CN114361429B - 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
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 30
- 239000011593 sulfur Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 12
- 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
- 239000002002 slurry Substances 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- 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 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
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 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
- 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
- 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
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 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
- 238000011161 development Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 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
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000707 layer-by-layer assembly Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910021392 nanocarbon 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
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000013329 compounding Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 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
- 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
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 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
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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of energy, in particular to a preparation method of a sulfur positive electrode material and a magnesium-sulfur battery assembly method thereof. The preparation method of the sulfur positive electrode material comprises the steps of preparing a few-layer Ti 3 C 2 Suspension, preparation of Nitrogen doped Ti 3 C 2 (N‑Ti 3 C 2 ) Material, preparation of S- (N-Ti) 3 C 2 ) A composite material; the magnesium-sulfur battery assembling method comprises a preparation method of a sulfur positive electrode material, and further 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 > 3 C 2 ) The positive electrode had 689mAh g ‑1 The initial discharge specific capacity still has 380mAh g after 13 circles ‑1 Is a specific discharge capacity of (a). Description of Nitrogen doped Ti 3 C 2 Is a good sulfur-sink material and can be practically applied to magnesium-sulfur batteries.
Description
Technical Field
The invention relates to the technical field of energy, in particular to a preparation method of a sulfur positive electrode material and a magnesium-sulfur battery assembly method thereof.
Background
The 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 is difficult to avoid some safety problems, and it is necessary to prevent overcharge or overdischarge, and furthermore, the storage difficulty of lithium resources and dendrite problems formed during the operation of the battery prevent the sustainable development of lithium ion batteries. Accordingly, more and more research is being directed to the development of other chargeable and dischargeable metal ion batteries, including magnesium ion batteries and magnesium metal batteries. The magnesium battery is easy to prepare, has thermal dynamic stability in the charge and discharge process, and can overcome various defects of the lithium battery. On one hand, the magnesium is abundant in the crust, and the content of the magnesium is 10000 times of that of lithium, so that the cost of the magnesium electrode is much lower than that of the lithium electrode, and on the other hand, the metal magnesium has better chemical stability, and the magnesium anode is not bothered by SEI film formation during charging. However, the lower mobility of magnesium ions in the corresponding cathode materials is a major obstacle to the development of magnesium battery technology, while also slowing down the development of matched anode materials and electrolytes.
Sulfur has higher volume theoretical specific capacity, is an ideal magnesium ion battery anode material and can be used for magnesium sulfur batteries. The commercialized second generation magnesium ion battery electrolyte (APC) can easily react with elemental sulfur because of its strong nucleophilicity, and is not suitable for magnesium sulfur batteries. To solve this problem, J.Muldool was first directed to non-nucleophilic MgHMDSCl/AlCl in 2011 3 The THF electrolyte was applied to a magnesium sulfur battery that was operated for only two charge and discharge cycles. Thereafter, stable Mg (CB 11H 11) 2 The tetraglyme electrolyte is applied to a magnesium-sulfur battery, and the electrochemical performance of the battery is improved. Zhao-Karger is further treated with MgHMDS 2 /AlCl 3 THF electrolyte is applied to magnesium-sulfur battery, and the battery can still keep 260mA h g after 20 circles of circulation -1 . In addition, mgCl 2 /AlCl 3 THF was also used in magnesium sulfur batteries, all exhibiting superior electrochemical activity. Commercial magnesium salt Mg (TFSI) 2 The ether solution has high solubility in the ether solution, is non-nucleophilic at the same time, and has the prospect of being applied to magnesium-sulfur batteries. Se-Young Ha first uses Mg (TFSI) 2 The electrolyte of the glyme/diglyme is successfully applied to magnesium ion batteries, has strong oxidation resistance, low viscosity and allows reversible magnesium deposition/extraction. Thereafter, wang Chunsheng Mg (TFSI) 2 /MgCl 2 DME is applied to magnesium sulphur batteries which exhibit excellent electrochemical properties of high specific capacity, long cycle life, while they have also studied Mg (TFSI) 2 /I 2 Use of a DME electrolyte in a magnesium sulphur cell.
Similar to lithium sulfur batteryThe pool is applied to the magnesium-sulfur battery, and a proper host material is needed for the elemental sulfur, so that the defect of poor conductivity of the elemental sulfur is overcome, and the mutual conversion of polysulfides generated in the charging and discharging processes of the magnesium-sulfur battery can be promoted. In recent years, two-dimensional transition metal carbon/nitride (abbreviated as MXene) materials have been one of the most focused research subjects in the electrochemical energy storage field due to their excellent electrical conductivity and high volume capacity. MXene is represented by formula M n+1 X n T x (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 calculations indicate that typical MXene materials Ti 3 C 2 Has higher Mg 2+ Ion storage capacity. Min Xu et al propose a simple strategy by layering (d) -Ti 3 C 2 T x The common cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is inserted between the layers in advance to separate the layers (d) -Ti 3 C 2 T x The electrode has magnesium storage capacity, and uses APC solvent as electrolyte, (d) -Ti 3 C 2 T x CTAB electrode at 50mA g -1 Has a current density of 300mAh cm -3 High reversible volume specific capacity of (d) -Ti 3 C 2 T x CTAB has excellent rate performance and good cycle stability. However, the application of MXene two-dimensional materials in magnesium-sulfur batteries has not been studied.
Accordingly, those skilled in the art have been working to develop a method for preparing a sulfur positive electrode material and a method for assembling a magnesium sulfur battery thereof.
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 Ti 3 C 2 The material is applied to magnesium ion batteries with higher mass and volume energy density. By effecting synthesis of Ti 3 C 2 Suspension and further synthesis of N-Ti by liquid phase electrostatic self-assembly method 3 C 2 The process conditions of the (B) and (C) are that N-Ti is prepared 3 C 2 The S- (N-Ti) is prepared by further melting and compounding the nano-sheet-like micro-morphology of graphene and sublimed sulfur 3 C 2 ) A composite material. The composite material is matched with Mg (TFSI) 2 /2AlCl 3 The assembled magnesium-sulfur battery 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:
step 1, preparing few-layer Ti 3 C 2 Suspension:
adding 1,2,3g lithium fluoride into 20,30,40mL concentrated hydrochloric acid, stirring for 5-20min, and adding 1g Ti 3 AlC 2 Reacting for 24-48h at 40-80 ℃; adding deionized water into the reaction product, centrifuging for several times (4000 rpm) to obtain precipitate until the pH value of the supernatant approaches 6.0, adding 100-200mL deionized water into the precipitate, and adding N at 0-20deg.C 2 Stirring for 1-4h under the atmosphere; then, centrifuging the product obtained after ultrasonic treatment for 10-30min (4000 rpm) to remove substrate precipitate, adding a proper amount of deionized water, and centrifuging for 5-15min (10000 rpm) to remove substrate precipitate; finally obtain few-layer Ti 3 C 2 Suspension (1-4 mg mL) -1 ) And Ti in suspension 3 C 2 Presenting a nano sheet shape;
step 2, preparing nitrogen doped Ti 3 C 2 (N-Ti 3 C 2 ) Materials:
dispersing 1-3g melamine into 30mL absolute ethyl alcohol, vigorously stirring for 0.5-2h, then adding 1-5mL concentrated hydrochloric acid, continuously stirring for 1-3h, and sending into an oven to dry the solvent; grinding the obtained white solid particles into powder, and centrifugally washing for many times by using water and absolute ethyl alcohol to obtain melamine powder with positive polarity on the surface; 50mL of few-layer Ti is taken 3 C 2 Dissolving the suspension and 100mg of melamine powder with the surface being electropositive in 50mL of dilute hydrochloric acid, generating a large amount of floccules in the suspension, centrifuging the product with deionized water for 3 times (4000 rpm) to remove supernatant, and freeze-drying the precipitate to be used as a precursor; finally, the precursor is at N 2 Heating for 1-4h (400-700 ℃) under the atmosphere to obtain the nitrogen doped Ti 3 C 2 A material;
step 3, preparing S-(N-Ti 3 C 2 ) Composite material:
0.6g of sublimed sulfur and 0.4g of nitrogen doped Ti 3 C 2 Grinding for 20min, placing in a tube furnace, and adding N 2 Preserving the temperature for 12h at 155 ℃ in the atmosphere, and naturally cooling to obtain the S- (N-Ti) sulfur anode material 3 C 2 ) A composite material.
Further, the ultrasonic power in the step 1 of the preparation method of the sulfur cathode material is 100W. Under the power condition, the product can be obtained efficiently and rapidly, long-time waiting is avoided, the cost is reduced, and the breakage of the nano-sheets in the product can be prevented.
The method for preparing a sulfur cathode material according to claim 1, wherein the stirring in the step 1 and the step 2 is any one of manual stirring, mechanical stirring, electromagnetic stirring, vibration stirring and ultrasonic stirring.
Further, the method for producing a sulfur cathode material according to claim 1, wherein the drying time in step 2 is 2 hours or longer. The drying time is too short, and the solvent cannot be fully volatilized, so that the subsequent reaction efficiency is affected.
Further, the method for producing a sulfur cathode material according to claim 1, wherein the time for freeze-drying in step 2 is 2 hours or longer. The drying time is too short, the solvent cannot be volatilized sufficiently, and a product with a specific morphology cannot be obtained, resulting in a reduction in the final experimental efficiency.
Further, the method for preparing a sulfur cathode material according to claim 1, wherein the grinding in step 3 is manual grinding or mechanical grinding.
The invention also relates to a magnesium-sulfur battery assembling method, which comprises a preparation method adopting a sulfur positive electrode material, and further comprises the following steps:
step S1, preparation of Mg (TFSI) 2 /2AlCl 3 2LiTFSI/diglyme electrolyte:
292Mg Mg (TFSI) 2 1mL of diethylene glycol dimethyl ether was added, stirred for 12h, and 134mg of AlCl was added 3 Stirring for 12 hr, adding 287Mg LiTFSI, and stirring for 12 hr to obtain Mg (TFSI) 2 /2AlCl 3 2LiTFSI/diglyme electrolyte;
step S2, assembling Mg// Mg (TFSI) 2 /2AlCl 3 /2LiTFSI/diglyme//S-(N-Ti 3 C 2 ) Magnesium-sulfur battery:
taking 0.7g of S- (N-Ti) anode material 3 C 2 ) Grinding the composite material, 0.2g of nano carbon powder and 0.1g of PVDF in a mortar for 20min, adding a proper amount of N-methylpyrrolidone to prepare uniform slurry, coating the slurry on carbon aluminum foil, baking at 80 ℃ for 8h, slicing and placing the slurry in a glove box for later use; when the magnesium-sulfur secondary battery is assembled, the cut positive plate is placed on the positive plate shell, the glass fiber diaphragm is covered, the electrolyte is dripped, then the magnesium plate, the spring gasket and the spring piece are covered, and finally the negative plate shell is covered; and packaging under a press to obtain the magnesium-sulfur battery.
Further, the magnesium-sulfur battery in the step S2 of the assembling method of the magnesium-sulfur battery is button-shaped.
Further, the press machine in the step S2 of the magnesium-sulfur battery assembling method is a servo press machine.
The invention also relates to a magnesium-sulfur battery, which comprises the magnesium-sulfur battery manufactured by adopting the magnesium-sulfur battery assembly method.
The beneficial effects of the invention are as follows: efficient preparation of Nitrogen doped Ti 3 C 2 (N-Ti 3 C 2 ) And S- (N-Ti) 3 C 2 ) Composite material, typically three-dimensional MAX phase Ti by etching 3 AlC 2 Obtaining less-layer Ti 3 C 2 Accurate preparation of MXene, and further synthesis of N-Ti by liquid-phase electrostatic self-assembly method 3 C 2 . The N-Ti prepared 3 C 2 Has the microcosmic appearance similar to that of graphene nano sheets, and is further fused and compounded with sublimed sulfur to prepare S- (N-Ti) 3 C 2 ) A composite material. The composite material is matched with Mg (TFSI) 2 /2AlCl 3 The assembled magnesium-sulfur battery has higher charge-discharge specific capacity and better cycle performance, which shows that the MXene material has great application potential in the field of magnesium-sulfur batteriesForce and value.
The invention solves the defect that the current MXene material is rarely applied to the magnesium-sulfur battery, and provides N-Ti 3 C 2 And S- (N-Ti) 3 C 2 ) Is a synthetic process of Mg (TFSI) 2 /2AlCl 3 The magnesium-sulfur battery assembled by the preparation method of the LiTFSI/diglyme electrolyte has higher charge-discharge specific capacity and better cycle performance.
The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.
Drawings
FIG. 1 Ti 3 C 2 SEM image of the suspension droplets of (a) after air-drying on a silicon wafer;
fig. 2 Ti 3 C 2 SEM image of the suspension after freeze-drying;
fig. 3 Ti 3 C 2 XRD pattern of powder obtained after freeze-drying of suspension;
FIG. 4N-Ti 3 C 2 SEM image of powder;
FIG. 5N-Ti 3 C 2 XRD pattern of the powder;
FIG. 6S- (N-Ti) 3 C 2 ) SEM images of (a);
FIG. 7 100mA g -1 Cycling performance of magnesium-sulfur battery at current density;
FIG. 8 100mA g -1 The first three cycles of charge-discharge voltage-specific capacity curves of the magnesium-sulfur battery under the current density.
Detailed Description
The following description of the preferred embodiments of the present invention refers to the accompanying drawings, which make the technical contents thereof more clear and easy to understand. The present invention may be embodied in many different forms of embodiments and the scope of the present invention is not limited to only the embodiments described herein.
In the drawings, like structural elements are referred to by like reference numerals and components having similar structure or function are referred to by like reference numerals. The dimensions and thickness of each component shown in the drawings are arbitrarily shown, and the present invention is not limited to the dimensions and thickness of each component. The thickness of the components is exaggerated in some places in the drawings for clarity of illustration.
Example 1
The invention provides a preparation method of a sulfur positive electrode material, which comprises the following steps:
step 1, preparing few-layer Ti 3 C 2 Suspension:
adding 1,2,3g lithium fluoride into 20,30,40mL concentrated hydrochloric acid, stirring for 5-20min, and adding 1g Ti 3 AlC 2 Reacting for 24-48h at 40-80 ℃; adding deionized water into the reaction product, centrifuging for several times (4000 rpm) to obtain precipitate until the pH value of the supernatant approaches 6.0, adding 100-200mL deionized water into the precipitate, and adding N at 0-20deg.C 2 Stirring for 1-4h under the atmosphere; then, centrifuging the product obtained after ultrasonic treatment for 10-30min (4000 rpm) to remove substrate precipitate, adding a proper amount of deionized water, and centrifuging for 5-15min (10000 rpm) to remove substrate precipitate; finally obtain few-layer Ti 3 C 2 Suspension (1-4 mg mL) -1 ) And Ti in suspension 3 C 2 Presenting a nano sheet shape;
step 2, preparing nitrogen doped Ti 3 C 2 (N-Ti 3 C 2 ) Materials:
dispersing 1-3g melamine into 30mL absolute ethyl alcohol, vigorously stirring for 0.5-2h, then adding 1-5mL concentrated hydrochloric acid, continuously stirring for 1-3h, and sending into an oven to dry the solvent; grinding the obtained white solid particles into powder, and centrifugally washing for many times by using water and absolute ethyl alcohol to obtain melamine powder with positive polarity on the surface; 50mL of few-layer Ti is taken 3 C 2 Dissolving the suspension and 100mg of melamine powder with the surface being electropositive in 50mL of dilute hydrochloric acid, generating a large amount of floccules in the suspension, centrifuging the product with deionized water for 3 times (4000 rpm) to remove supernatant, and freeze-drying the precipitate to be used as a precursor; finally, the precursor is at N 2 Heating for 1-4h (400-700 ℃) under the atmosphere to obtain the nitrogen doped Ti 3 C 2 A material;
step 3, preparing S- (N-Ti) 3 C 2 ) Composite material：
0.6g of sublimed sulfur and 0.4g of nitrogen doped Ti 3 C 2 Grinding for 20min, placing in a tube furnace, and adding N 2 Preserving the temperature for 12h at 155 ℃ in the atmosphere, and naturally cooling to obtain the S- (N-Ti) sulfur anode material 3 C 2 ) A composite material.
The invention also relates to a magnesium-sulfur battery assembling method, which comprises a preparation method adopting a sulfur positive electrode material, and further comprises the following steps:
step S1, preparation of Mg (TFSI) 2 /2AlCl 3 2LiTFSI/diglyme electrolyte:
292Mg Mg (TFSI) 2 1mL of diethylene glycol dimethyl ether was added, stirred for 12h, and 134mg of AlCl was added 3 Stirring for 12 hr, adding 287Mg LiTFSI, and stirring for 12 hr to obtain Mg (TFSI) 2 /2AlCl 3 2LiTFSI/diglyme electrolyte;
step S2, assembling Mg// Mg (TFSI) 2 /2AlCl 3 /2LiTFSI/diglyme//S-(N-Ti 3 C 2 ) Magnesium-sulfur battery:
taking 0.7g of S- (N-Ti) anode material 3 C 2 ) Grinding the composite material, 0.2g of nano carbon powder and 0.1g of PVDF in a mortar for 20min, adding a proper amount of N-methylpyrrolidone to prepare uniform slurry, coating the slurry on carbon aluminum foil, baking at 80 ℃ for 8h, slicing and placing the slurry in a glove box for later use; when the magnesium-sulfur secondary battery is assembled, the cut positive plate is placed on the positive plate shell, the glass fiber diaphragm is covered, the electrolyte is dripped, then the magnesium plate, the spring gasket and the spring piece are covered, and finally the negative plate shell is covered; and packaging under a press 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 assembly method.
Ti 3 C 2 After preparation, the detection results are shown in fig. 1, fig. 2 and fig. 3. FIG. 1 shows Ti 3 C 2 SEM image of the suspension droplets after drying on the silicon wafer; FIG. 2 shows Ti 3 C 2 SEM image of the suspension after freeze-drying; FIG. 3 shows Ti 3 C 2 XRD pattern of powder obtained after freeze-drying of suspension; FIG. 1, FIG. 2, FIG.3 all prove that the Ti is less 3 C 2 Is a successful preparation of (a).
N-Ti 3 C 2 After preparation, the detection results are shown in FIG. 4 and FIG. 5, and FIG. 4 shows N-Ti 3 C 2 SEM images of the powder show that the material has a shape similar to a graphene nano sheet layer after nitrogen doping and shows a fluffy and porous structure; FIG. 5 shows N-Ti 3 C 2 XRD pattern of the powder, which proves that the N element is successfully introduced into Ti 3 C 2 Causing a partial change in the structure. S- (Ti) 3 C 2 ) After preparation, the results of the test are shown in FIG. 6, and FIG. 6 shows S- (N-Ti) 3 C 2 ) SEM image of (c) showing Ti 3 C 2 The nanosheets are sulfur-loaded and the surface becomes rough.
And placing the assembled magnesium-sulfur battery in a blue electric testing instrument for constant current charge and discharge test, wherein the test results are shown in fig. 7 and 8. FIG. 7 shows 100mA g -1 Cycling performance of magnesium-sulfur battery at current density; FIG. 8 shows 100mA g -1 The first three cycles of charge-discharge voltage-specific capacity curves of the magnesium-sulfur battery under the current density. The results in FIG. 7 show 100mA g -1 The S- (N-Ti 3C 2) positive electrode has 689mAh g under the current density -1 The initial discharge specific capacity still has 380mAh g after 13 circles -1 Is a specific discharge capacity of (a). The results of fig. 8 show that the magnesium sulfur battery undergoes electrochemical reaction of polysulfide interconversion during charge and discharge. This shows that the nitrogen doped Ti3C2 is a good sulfur sink material and can be practically applied to magnesium-sulfur batteries.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The preparation method of the sulfur cathode material is characterized by comprising the following steps:
step 1, preparing few-layer Ti 3 C 2 Suspension:
adding 1,2,3g lithium fluoride into 20,30,40, mL concentrated hydrochloric acid, stirring for 5-20min, and adding 1g Ti 3 AlC 2 Reacting 24-48h at 40-80 ℃; adding deionized water into the reaction product, centrifuging at 4000rpm for several times to obtain precipitate until the pH value of supernatant is close to 6.0, adding 100-200mL deionized water into the precipitate, and adding N at 0-20deg.C 2 Stirring for 1-4h under the atmosphere; then, centrifuging the product obtained after ultrasonic treatment at 4000rpm for 10-30min to remove substrate precipitate, adding a proper amount of deionized water, and centrifuging at 10000rpm for 5-15min to remove substrate precipitate; finally, a few layers of 1-4mg mL are obtained -1 Ti 3 C 2 Suspension, and Ti in suspension 3 C 2 Presenting a nano sheet shape;
step 2, preparing nitrogen doped Ti 3 C 2 Material N-Ti 3 C 2 ：
Dispersing 1-3g melamine into 30mL absolute ethyl alcohol, vigorously stirring for 0.5-2h, then adding 1-5mL concentrated hydrochloric acid, continuously stirring for 1-3h, and sending into an oven to dry the solvent; grinding the obtained white solid particles into powder, and centrifugally washing for many times by using water and absolute ethyl alcohol to obtain melamine powder with positive polarity on the surface; taking 50mL few layers of Ti 3 C 2 The suspension and melamine powder with the surface of 100mg being electropositive are dissolved in dilute hydrochloric acid of 50mL together, a large amount of floccules appear in the suspension, the product is centrifuged for 3 times at 4000rpm with deionized water, the supernatant is removed, and the precipitate is freeze-dried to be used as a precursor; finally, the precursor is at N 2 Heating at 400-700 deg.c for 1-4 hr to obtain nitrogen doped Ti 3 C 2 A material;
step 3, preparing S- (N-Ti) 3 C 2 ) Composite material:
sublimating sulfur 0.6g and doping Ti with nitrogen 0.4g 3 C 2 Grinding for 20min, placing in a tube furnace, and adding N 2 Preserving heat at 155 ℃ under atmosphere for 12h, and naturally cooling to obtain S- (N-Ti) sulfur anode material 3 C 2 ) A composite material.
2. The method for preparing a sulfur cathode material as claimed in claim 1, wherein the ultrasonic power in the 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 performed by any one of manual stirring, mechanical stirring, electromagnetic stirring, vibration stirring and ultrasonic stirring.
4. The method for producing a sulfur cathode material as defined in claim 1, wherein said drying time in step 2 is 2 hours or more.
5. The method for producing a sulfur cathode material according to claim 1, wherein the time for freeze-drying in step 2 is 2 hours or longer.
6. The method for producing a sulfur cathode material as claimed in claim 1, wherein the grinding in step 3 is manual grinding or mechanical grinding.
7. A method for assembling a magnesium-sulfur battery, comprising the steps of:
step S1, preparation of Mg (TFSI) 2 /2AlCl 3 2LiTFSI/diglyme electrolyte:
292Mg Mg (TFSI) 2 1mL of diethylene glycol dimethyl ether was added, stirred 12h, and 134mg of AlCl was added 3 Stirring 12 to h, adding 287 to Mg LiTFSI, and stirring 12 to h to obtain Mg (TFSI) 2 /2AlCl 3 2LiTFSI/diglyme electrolyte;
step S2, assembling Mg// Mg (TFSI) 2 /2AlCl 3 /2LiTFSI/diglyme//S-(N-Ti 3 C 2 ) Magnesium-sulfur battery:
taking 0.7 of g of S- (N-Ti) sulfur anode material 3 C 2 ) Composite material, 0.2. 0.2g nmGrinding rice carbon powder and 0.1g PVDF in a mortar for 20min, adding proper amount of N-methyl pyrrolidone to prepare uniform slurry, coating the slurry on carbon aluminum foil, baking the slurry at 80 ℃ for 8h, slicing the slurry and placing the sliced slurry in a glove box for later use; when the magnesium-sulfur secondary battery is assembled, the cut positive plate is placed on the positive plate shell, the glass fiber diaphragm is covered, the electrolyte is dripped, then the magnesium plate, the spring gasket and the spring piece are covered, and finally the negative plate shell is covered; and packaging under a press to obtain the magnesium-sulfur battery.
8. The method of assembling a magnesium sulfur battery according to claim 7, wherein the shape of the magnesium sulfur battery in step S2 is button-shaped.
9. The method of assembling a magnesium sulfur battery according to claim 7, wherein the press in step S2 is a servo press.
10. A magnesium-sulfur battery fabricated by the method of assembling a magnesium-sulfur battery according to claim 7.
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| CN110336034A (en) * | 2019-07-11 | 2019-10-15 | 安徽师范大学 | A kind of N doping lithium sulfur battery anode material, preparation method and applications |
| CN110611095A (en) * | 2019-09-17 | 2019-12-24 | 肇庆市华师大光电产业研究院 | Preparation method and application of lithium-sulfur battery positive electrode material |
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| CN110336034A (en) * | 2019-07-11 | 2019-10-15 | 安徽师范大学 | A kind of N doping lithium sulfur battery anode material, preparation method and applications |
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