CN116282136B - Preparation method of in-situ vertically grown tin sulfide nanosheets - Google Patents
Preparation method of in-situ vertically grown tin sulfide nanosheets Download PDFInfo
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 239000002135 nanosheet Substances 0.000 title claims abstract description 21
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 32
- 229910006404 SnO 2 Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000002064 nanoplatelet Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- -1 sulfur ions Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Abstract
The invention discloses a preparation method of in-situ vertically grown tin sulfide nano-sheets, which prepares SnO by a hydrothermal method 2 ‑TiO 2 The nano hollow sphere is used as a precursor; dispersing the precursor and sulfur source in water solution in proper proportion, performing vulcanization reaction under hydrothermal condition, cleaning, and drying to obtain SnO 2 ‑TiO 2 SnS vertically grown on nano hollow sphere in situ 2 A nano-sheet battery cathode material. The invention directionally controls the SnS by adjusting the reaction time and the reaction temperature 2 The growth of the nano-sheet is used for regulating and controlling the morphology structure, improving the stability of the material structure and SnS 2 The generation of the nano-sheet is beneficial to the electron transfer, improves the conductivity of the material, reduces the electrochemical polarization, and improves the electrochemical performance of the material.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a preparation method of in-situ vertically grown tin sulfide nanosheets.
Background
Lithium ion batteries are distinguished by their high efficiency and cleanliness characteristics. However, the cost and energy density of lithium ion batteries still do not meet the energy storage requirements of the market, and researchers are therefore required to develop alternative batteries to meet the demands of higher energy densities at low cost. TiO (titanium dioxide) 2 Vanadium pentoxide (V) 2 O 5 ) Ferric oxide (Fe) 2 O 3 ）、SnO 2 These metal oxides have proven to be effective in improving the performance of the cathode material of the battery. Among them, tin oxide nanoparticles have the characteristics of high environmental friendliness, easy preparation, high chemical stability and high energy density, and are widely focused.
Chinese patent No. CN 112582552A provides a process for preparing tin dioxide/metal sulfide composite film material. The acid generated by the decomposition of stannous chloride in the process of generating stannic oxide by hydrolytic oxidation is utilized to hydrolyze sulfur source compounds in the solution to generate sulfur ions, so that the sulfur source compounds are combined with metal ions in the solution. Under normal temperature, metal sulfide is formed in situ during the stirring and synthesizing process of tin dioxide. Under the condition of stirring at normal temperature, the reaction degree of tin oxide and metal sulfide can not be directionally controlled, and the sulfuration is uneven.
SnO 2 As a battery negative electrode material, there are phenomena such as volume expansion, low ion mobility, poor electron conductivity, and the like. Thus, tiO is used in the present invention 2 With SnO 2 Compounding to form SnO 2 -TiO 2 The nano hollow sphere has stable solid-electrolyte interphase (SEI), is favorable for maintaining stable structure during lithiation and delithiation, and enhances electrochemical performance. At the same time, tin-based sulfide SnS 2 Is a natural two-dimensional semiconductor with a narrow bandgap of 2.35 eV, which results in SnS 2 The base material has good optical and electrical properties. Through interface engineering regulation and control, the preparation method is as follows 2 -TiO 2 In-situ vulcanizing the nano hollow sphere to obtain the nano hollow sphere with the following characteristicsThe battery cathode material with high carrier mobility reduces ion migration potential barrier and accelerates electron transfer, thereby generating rapid interface oxidation-reduction reaction in the charge-discharge process.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of in-situ vertically grown tin sulfide nano-sheets, which comprises the following steps: s1 preparing SnO by hydrothermal method 2 -TiO 2 A precursor of the nano hollow sphere; s2, dispersing the precursor and a sulfur source in an aqueous solution, carrying out a vulcanization reaction under a hydrothermal condition, cleaning after the reaction is finished, and drying to obtain the in-situ vertically grown tin sulfide nano-sheet.
Further, the hydrothermal method is utilized to prepare SnO 2 -TiO 2 The specific steps of the nano hollow sphere precursor are as follows:
s1, oxalic acid is dissolved in ethanol to obtain oxalic acid alcohol solution A;
s2, stannous chloride is dissolved in ethanol to obtain a solution B;
s3, slowly adding the solution B into the solution A, and uniformly stirring the turbid liquid by using a magnetic stirrer until the turbid liquid becomes a clear mixed solution C;
s4, adding a titanium source into the mixed solution C under magnetic stirring to prepare a mixed solution D;
s5, transferring the mixed solution D prepared in the step S4 to a hydrothermal reaction kettle, performing hydrothermal reaction, cooling after the reaction is finished, cleaning, drying in a baking oven, and calcining in a tube furnace to obtain SnO 2 -TiO 2 A precursor of the nano hollow sphere.
In the step S1, the concentration of the solution A is 1-3 mol/L; in the step S2, the concentration of the solution B is 0.01-0.03 mol/L.
Further, in step S4, the titanium source is titanium tetrachloride, titanyl sulfate or tetrabutyl titanate; the molar ratio of stannous chloride to titanium source is 0.5-2: 1.
further, in step S5, the hydrothermal reaction is performed at a temperature of 100 to 180 ℃ for a reaction time of 5 to 20 hours (for the purpose of controlling SnO) 2 And TiO 2 Morphology and synthesis speed), reaction junctionAfter the bundling, alternately cleaning by using ethanol and purified water; the drying temperature is 60-80 ℃, the time is 5-20 h, the calcination is performed in an air atmosphere, the calcination temperature is 300-400 ℃, and the time is 3-10 h.
Further, dispersing the precursor and the sulfur source in an aqueous solution to finally obtain the in-situ vertically grown tin sulfide nano-sheet, wherein the specific process is as follows:
(1) SnO is taken 2 -TiO 2 Dispersing the precursor powder of the nano hollow spheres in deionized water solution to obtain a dispersion E;
(2) Adding a sulfur source into the dispersion E under magnetic stirring to prepare a dispersion F;
(3) Transferring the dispersion liquid F prepared in the step (2) to a hydrothermal reaction kettle, performing hydrothermal reaction, cooling after the reaction is finished, cleaning, and drying in an oven to obtain the in-situ vertically grown tin sulfide nano-sheet.
Further, in step (1), snO 2 -TiO 2 The mass of the precursor powder of the nano hollow sphere is 0.1-0.5 g.
Further, in the step (2), the sulfur source is thiourea, thioacetamide or sodium sulfide; the molar ratio of the sulfur source to the tin oxide is 2-5: 1.
in the step (3), the temperature of the hydrothermal reaction is 130-200 ℃ and the reaction time is 10-20 hours, (in order to control the reaction degree of vulcanization, the faster the vulcanization reaction is, the formation of a tin sulfide sheet structure is affected), and after the reaction is finished, ethanol and purified water are used for cleaning alternately; the drying temperature is 60-80 ℃, and the reaction time is 5-20 h.
The invention has the beneficial effects that:
(1) The invention relates to a preparation method of in-situ vertical growth tin sulfide nano-sheet, which is characterized in that SnO 2 -TiO 2 The tin sulfide nanosheet heterojunction material vertically grows on the nano hollow sphere in situ, is prepared in two steps by adopting a hydrothermal method, and has the advantages of simple synthesis method, easiness in operation, mild conditions and short sample preparation period.
(2) The invention provides a preparation method, which comprises the following steps of 2 Is mutually coupled with narrow band gap transition metal sulfide,preparing SnO 2 -TiO 2 In-situ vertical growth of SnS on nano hollow sphere 2 SnS of nanosheets 2 -TiO 2 A negative electrode battery material. Directional control of SnS by controlling the time and temperature of the reaction 2 Growth of nanoplatelets. Meanwhile, the hollow sphere is beneficial to increasing the contact area of the reaction, providing more active sites and reducing the ion transmission distance, thereby accelerating the transmission rate. Tin oxide is present in TiO due to its slower growth 2 Inside the sphere, is vulcanized into sheet SnS in a vulcanization reaction 2 Exhibiting vertical growth from inside to outside. The formation of tin sulfide is favorable for the formation of heterojunction, is convenient for improving the electron mobility of tin dioxide and is favorable for the implementation of interface oxidation-reduction reaction in the charge-discharge process.
(3) The invention provides a preparation method of SnS 2 The nano-sheet is self-SnO 2 -TiO 2 Is vertically grown in the sphere and is connected with TiO 2 Forming heterojunction is beneficial to promoting migration of electrons.
Drawings
FIG. 1 is an SEM image of in-situ vertically grown tin sulfide nanoplatelets prepared in example 1;
FIG. 2 is a Mapping graph of in-situ vertically grown tin sulfide nanoplatelets prepared in example 1;
FIG. 3 is an XRD pattern of in situ vertically grown tin sulfide nanoplatelets prepared in example 1;
FIG. 4 is an in situ vertically grown tin sulfide nanoplatelets prepared in examples 1-4 as electrodes at current densities of 200, 300, 500, 1000, 2000, 3000, 5000 mA g -1 A lower rate performance graph;
FIG. 5 is an in situ vertically grown tin sulfide nanoplatelets prepared in examples 1-4 as electrodes at a current density of 500 mA g -1 The following cycle performance graph.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
Example 1
a、SnO 2 -TiO 2 Preparation of the precursor
Dissolving 10 g oxalic acid in 60 mL ethanol to obtain oxalic acid alcohol solution, dissolving 0.5g stannous chloride in 20 ml ethanol, adding 2 ml tetrabutyl titanate into the oxalic acid alcohol solution, stirring uniformly, and reacting at 100deg.C for 5 h; alternately cleaning with ethanol and deionized water twice, and drying in a 70 deg.C constant temperature drying oven for 12 h to obtain white powder; then calcining the sample at 400 ℃ for 3 h to obtain nanosphere SnO 2 -TiO 2 A precursor.
b、SnS 2 -TiO 2 Is prepared from
0.2 g SnO is weighed 2 -TiO 2 Dispersing the precursor in 70 mL deionized water, weighing 0.14 g thioacetamide, dissolving in the solution, reacting at 130deg.C for 10 h, alternately cleaning with ethanol and deionized water twice, and drying in a 60 deg.C drying oven for 10 h to obtain SnO 2 -TiO 2 In-situ vertical uniform growth of SnS on nano hollow sphere 2 A nanoplatelet material.
Example 2: this example differs from example 1 in that in step a, snO 2 -TiO 2 The hydrothermal reaction time in the preparation of the precursor was 15 h.
Example 3: this example differs from example 1 in that in step a, snO 2 -TiO 2 In the preparation of (2), the hydrothermal reaction time is 15 h; in step b, snS 2 -TiO 2 In the preparation of (2), the hydrothermal reaction temperature was 180 ℃.
Example 4: this example differs from example 1 in that in step a, snO 2 -TiO 2 In the preparation of (2), the hydrothermal reaction time is 15 h; in step b, snS 2 -TiO 2 In the preparation of (2), the hydrothermal reaction temperature was 180℃and the time was 18 h.
As can be seen from the electron micrograph of FIG. 1, snS prepared in example 1 2 The nano-sheets uniformly grow on SnO 2 -TiO 2 The nanometer hollow sphere;
as can be seen from the element distribution diagram of fig. 2, the material prepared in example 1 mainly contains four elements of Sn, S, ti and O, and the Ti and O elements are uniformly distributed in the sample, and the S and Sn elements mainly exist in the region where the nanoplatelets are located.
As can be seen from fig. 3, after the vulcanization reaction, the diffraction peaks of the sample are significantly changed, and new diffraction peaks appear at 2θ=15.0 °, 20.2 °, 30.2 °, 41.9 °, etc., which proves that SnS in example 1 2 Is a successful synthesis of (a).
As can be seen from fig. 4 and 5, by regulating SnO 2 -TiO 2 Time of solvothermal reaction during preparation of nano hollow spheres and SnS 2 -TiO 2 The prepared lithium ion battery anode material shows different test results. This is due to SnO 2 -TiO 2 In the preparation of the hollow sphere, snO 2 The growth speed of (2) is slower, and the reaction time is prolonged to lead the reaction time to be towards TiO 2 The hollow sphere inner shells are gathered. SnS (SnS) 2 -TiO 2 The increase of the temperature and the time of the hydrothermal reaction can increase SnO 2 -TiO 2 SnO in the material 2 Is (under proper conditions) SnS 2 The generation of the nano-sheet is beneficial to the electron transfer, improves the conductivity of the material, reduces the electrochemical polarization and improves the electrochemical performance of the material.
Claims (2)
1. The preparation method of the in-situ vertical growth tin sulfide nano sheet is characterized by comprising the following steps: s1, preparing a SnO2-TiO2 nano hollow sphere precursor by a hydrothermal method; s2, dispersing the precursor and a sulfur source in an aqueous solution, carrying out a vulcanization reaction under a hydrothermal condition, cleaning after the reaction is finished, and drying to obtain the in-situ vertically grown tin sulfide nano-sheet;
the specific steps of step S1 are as follows:
(1) Oxalic acid is dissolved in ethanol to obtain oxalic acid alcohol solution A;
(2) Dissolving stannous chloride in ethanol to obtain a solution B;
(3) Slowly adding the solution B into the solution A, and uniformly stirring the turbid liquid by using a magnetic stirrer until the turbid liquid becomes a clear mixed solution C;
(4) Adding a titanium source into the mixed solution C under magnetic stirring to prepare a mixed solution D;
(5) Transferring the mixed solution D prepared in the step (4) to a hydrothermal reaction kettle for hydrothermal reaction, cooling after the reaction is finished, cleaning, drying in a baking oven, and calcining in a tube furnace to obtain a SnO2-TiO2 nano hollow sphere precursor, wherein in the step (4), the titanium source is titanium tetrachloride, titanyl sulfate or tetrabutyl titanate; the molar ratio of stannous chloride to titanium source is 0.2-2: 1, a step of;
the specific process of step S2 is as follows:
(1) Dispersing precursor powder of SnO2-TiO2 nano hollow spheres in deionized water solution to obtain a dispersion E;
(2) Adding a sulfur source into the dispersion E under magnetic stirring to prepare a dispersion F;
(3) Transferring the dispersion liquid F prepared in the step (2) to a hydrothermal reaction kettle, performing hydrothermal reaction, cooling after the reaction is finished, cleaning, and drying in an oven to obtain the in-situ vertically grown tin sulfide nano-sheet; in the step (1), the mass of the SnO2-TiO2 nano hollow sphere precursor powder is 0.1-0.5 g; in the step (2), the sulfur source is thioacetamide; the molar ratio of the sulfur source to the tin oxide is 2-2.156: 1, a step of; in the step (3), the temperature of the hydrothermal reaction is 130 ℃, the reaction time is 10-15 h, and after the reaction is finished, ethanol and purified water are used for cleaning alternately; the drying temperature is 60-80 ℃, and the reaction time is 5-20 h.
2. The method for preparing in-situ vertically grown tin sulfide nano-sheets according to claim 1, wherein in the step S1, the concentration of the solution A is 1-3 mol/L; in the step S2, the concentration of the solution B is 0.01-0.03 mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310596488.8A CN116282136B (en) | 2023-05-25 | 2023-05-25 | Preparation method of in-situ vertically grown tin sulfide nanosheets |
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| Application Number | Priority Date | Filing Date | Title |
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