator, the main preparation method comprises the steps of coating polar and nonpolar materials on the separator to modify the separator, wherein the separator-modified materials mainly comprise carbon materials, polymers, inorganic metallics and the like to modify the separator, the pore structure of the carbon materials can effectively relieve the shuttle of polysulfide and improve the conductivity, the polysulfide is adsorbed, but the pure carbon materials are nonpolar and have very limited physical adsorption to the polysulfide. Currently, researchers have used metal oxides and sulfides, such as TiO 2、MoO2、ZnS、MoS2, in lithium sulfur battery separator materials to catalyze and convert polysulfides by metal-sulfur bond bonding. In general, the modified materials of the separator layer can effectively alleviate the shuttle reaction to improve the battery performance, but due to various problems of equipment cost, etc., the research on functional separator materials is now only at laboratory level. Therefore, in order to simplify the manufacturing process and reduce the production cost, further development of a novel functional diaphragm is required, and industrial production is expected to be realized.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a ZnS/MoO 2 composite material and a preparation method thereof, a lithium-sulfur battery diaphragm and a preparation method thereof, and a lithium-sulfur battery, wherein the preparation method is simple and easy to control, is suitable for industrial production, and has excellent cycle stability and high discharge specific capacity.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.1-0.4 g of MoO 2 into 10-25 g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, 10-20 g of deionized water is added and stirred uniformly, so as to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 10-20 g of deionized water into the sodium sulfide, and uniformly stirring the mixture to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring to obtain a mixed solution A;
2) Cleaning the mixed solution A, and drying the collected solid matters to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, heating the product B from room temperature to 300-500 ℃ for presintering for 1-3 h at a heating rate of 5-10 ℃/min under argon atmosphere, heating the product B to 700-900 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 0.5-2 h, and naturally cooling the product B to room temperature to obtain the ZnS/MoO 2 composite.
Further, the MoO 2 in the step 1) is prepared by the following method:
1.1 Taking 0.2-0.5 g of sodium molybdate and 0.4-1.0 g of hydroxylamine hydrochloride, respectively placing into two beakers, adding 8-15 g of deionized water into each of the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 90-120 ℃ and stirring for 7-13 h to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and under the argon atmosphere, heating the product D from room temperature to 300-400 ℃ at a heating rate of 5-10 ℃/min for presintering for 0.5-2 h, then heating the product D to 700-800 ℃ and preserving the heat for 0.5-2 h to obtain MoO 2.
Further, the washing in the step 2) is to wash with ultrapure water and absolute ethyl alcohol respectively and carry out suction filtration for 3 times; or respectively centrifugally washing with ultrapure water and absolute ethanol for 3 times at 8000rpm, wherein the centrifugal washing time is 15min each time.
A ZnS/MoO 2 composite.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Firstly grinding ZnS/MoO 2 composite material into powder, and then according to the mass ratio (0.5-1): (0.5-3): (6-9) uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1: (1.4-2), dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial lithium sulfur diaphragm, and drying to obtain the lithium sulfur battery diaphragm.
Further, the commercial lithium sulfur battery separator in the step 2) is any one of a polypropylene separator, a polyethylene/polypropylene double-layer separator or a polyethylene/polypropylene/polyethylene triple-layer separator.
A lithium sulfur battery separator.
A lithium sulfur battery has an initial charge-discharge capacity of 700mAh g -1 at a current density of 5C and a charge-discharge capacity of 688mAhg -1 after 200 cycles.
Compared with the prior art, the invention has the following technical effects:
1) The ZnS/MoO 2 composite material prepared by the method is similar to a hexagonal prism in shape, can provide more catalytic active sites, can accelerate the conversion kinetics of lithium polysulfide by modifying a commercial lithium sulfur battery diaphragm, has better conductivity and adsorption effect on the lithium polysulfide, and can better inhibit the shuttle effect of polysulfide, thereby improving the utilization rate of active substance sulfur and remarkably improving the cycle stability and specific discharge capacity of a lithium sulfur battery; in addition, znS is beneficial to reducing the diffusion distance of Li + in a solid phase, improving the diffusion rate of Li + and accelerating the electrochemical reaction kinetics rate, and the lithium sulfur battery diaphragm modified by ZnS/MoO 2 effectively ensures the cycling stability and the rapid charge and discharge capability of the lithium sulfur battery through the synergistic effect of MoO 2 and ZnS.
2) The preparation method of the ZnS/MoO 2 composite material and the lithium-sulfur battery diaphragm has the advantages of simple process, short period, easy control of process conditions, high repeatability of products, good uniformity, contribution to large-scale production and capability of overcoming the defects of complex operation, low repeatability and difficulty in large-scale production in the process of preparing the diaphragm material in the prior art.
3) The ZnS/MoO 2 modified lithium-sulfur battery diaphragm prepared by the method provided by the invention enables the initial charge-discharge capacity of the battery to be 700mAh g -1 under the high current density of 5C, and after 200 cycles, the charge-discharge capacity of the battery is 688mAh g -1, so that the battery has excellent cycle stability, high specific discharge capacity and quick charge-discharge capacity.
Drawings
FIG. 1 is an SEM image of ZnS/MoO 2 composite prepared in example 1 of the present invention;
FIG. 2 is an XRD spectrum of ZnS/MoO 2 composite prepared in example 1 of the present invention;
FIG. 3 is a graph showing the cycle performance of ZnS/MoO 2 composite prepared in example 1 of the present invention;
Fig. 4 is a charge-discharge curve of a lithium sulfur battery assembled by a lithium sulfur separator containing ZnS/MoO 2 composite material prepared in example 1 of the present invention at 5C current density at different cycle times.
Detailed Description
The following examples illustrate the invention in further detail.
Example 1
The preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.1g of MoO 2 into 12g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, 10g of deionized water is added and stirred uniformly, so as to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 10g of deionized water into the sodium sulfide, and uniformly stirring to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring for 10min to obtain a mixed solution A; wherein MoO 2 is prepared by the following method:
1.1 Taking 0.2g of sodium molybdate and 0.4g of hydroxylamine hydrochloride, respectively placing the sodium molybdate and the hydroxylamine hydrochloride into two beakers, adding 8g of deionized water into each of the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 90 ℃ and magnetically stirring for 7 hours to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and pre-burning for 0.5h from room temperature to 300 ℃ at a heating rate of 5 ℃/min under argon atmosphere, then heating to 700 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h to obtain MoO 2;
2) The mixed solution A is centrifugally washed for 3 times by ultrapure water and absolute ethyl alcohol at the rotating speed of 8000rpm respectively, and each time is centrifugally washed for 15 minutes, and the collected solid matters are dried to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, and under the argon atmosphere, heating the product B from room temperature to 300 ℃ at a heating rate of 5 ℃/min for presintering for 1h, heating the product B to 700 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 0.5h to obtain the ZnS/MoO 2 composite material.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Grinding ZnS/MoO 2 composite material into powder, and then according to the mass ratio of 1:3: and 6, uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1:1.4, dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial Celgrad (PP) lithium sulfur diaphragm, and drying for 12 hours at 55 ℃ by using an oven to obtain the lithium sulfur battery diaphragm.
When the lithium-sulfur battery is assembled: the lithium-sulfur battery separator prepared in example 1 was punched into a disc with a diameter of 19mm, used as a battery separator, a sulfur/carbon composite material was used as a battery positive electrode, lithium metal was used as a negative electrode, a CR2032 type battery case was used, an electrolyte was 1.0M bis (trifluoromethanesulfonyl) imide lithium LITFSI, a mixed solvent was DME/DOL (volume ratio of 1:1), and an additive was 1.0% LiNO 3, wherein the sulfur/carbon composite material consisted of sublimed sulfur and acetylene black, and the mass fraction of sublimed sulfur in the composite material was 60 to 70wt%.
The method for preparing the sulfur/carbon composite material comprises the following steps:
Step 1, according to the mass ratio (3-4): (6-7), placing acetylene black and sublimed sulfur into a mortar, and fully grinding and mixing to obtain a product E;
and 2, heating the product E to 155 ℃ in a 50ml hydrothermal reaction kettle, preserving heat for 12-36 h, and naturally cooling to room temperature to obtain the sulfur/carbon composite material.
As can be seen from fig. 1, the ZnS/MoO 2 composite prepared in example 1 has a surface morphology of a compass shape, and MoO 2 is distributed on the surface of ZnS.
As seen in fig. 2, the ZnS/MoO 2 composite material has no significant hetero-peaks.
As shown in fig. 3, in the lithium sulfur battery assembled by using the ZnS/MoO 2 modified lithium sulfur battery diaphragm prepared in example 1, the initial charge-discharge capacity of the battery can reach 700mAh g -1 at a current density of 5C, after 200 cycles, the charge-discharge capacity can still be 688mAh g -1, and the average attenuation rate per cycle is 0.0057%.
As can be seen from fig. 4, the lithium sulfur battery assembled with ZnS/MoO 2 modified lithium sulfur battery separator prepared in example 1, at a high current density of 5C, exhibited two discharge plateau and one charge plateau, demonstrating that the lithium sulfur battery assembled with ZnS/MoO 2 modified lithium sulfur battery separator still has rapid electrochemical kinetics at high current density.
Example 2
The preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.2g of MoO 2 in 16g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, 12g of deionized water is added and stirred uniformly, so as to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 12g of deionized water into the sodium sulfide, and uniformly stirring to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring for 18min to obtain a mixed solution A; wherein MoO 2 is prepared by the following method:
1.1 Taking 0.3g of sodium molybdate and 0.5g of hydroxylamine hydrochloride, respectively placing the sodium molybdate and the hydroxylamine hydrochloride into two beakers, adding 10g of deionized water into the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 100 ℃ and magnetically stirring for 8 hours to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and pre-burning for 1h from room temperature to 330 ℃ at a heating rate of 6 ℃/min under argon atmosphere, then heating to 720 ℃ at a heating rate of 6 ℃/min, and preserving heat for 1.5h to obtain MoO 2;
2) The mixed solution A is centrifugally washed for 3 times by ultrapure water and absolute ethyl alcohol at the rotating speed of 8000rpm respectively, and each time is centrifugally washed for 15 minutes, and the collected solid matters are dried to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, and pre-sintering for 1.5 hours at the temperature rising rate of 6 ℃/min from room temperature to 350 ℃ in the presence of argon, and then heating to 750 ℃ at the temperature rising rate of 6 ℃/min and preserving heat for 1 hour to obtain the ZnS/MoO 2 composite material.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Grinding ZnS/MoO 2 composite material into powder, and then according to the mass ratio of 1:2: and 7, uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1:1.7, dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial Celgrad (PP) lithium sulfur diaphragm, and drying for 15 hours at 60 ℃ by using an oven to obtain the lithium sulfur battery diaphragm.
Example 3
The preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.3g of MoO 2 in 19g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, and 16g of deionized water is added and stirred uniformly to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 16g of deionized water into the sodium sulfide, and uniformly stirring to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring for 25min to obtain a mixed solution A; wherein MoO 2 is prepared by the following method:
1.1 Taking 0.4g of sodium molybdate and 0.6g of hydroxylamine hydrochloride, respectively placing the sodium molybdate and the hydroxylamine hydrochloride into two beakers, adding 12g of deionized water into the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 110 ℃ and magnetically stirring for 10 hours to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and pre-burning for 1.5 hours at the temperature rising rate of 8 ℃/min from room temperature to 350 ℃ under the argon atmosphere, then, heating the product D to 750 ℃ at the temperature rising rate of 8 ℃/min and preserving heat for 1 hour to obtain MoO 2;
2) The mixed solution A is centrifugally washed for 3 times by ultrapure water and absolute ethyl alcohol at the rotating speed of 8000rpm respectively, and each time is centrifugally washed for 15 minutes, and the collected solid matters are dried to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, and pre-sintering for 2.5 hours from room temperature to 400 ℃ at a heating rate of 8 ℃/min under argon atmosphere, heating to 850 ℃ at a heating rate of 8 ℃/min, and preserving heat for 1.5 hours to obtain the ZnS/MoO 2 composite.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Grinding ZnS/MoO 2 composite material into powder, and then according to the mass ratio of 1:1:8, uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1:1.8, dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial polyethylene lithium sulfur diaphragm, and drying for 18 hours at 65 ℃ by using an oven to obtain the lithium sulfur battery diaphragm.
Example 4
The preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.4g of MoO 2 in 23g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, 18g of deionized water is added and stirred uniformly, so as to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 18g of deionized water into the sodium sulfide, and uniformly stirring to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring for 30min to obtain a mixed solution A; wherein MoO 2 is prepared by the following method:
1.1 Taking 0.5g of sodium molybdate and 0.8g of hydroxylamine hydrochloride, respectively placing the sodium molybdate and the hydroxylamine hydrochloride into two beakers, adding 14g of deionized water into the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 120 ℃ and magnetically stirring for 12 hours to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and pre-burning for 2 hours from room temperature to 400 ℃ at a heating rate of 10 ℃/min under argon atmosphere, then heating to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 0.5 hour to obtain MoO 2;
2) Respectively cleaning the mixed solution A with ultrapure water and absolute ethyl alcohol, carrying out suction filtration for 3 times, and drying the collected solid matters to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, heating the product B from room temperature to 500 ℃ for presintering for 3 hours at a heating rate of 10 ℃/min under an argon atmosphere, heating the product B to 800 ℃ at a heating rate of 10 ℃/min, and preserving the heat for 2 hours to obtain the ZnS/MoO 2 composite material.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Grinding the ZnS/MoO 2 composite material into powder, and then according to the mass ratio of 0.5:0.5:9, uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1:2, dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial polyethylene/polypropylene double-layer lithium sulfur diaphragm, and drying for 21 hours at 70 ℃ by using an oven to obtain the lithium sulfur battery diaphragm.
Example 5
The preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.25g of MoO 2 in 25g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, and 20g of deionized water is added and stirred uniformly to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 20g of deionized water into the sodium sulfide, and uniformly stirring to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring for 13min to obtain a mixed solution A; wherein MoO 2 is prepared by the following method:
1.1 Taking 0.35g of sodium molybdate and 0.7g of hydroxylamine hydrochloride, respectively placing the sodium molybdate and the hydroxylamine hydrochloride into two beakers, adding 15g of deionized water into each of the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 120 ℃ and magnetically stirring for 13 hours to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and pre-burning for 1h from room temperature to 380 ℃ at a heating rate of 9 ℃/min under argon atmosphere, then heating to 780 ℃ at a heating rate of 9 ℃/min and preserving heat for 2h to obtain MoO 2;
2) Respectively cleaning the mixed solution A with ultrapure water and absolute ethyl alcohol, carrying out suction filtration for 3 times, and drying the collected solid matters to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, and pre-burning for 1h from room temperature to 450 ℃ at a heating rate of 9 ℃/min under an argon atmosphere, heating to 900 ℃ at a heating rate of 9 ℃/min, and preserving heat for 0.5h to obtain the ZnS/MoO 2 composite material.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Grinding ZnS/MoO 2 composite material into powder, and then according to the mass ratio of 0.75:1.75:7.5, uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1:1.6, dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial polyethylene/polypropylene/polyethylene three-layer lithium sulfur diaphragm, and drying for 24 hours at 75 ℃ by using an oven to obtain the lithium sulfur battery diaphragm.
Example 6
The preparation method of the ZnS/MoO 2 composite material comprises the following steps:
1) Firstly, uniformly dispersing 0.15g of MoO 2 in 10g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, 14g of deionized water is added and stirred uniformly, so as to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 14g of deionized water into the sodium sulfide, and uniformly stirring to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring for 20min to obtain a mixed solution A; wherein MoO 2 is prepared by the following method:
1.1 Taking 0.25g of sodium molybdate and 1.0g of hydroxylamine hydrochloride, respectively placing the sodium molybdate and the hydroxylamine hydrochloride into two beakers, adding 9g of deionized water into the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;
1.2 Heating the mixed solution C to 105 ℃ and magnetically stirring for 9 hours to remove the solvent, and drying to obtain a product D;
1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, and pre-burning for 2 hours from room temperature to 315 ℃ at a heating rate of 7 ℃/min under argon atmosphere, then heating to 770 ℃ at a heating rate of 7 ℃/min, and preserving heat for 0.5 hour to obtain MoO 2;
2) Respectively cleaning the mixed solution A with ultrapure water and absolute ethyl alcohol, carrying out suction filtration for 3 times, and drying the collected solid matters to obtain a product B;
3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, and under the argon atmosphere, heating the product B from room temperature to 350 ℃ at a heating rate of 7 ℃/min for presintering for 1h, heating the product B to 700 ℃ at a heating rate of 7 ℃/min, and preserving the heat for 1.5h to obtain the ZnS/MoO 2 composite material.
A method of making a lithium sulfur battery separator comprising the steps of:
1) Grinding the ZnS/MoO 2 composite material into powder, and then according to the mass ratio of 0.65:2.5:6.5, uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1:1.5, dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;
2) And uniformly coating the coating slurry on one side surface of a commercial Celgrad (PP) lithium sulfur diaphragm, and drying for 20 hours at 75 ℃ by using an oven to obtain the lithium sulfur battery diaphragm.
Claims (7)
- The preparation method of the ZnS/MoO 2 composite material is characterized by comprising the following steps:1) Firstly, uniformly dispersing 0.1-0.4 g of MoO 2 into 10-25 g of deionized water to obtain MoO 2 solution; and then according to the mole ratio of Mo atoms to Zn atoms of 1:1, zinc chloride is taken, 10-20 g of deionized water is added and stirred uniformly, so as to obtain zinc chloride solution; then the mass ratio of zinc chloride to sodium sulfide is 1:2, weighing sodium sulfide, adding 10-20 g of deionized water into the sodium sulfide, and uniformly stirring the mixture to obtain a sodium sulfide solution; finally, sequentially adding the zinc chloride solution and the sodium sulfide solution into the MoO 2 solution, and ultrasonically stirring to obtain a mixed solution A; the MoO 2 is prepared by the following method:1.1 Taking 0.2-0.5 g of sodium molybdate and 0.4-1.0 g of hydroxylamine hydrochloride, respectively placing into two beakers, adding 8-15 g of deionized water into each of the two beakers, uniformly stirring to obtain a sodium molybdate solution and a hydroxylamine hydrochloride solution respectively, and mixing the sodium molybdate solution and the hydroxylamine hydrochloride solution to obtain a mixed solution C;1.2 Heating the mixed solution C to 90-120 ℃ and stirring for 7-13 h to remove the solvent, and drying to obtain a product D;1.3 Fully grinding the product D, then placing the ground product D into a tube furnace, heating the product D from room temperature to 300-400 ℃ for presintering for 0.5-2 h at a heating rate of 5-10 ℃/min under argon atmosphere, heating the product D to 700-800 ℃ at a heating rate of 5-10 ℃/min, and preserving the temperature for 0.5-2 h to obtain MoO 2;2) Cleaning the mixed solution A, and drying the collected solid matters to obtain a product B;3) And (3) fully grinding the product B, placing the ground product B in a tube furnace, heating the product B from room temperature to 300-500 ℃ for presintering for 1-3 h at a heating rate of 5-10 ℃/min under argon atmosphere, heating the product B to 700-900 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 0.5-2 h, and naturally cooling the product B to room temperature to obtain the ZnS/MoO 2 composite.
- 2. The method for preparing ZnS/MoO 2 composite according to claim 1, wherein the washing in step 2) is carried out with ultrapure water and absolute ethanol respectively and suction-filtered 3 times; or respectively centrifugally washing with ultrapure water and absolute ethanol for 3 times at 8000rpm for 15min each.
- 3. A ZnS/MoO 2 composite prepared by the process of any one of claims 1 to 2.
- 4. A method for preparing a lithium sulfur battery separator by using the ZnS/MoO 2 composite material according to claim 3, comprising the steps of:1) Firstly grinding ZnS/MoO 2 composite material into powder, and then according to the mass ratio (0.5-1): (0.5-3): (6-9) uniformly mixing binder PVDF, acetylene black and ZnS/MoO 2 powder to obtain a sample to be coated, wherein the mass ratio of the sample to be coated to NMP is 1: (1.4-2), dissolving a sample to be coated in NMP, and stirring at a high speed to obtain coating slurry;2) And uniformly coating the coating slurry on one side surface of a commercial lithium sulfur diaphragm, and drying to obtain the lithium sulfur battery diaphragm.
- 5. The method for preparing a lithium sulfur battery separator according to claim 4, wherein the commercial lithium sulfur battery separator of step 2) is any one of a polypropylene separator, a polyethylene/polypropylene double-layer separator, or a polyethylene/polypropylene/polyethylene triple-layer separator.
- 6. A lithium sulfur battery separator made by the method of claim 5.
- 7. A lithium sulfur battery comprising the lithium sulfur battery separator of claim 6, wherein the initial charge-discharge capacity is 700mAh g -1 at a current density of 5C, and after 200 cycles, the charge-discharge capacity is 688mAh g -1.
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