CN114361429A - Preparation method of sulfur positive electrode material and magnesium-sulfur battery assembly method thereof - Google Patents
Preparation method of sulfur positive electrode material and magnesium-sulfur battery assembly method thereof Download PDFInfo
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- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 53
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- 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 description 5
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 4
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000000707 layer-by-layer assembly Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of energy sources, in particular to a preparation method of a sulfur anode material and a magnesium-sulfur battery assembly method thereof. The preparation method of the sulfur anode material comprises the steps of preparing few layers of Ti3C2Suspension, preparation of Nitrogen doped Ti3C2(N‑Ti3C2) Material and preparation of S- (N-Ti)3C2) A composite material; the magnesium-sulfur battery assembly method comprises a preparation method of a sulfur positive electrode material, and also comprises the steps of preparing electrolyte and assembling the magnesium-sulfur battery; the assembled magnesium-sulfur battery has excellent electrochemical performance and S- (N-Ti) under the current density of 100mA g < -1 >3C2) The positive electrode has 689mAh g‑1The specific capacity of initial discharge is determined,and still has 380mAh g after circulating for 13 circles‑1Specific discharge capacity of (2). Illustrating nitrogen doping of Ti3C2Is a good sulfur-containing material and can be practically applied to magnesium-sulfur batteries.
Description
Technical Field
The invention relates to the technical field of energy sources, in particular to a preparation method of a sulfur anode material and a magnesium-sulfur battery assembly method thereof.
Background
Increasing energy demand has prompted the widespread development of advanced electrical energy storage devices. Lithium ion batteries are widely used as an important energy carrier in daily life and modern industry. However, this type of battery has difficulty in avoiding some safety problems, requires prevention of overcharge or overdischarge, and, in addition, storage difficulties of lithium resources and dendrite formation problems during battery operation hinder sustainable development of lithium ion batteries. Accordingly, there is an increasing research effort towards developing other rechargeable metal-ion batteries, including magnesium-ion batteries and magnesium-metal batteries. The magnesium battery is easy to prepare, has thermodynamic stability in the charging and discharging processes, and can overcome various defects of the lithium battery. On one hand, magnesium is rich in the earth crust, the content of magnesium is 10000 times of that of lithium, so that the cost of a magnesium electrode is extremely lower than that of a lithium battery, and on the other hand, metal magnesium has better chemical stability, and a magnesium anode is not disturbed by SEI film formation during charging. However, the low mobility of magnesium ions in the corresponding positive electrode materials is a major obstacle to the development of magnesium battery technology, and also slows down the development of matched negative electrode materials and electrolytes.
The sulfur is an ideal magnesium ion battery anode material due to the higher volume theoretical specific capacity, and can be used for magnesium sulfur batteries. The second generation of commercial magnesium ion battery electrolyte (APC) can easily react with elemental sulfur due to its strong nucleophilicity, and is not suitable for magnesium sulfur batteries. To solve this problem, Muldooon first introduced non-nucleophilic MgHMDSCl/AlCl in 20113the/THF electrolyte was applied to a magnesium sulfur cell which only operated two charge-discharge cycles. Thereafter, stabilized Mg (CB11H11)2The/tetraglyme electrolyte is applied to the magnesium-sulfur battery, and the electrochemical performance of the battery is improved. ZHao-Karger and MgHMDS2/AlCl3the/THF electrolyte is applied to the magnesium-sulfur battery, and the battery can still maintain 260mA h g after being circulated for 20 circles-1. Removing deviceThus, MgCl2/AlCl3the/THF is also applied to magnesium-sulfur batteries, and both show excellent electrochemical activity. Commercial magnesium salt Mg (TFSI)2The ionic liquid has high solubility in ether solution, and the ether solution is non-nucleophilic at the same time, so that the ionic liquid has a prospect of being applied to magnesium-sulfur batteries. Se-Young Ha firstly converts Mg (TFSI)2The/glyme/diglyme electrolyte is successfully applied to the magnesium ion battery, has stronger oxidation resistance and lower viscosity, and allows reversible magnesium deposition/desorption. Later, Wangchun produced Mg (TFSI)2/MgCl2Application of/DME to magnesium-sulfur batteries exhibiting excellent electrochemical performance with high specific capacity and long cycle life, and they also studied Mg (TFSI)2/I2Application of DME electrolyte in magnesium-sulfur battery.
Similar to lithium sulfur batteries, elemental sulfur applied to magnesium sulfur batteries requires a suitable host material, makes up for the deficiency of poor conductivity of elemental sulfur, and can promote interconversion of polysulfides generated during charging and discharging of magnesium sulfur batteries. In recent years, a two-dimensional transition metal carbon/nitride (MXene) material has been one of the most focused research subjects in the field of electrochemical energy storage due to its excellent electrical conductivity and high volume capacity. MXene is represented by formula Mn+1XnTx(n ═ 1,2, 3) wherein M is an early transition metal element, X represents carbon or nitrogen, and T represents a surface functional group (-O, -OH and-F). Theoretical calculation shows that typical MXene material Ti3C2Has higher Mg content2+Ion storage capacity. Min Xu et al propose a simple strategy by layering (d) -Ti3C2TxThe layers were separated by preliminarily inserting cetyltrimethylammonium bromide (CTAB), a common cationic surfactant, to thereby obtain (d) -Ti3C2TxThe electrode has magnesium storage capacity, and takes APC solvent as electrolyte, (d) -Ti3C2TxCTAB electrode at 50mA g-1Has a current density of 300mAh cm-3High reversible volumetric specific capacity of (d) -Ti3C2TxCTAB has excellent rate performance and good cycle stability. However, MXene two-dimensional material in magnesium-sulfur batteryThe application was not studied.
Therefore, those skilled in the art have made efforts to develop a method for preparing a sulfur positive electrode material and a method for assembling a magnesium-sulfur battery using the same.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is how to technically realize Ti3C2The application of the material in magnesium ion batteries with higher mass and volume energy density. By effecting the synthesis of Ti3C2Suspension and further synthesis of N-Ti by liquid-phase electrostatic self-assembly method3C2Process conditions of (1), preparation of the resulting N-Ti3C2Has the micro-morphology of nano-sheet like graphene, and is further subjected to melting and compounding with sublimed sulfur to prepare S- (N-Ti)3C2) A composite material. The composite material is matched with Mg (TFSI)2/2AlCl3A magnesium-sulfur battery assembled by/2 LiTFSI/diglyme electrolyte has higher charge-discharge specific capacity and better cycle performance
In order to achieve the above object, the present invention provides a method for preparing a sulfur positive electrode material, comprising the steps of:
adding 1,2,3g of lithium fluoride into 20,30,40mL of concentrated hydrochloric acid, stirring for 5-20min, and adding 1g of Ti3AlC2Reacting for 24-48h at 40-80 ℃; adding the reaction product into deionized water, centrifuging for multiple times (4000rpm) to obtain precipitate until the pH value of the supernatant is close to 6.0, adding 100-200mL deionized water into the precipitate, and performing N precipitation at 0-20 deg.C2Stirring for 1-4h under atmosphere; then, centrifuging the product obtained after ultrasonic treatment for 10-30min (4000rpm) to remove substrate precipitates, adding a proper amount of deionized water, and centrifuging for 5-15min (10000rpm) to remove substrate precipitates; finally obtaining the few-layer Ti3C2Suspension (1-4mg mL)-1) And Ti in suspension3C2Presenting a nano-sheet morphology;
dispersing 1-3g of melamine into 30mL of absolute ethyl alcohol, violently stirring for 0.5-2h, then adding 1-5mL of concentrated hydrochloric acid, continuously stirring for 1-3h, and sending into an oven to dry the solvent; then, grinding the obtained white solid particles into powder, and centrifugally washing the powder for multiple times by using water and absolute ethyl alcohol to obtain melamine powder with electropositive surface; taking 50mL of few-layer Ti3C2Dissolving the suspension and 100mg of melamine powder with electropositive surface in 50mL of dilute hydrochloric acid to obtain a large amount of floccules, centrifuging the product with deionized water for 3 times (4000rpm), removing supernatant, and freeze-drying the precipitate to obtain a precursor; finally, the precursor is in N2Heating for 1-4h (400-3C2A material;
0.6g of sublimed sulphur and 0.4g of nitrogen doped Ti3C2Grinding for 20min, and placing in a tube furnace, N2Preserving the heat for 12 hours at 155 ℃ in the atmosphere, and naturally cooling to obtain the sulfur anode material S- (N-Ti)3C2) A composite material.
Further, the ultrasonic power in step 1 of the preparation method of the sulfur cathode material is 100W. Under the power condition, the high-efficiency and quick product obtaining can be ensured, the long-time waiting is avoided, the cost is reduced, and the breakage of the nanosheets in the product can be prevented.
Further, the method for preparing a sulfur cathode material according to claim 1, wherein the stirring in step 1 and step 2 is any one of manual stirring, mechanical stirring, electromagnetic stirring, vibration stirring and ultrasonic stirring.
Further, the method for producing a sulfur positive electrode material according to claim 1, wherein the time for the baking in step 2 is 2 hours or more. The drying time is too short, the solvent can not be fully volatilized, and the subsequent reaction efficiency improvement is influenced.
Further, the method for producing a sulfur positive electrode material according to claim 1, wherein the time of freeze-drying in step 2 is 2 hours or more. The drying time is too short, the solvent cannot be sufficiently volatilized, and a product with a specific morphology cannot be obtained, so that the final experimental efficiency is reduced.
Further, the method for producing a sulfur positive electrode material according to claim 1, wherein the grinding in step 3 is performed by hand grinding or mechanical grinding.
The invention also relates to a magnesium-sulfur battery assembly method, which comprises a preparation method adopting the sulfur anode material and also comprises the following steps:
step S1, preparing Mg (TFSI)2/2AlCl32LiTFSI/diglyme electrolyte:
292Mg of Mg (TFSI)2Adding 1mL of diethylene glycol dimethyl ether, stirring for 12h, and adding 134mg of AlCl3Stirring for 12h, adding 287mg of LiTFSI, and stirring for 12h to obtain Mg (TFSI)2/2AlCl32LiTFSI/diglyme electrolyte;
step S2, assembling Mg// Mg (TFSI)2/2AlCl3/2LiTFSI/diglyme//S-(N-Ti3C2) A magnesium-sulfur battery:
0.7g of the sulfur positive electrode material S- (N-Ti) was taken3C2) Putting the composite material, 0.2g of nano carbon powder and 0.1g of PVDF into a mortar, fully grinding for 20min, adding a proper amount of N-methyl pyrrolidone to prepare uniform slurry, coating the uniform slurry on a carbon aluminum foil, drying for 8h at 80 ℃, slicing and placing in a glove box for later use; when the magnesium-sulfur secondary battery is assembled, the cut positive plate is placed on a positive shell, a glass fiber diaphragm is covered, electrolyte is dripped, a magnesium plate, a spring gasket and a spring piece are covered, and finally a negative shell is covered; and packaging under a press machine to obtain the magnesium-sulfur battery.
Further, in the magnesium sulfur battery assembly method, the shape of the magnesium sulfur battery is a button shape in step S2.
Further, in the step S2 of the magnesium-sulfur battery assembling method, the press is a servo press.
The invention also relates to a magnesium-sulfur battery, which comprises the magnesium-sulfur battery manufactured by adopting the magnesium-sulfur battery assembling method.
According to the inventionThe beneficial effects are that: efficient preparation of nitrogen-doped Ti3C2(N-Ti3C2) And S- (N-Ti)3C2) Composite material, by etching typical three-dimensional MAX-phase Ti3AlC2Obtaining a few layers of Ti3C2The MXene is precisely prepared, and the N-Ti is further synthesized by utilizing a liquid-phase electrostatic self-assembly method3C2. Preparing the obtained N-Ti3C2Has the microscopic morphology of the graphene-like nano sheet, and is further subjected to melt compounding with sublimed sulfur to prepare S- (N-Ti)3C2) A composite material. The composite material is matched with Mg (TFSI)2/2AlCl3The magnesium-sulfur battery assembled by the/2 LiTFSI/diglyme electrolyte has higher charge-discharge specific capacity and better cycle performance, and shows that the MXene material has great application potential and value in the field of magnesium-sulfur batteries.
The invention solves the defect that the prior MXene material is rarely applied to the magnesium-sulfur battery, and provides N-Ti3C2And S- (N-Ti)3C2) And Mg (TFSI)2/2AlCl3The magnesium-sulfur battery assembled by the method has higher charge-discharge specific capacity and better cycle performance.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 Ti3C2SEM image of the suspension liquid drop on a silicon wafer after being dried;
FIG. 2 Ti3C2SEM pictures of the suspension after freeze-drying;
FIG. 3 Ti3C2The XRD pattern of the powder obtained after freeze drying of the suspension;
FIG. 4N-Ti3C2SEM image of the powder;
FIG. 5N-Ti3C2XRD pattern of the powder;
FIG. 6S- (N-Ti)3C2) SEM picture of (1);
drawing 7100mA g-1The cycle performance of the magnesium-sulfur battery under current density;
FIG. 8100 mA g-1The voltage-specific capacity curve of the first three circles of charge and discharge of the magnesium-sulfur battery under the current density.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
In the drawings, structurally identical elements are represented by like reference numerals, and structurally or functionally similar elements are represented by like reference numerals throughout the several views. The size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component. The thickness of the components may be exaggerated where appropriate in the figures to improve clarity.
Example 1
The invention provides a preparation method of a sulfur anode material, which comprises the following steps:
adding 1,2,3g lithium fluoride into 20,30,40mL concentrated hydrochloric acid, stirring for 5-20min, and adding 1g Ti3AlC2Reacting for 24-48h at 40-80 ℃; adding the reaction product into deionized water, centrifuging for multiple times (4000rpm) to obtain precipitate until the pH value of the supernatant is close to 6.0, adding 100-200mL deionized water into the precipitate, and performing N precipitation at 0-20 deg.C2Stirring for 1-4h under atmosphere; then, centrifuging the product obtained after ultrasonic treatment for 10-30min (4000rpm) to remove substrate precipitates, adding a proper amount of deionized water, and centrifuging for 5-15min (10000rpm) to remove substrate precipitates; finally obtaining the few-layer Ti3C2Suspension (1-4mg mL)-1) And Ti in suspension3C2Presenting a nano-sheet morphology;
1-3g of melamine was dispersed in 30mL of anhydrousViolently stirring in ethanol for 0.5-2h, then adding 1-5mL of concentrated hydrochloric acid, continuously stirring for 1-3h, and sending into an oven to dry the solvent; then, grinding the obtained white solid particles into powder, and centrifugally washing the powder for multiple times by using water and absolute ethyl alcohol to obtain melamine powder with electropositive surface; taking 50mL of few-layer Ti3C2Dissolving the suspension and 100mg of melamine powder with electropositive surface in 50mL of dilute hydrochloric acid to obtain a large amount of floccules, centrifuging the product with deionized water for 3 times (4000rpm), removing supernatant, and freeze-drying the precipitate to obtain a precursor; finally, the precursor is in N2Heating for 1-4h (400-3C2A material;
0.6g of sublimed sulphur and 0.4g of nitrogen doped Ti3C2Grinding for 20min, and placing in a tube furnace, N2Preserving the heat for 12 hours at 155 ℃ in the atmosphere, and naturally cooling to obtain the sulfur anode material S- (N-Ti)3C2) A composite material.
The invention also relates to a magnesium-sulfur battery assembly method, which comprises a preparation method adopting the sulfur anode material and also comprises the following steps:
step S1, preparing Mg (TFSI)2/2AlCl32LiTFSI/diglyme electrolyte:
292Mg of Mg (TFSI)2Adding 1mL of diethylene glycol dimethyl ether, stirring for 12h, and adding 134mg of AlCl3Stirring for 12h, adding 287mg of LiTFSI, and stirring for 12h to obtain Mg (TFSI)2/2AlCl32LiTFSI/diglyme electrolyte;
step S2, assembling Mg// Mg (TFSI)2/2AlCl3/2LiTFSI/diglyme//S-(N-Ti3C2) A magnesium-sulfur battery:
0.7g of the sulfur positive electrode material S- (N-Ti) was taken3C2) Placing the composite material, 0.2g of nano carbon powder and 0.1g of PVDF in a mortar, fully grinding for 20min, adding a proper amount of N-methyl pyrrolidone to prepare uniform slurry, coating the uniform slurry on a carbon aluminum foil, drying the uniform slurry at 80 ℃ for 8h, slicing the uniform slurry and then placing the uniform slurry on a piece of carbon aluminum foilPlacing the glove box in a glove box for later use; when the magnesium-sulfur secondary battery is assembled, the cut positive plate is placed on a positive shell, a glass fiber diaphragm is covered, electrolyte is dripped, a magnesium plate, a spring gasket and a spring piece are covered, and finally a negative shell is covered; and packaging under a press machine to obtain the magnesium-sulfur battery.
The invention also relates to a magnesium-sulfur battery, which comprises the magnesium-sulfur battery manufactured by adopting the magnesium-sulfur battery assembling method.
Ti3C2After preparation, the detection results are shown in fig. 1, fig. 2 and fig. 3. FIG. 1 shows Ti3C2SEM image of suspension liquid drop dried on silicon wafer; FIG. 2 shows Ti3C2SEM pictures of the suspension after freeze-drying; FIG. 3 shows Ti3C2The XRD pattern of the powder obtained after freeze drying of the suspension; FIGS. 1,2 and 3 all demonstrate that the Ti layer is less3C2The successful preparation.
N-Ti3C2After preparation, the results are shown in FIGS. 4 and 5, and N-Ti is shown in FIG. 43C2An SEM image of the powder shows that the material after nitrogen doping has a graphene-like nanosheet morphology and exhibits a fluffy and porous structure; FIG. 5 shows N-Ti3C2The XRD pattern of the powder proves that the N element is successfully introduced into the Ti3C2Causing a partial change in structure. S- (Ti)3C2) After preparation, the results are shown in FIG. 6, and FIG. 6 shows S- (N-Ti)3C2) SEM picture of (B) shows Ti3C2The surface becomes rough due to sulfur loading on the nano-sheets.
The assembled magnesium-sulfur battery is placed in a blue light tester to perform constant current charge and discharge test, and the test results are shown in fig. 7 and fig. 8. FIG. 7 shows 100mA g-1The cycle performance of the magnesium-sulfur battery under current density; FIG. 8 shows 100mA g-1The voltage-specific capacity curve of the first three circles of charge and discharge of the magnesium-sulfur battery under the current density. FIG. 7 shows the results for 100mA g-1The S- (N-Ti3C2) anode has 689mAh g at current density-1Initial specific discharge capacity and 380mAh g after 13 cycles-1Specific discharge capacity of (2). The results in FIG. 8 show that the magnesium-sulfur battery undergoes polysulfide during charge and dischargeAnd (3) electrochemical reaction of mutual conversion of substances. This indicates that nitrogen-doped Ti3C2 is a good sulfur-sink material and can be practically applied to magnesium-sulfur batteries.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A method for preparing a sulfur positive electrode material is characterized by comprising the following steps:
step 1, preparing few-layer Ti3C2Suspension:
adding 1,2,3g of lithium fluoride into 20,30,40mL of concentrated hydrochloric acid, stirring for 5-20min, and adding 1g of Ti3AlC2Reacting for 24-48h at 40-80 ℃; adding the reaction product into deionized water, centrifuging for multiple times (4000rpm) to obtain precipitate until the pH value of the supernatant is close to 6.0, adding 100-200mL deionized water into the precipitate, and performing N precipitation at 0-20 deg.C2Stirring for 1-4h under atmosphere; then, centrifuging the product obtained after ultrasonic treatment for 10-30min (4000rpm) to remove substrate precipitates, adding a proper amount of deionized water, and centrifuging for 5-15min (10000rpm) to remove substrate precipitates; finally obtaining the few-layer Ti3C2Suspension (1-4mg mL)-1) And Ti in suspension3C2Presenting a nano-sheet morphology;
step 2, preparing nitrogen-doped Ti3C2(N-Ti3C2) Materials:
dispersing 1-3g of melamine into 30mL of absolute ethyl alcohol, violently stirring for 0.5-2h, then adding 1-5mL of concentrated hydrochloric acid, continuously stirring for 1-3h, and sending into an oven to dry the solvent; then, grinding the obtained white solid particles into powder, and centrifugally washing the powder for multiple times by using water and absolute ethyl alcohol to obtain melamine powder with electropositive surface; taking 50mL of few-layer Ti3C2Suspension with 100mg surfaceDissolving electropositive melamine powder in 50mL of dilute hydrochloric acid, allowing a large amount of floccules to appear in the suspension, centrifuging the product with deionized water for 3 times (4000rpm), removing supernatant, and freeze-drying the precipitate to obtain a precursor; finally, the precursor is in N2Heating for 1-4h (400-3C2A material;
step 3, preparing S- (N-Ti)3C2) The composite material comprises the following components:
0.6g of sublimed sulphur and 0.4g of nitrogen doped Ti3C2Grinding for 20min, and placing in a tube furnace, N2Preserving the heat for 12 hours at 155 ℃ in the atmosphere, and naturally cooling to obtain the sulfur anode material S- (N-Ti)3C2) A composite material.
2. The method of claim 1, wherein the ultrasonic power of step 1 is 100W.
3. The method for preparing a sulfur cathode material according to claim 1, wherein the stirring in step 1 and step 2 is any one of manual stirring, mechanical stirring, electromagnetic stirring, vibration stirring and ultrasonic stirring.
4. The method of claim 1, wherein the drying time in step 2 is 2 hours or more.
5. The method according to claim 1, wherein the freeze-drying time in step 2 is 2 hours or more.
6. The method for preparing a sulfur positive electrode material according to claim 1, wherein the grinding in step 3 is performed by hand grinding or mechanical grinding.
7. A magnesium-sulfur battery assembly method comprising a preparation method using the sulfur positive electrode material according to any one of claims 1 to 6, further comprising the steps of:
step S1, preparing Mg (TFSI)2/2AlCl32LiTFSI/diglyme electrolyte:
292Mg of Mg (TFSI)2Adding 1mL of diethylene glycol dimethyl ether, stirring for 12h, and adding 134mg of AlCl3Stirring for 12h, adding 287mg of LiTFSI, and stirring for 12h to obtain Mg (TFSI)2/2AlCl32LiTFSI/diglyme electrolyte;
step S2, assembling Mg// Mg (TFSI)2/2AlCl3/2LiTFSI/diglyme//S-(N-Ti3C2) A magnesium-sulfur battery:
0.7g of the sulfur positive electrode material S- (N-Ti) was taken3C2) Putting the composite material, 0.2g of nano carbon powder and 0.1g of PVDF into a mortar, fully grinding for 20min, adding a proper amount of N-methyl pyrrolidone to prepare uniform slurry, coating the uniform slurry on a carbon aluminum foil, drying for 8h at 80 ℃, slicing and placing in a glove box for later use; when the magnesium-sulfur secondary battery is assembled, the cut positive plate is placed on a positive shell, a glass fiber diaphragm is covered, electrolyte is dripped, a magnesium plate, a spring gasket and a spring piece are covered, and finally a negative shell is covered; and packaging under a press machine to obtain the magnesium-sulfur battery.
8. A magnesium-sulfur battery produced by the magnesium-sulfur battery assembly method according to claim 7.
9. The method for assembling a magnesium-sulfur battery according to claim 7, wherein the magnesium-sulfur battery is in a button shape in step S2.
10. The magnesium-sulfur battery assembling method according to claim 7, wherein the press in step S2 is a servo press.
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