CN113005328B - Tin-selenium-sulfur ternary alloy cathode material for sodium ion battery and preparation method and application thereof - Google Patents
Tin-selenium-sulfur ternary alloy cathode material for sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN113005328B CN113005328B CN202110203064.1A CN202110203064A CN113005328B CN 113005328 B CN113005328 B CN 113005328B CN 202110203064 A CN202110203064 A CN 202110203064A CN 113005328 B CN113005328 B CN 113005328B
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- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 52
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- JPUIEYBUBJBWQJ-UHFFFAOYSA-N selanylidene(sulfanylidene)tin Chemical compound S=[Sn]=[Se] JPUIEYBUBJBWQJ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 title claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 21
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910020212 Na2SnO3 Inorganic materials 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229910000796 S alloy Inorganic materials 0.000 claims 3
- 239000011734 sodium Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 239000011669 selenium Substances 0.000 description 77
- 239000012071 phase Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002159 nanocrystal Substances 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000004434 sulfur atom Chemical group 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009827 uniform distribution Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- -1 SnSe Chemical class 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000004771 selenides Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910008772 Sn—Se Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C22C13/00—Alloys based on tin
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention provides a tin-selenium-sulfur ternary alloy cathode material for a sodium ion battery, and a preparation method and application thereof, wherein an oil bath method is adopted to prepare a SnSe nanocrystalline preform, and then the SnSe nanocrystalline preform and sublimed sulfur are mixed according to the weight ratio of 1: mixing the components according to the mass ratio of 0.08, pouring the mixture into a porcelain boat, and processing the mixture in a rapid heating sectional heat preservation mode under a vacuum atmosphere to obtain the nano-scale tin-selenium-sulfur ternary alloy. The invention discloses a tin-selenium-sulfur ternary alloy cathode material for a sodium ion battery, and a preparation method and application thereof, and provides nanoscale SnSe for the sodium ion battery, which is uniform in distribution and controllable in shape and size0.5S0.5The ternary alloy can buffer the volume change of the SnSe material in the sodium storage process and effectively solve the problem of Sn/Na2The Se is continuously coarsened, the electrochemical property and the cycling stability are effectively improved, and the Se can be independently used as a negative electrode material of a sodium-ion battery.
Description
Technical Field
The invention belongs to the technical field of preparation of alloys for a sodium ion battery cathode, and relates to a tin-selenium-sulfur ternary alloy cathode material for a sodium ion battery, and a preparation method and application thereof.
Background
Sodium is abundant in the earth crust and low in exploitation and processing cost, so that the sodium ion charging and discharging battery is expected to replace a lithium ion battery and be widely applied to working power supplies of various electronic products and power batteries of mobile equipment. Although the electrochemical storage mechanism of the sodium ion battery is similar to that of the lithium ion battery, the sodium ion has a large radius, so that the sodium ion is difficult to rapidly and reversibly deintercalate in the negative electrode materials of commercial lithium ion batteries such as graphite, and the rate performance of the sodium ion battery is greatly influenced. In contrast, tin-based anode materials are of great interest to researchers because of their high theoretical capacity, low voltage plateau, and good safety.
Common tin-based negative electrode materials include elemental tin (Sn), tin-based oxides (SnO )2) Tin-based sulfide (SnS )2) And tin-based selenides (SnSe )2). In comparison, tin-based selenides, particularly SnSe, have higher conductivity, abundant reserves and environmental friendliness, and meanwhile, SnSe is a layered transition metal chalcogenide compound, the layered structure and weak van der waals force between layers provide convenience for rapid de-intercalation of large-radius sodium ions, and in addition, SnSe has electrochemical sodium storage reaction similar to tin-based oxides and sulfides, and the sodium intercalation capacity contributed by conversion reaction and alloying reaction is up to 780mAh g-1. In conclusion, compared with tin-based cathode materials such as tin simple substance, tin-based oxide and sulfide, the SnSe has potential advantages and application prospects in the aspect of electrochemical energy storage, and can be used as a sodium ion battery cathode material with excellent performance.
Although SnSe has good conductivity as a negative electrode material of a sodium ion battery, conversion reaction products of Sn and Na2Se is spontaneously agglomerated under the drive of thermal induced recrystallization and surface energy reduction to generate coarsening growth, and coarsening is continuously carried out along with a cyclic process, so that the conversion reaction activity of SnSe is reduced, and simultaneously the SnSe is subjected to Na+There is a relatively large volume change of the electrode material during de-intercalation. The prior art achieves buffering the volume expansion of SnSe and simultaneously improves the conversion reaction activity of the SnSe by reducing the grain size of the SnSe and adopting a high-conductivity heterogeneous matrix and SnSe compounding. At present heterogeneous matrix is mainly adoptedA highly conductive carbon-based material is used. It has been reported that volume expansion of SnSe charge and discharge processes is buffered and conversion reactivity of SnSe is improved mainly by preparing a Composite of nano-sized SnSe and a highly conductive carbon material, such as SnSe/r-GO Composite with Enhanced pseudomorphic acid as a High-Performance and for Li-Ion batteries ACS stable Chemistry&Engineering.2019,7: 8637-. However, the composite material can only keep good reversibility of conversion reaction in a short-term cycle, because the high-conductivity carbon material can buffer the volume change of the SnSe material in the sodium storage process but cannot effectively solve the problem of Sn/Na2Se continues to coarsen.
Based on the above, the ternary tin-based alloy material SnS0.5Se0.5Can utilize self-conversion reaction products Sn and Na2S、Na2The multiphase interface formed by Se simultaneously inhibits the sodium storage intermediate phases from migrating and coarsening each other. At the same time, SnS0.5Se0.5The structure has the same layered crystal structure as SnSe, and the structure is favorable for the rapid de-intercalation of large-radius sodium ions between layers, so that SnS0.5Se0.5The ternary alloy material has potential advantages and application prospects in the aspect of electrochemical energy storage.
However, SnS0.5Se0.5The SnS is prepared by physical ball milling and chemical vapor deposition, and the two methods are used for preparing the SnS0.5Se0.5Large size, unsuitable for use as electrode material, SnS0.5Se0.5Relatively few reports are made on the application of electrode materials, and the main reason is that nano-scale SnS0.5Se0.5The preparation and the structure control of materials have difficulties, and at present, the material only relates to SnS0.5Se0.5The report on the electrode material is that Qiming Tang of Harbin university of industry and collaborators thereof prepare SnSe by adopting a hydrothermal method and a heat treatment process thereof0.5S0.5/C composite electrode (Ternary tin) selenium sulfide(SnSe0.5S0.5) nano alloy as the high performance and lithium-ion batteries, nano energy, 2017,41:377 386), but the selenium powder and the sulfur powder do not participate in the reaction in the form of ions in the early oil bath heating process, and the Sn powder and the sulfur powder cannot be guaranteed to be reacted2+Sufficiently contacting with Se and S to make SnS0.5Se0.5The inconsistent powder development speed leads to the prepared SnS0.5Se0.5The product has extremely uneven appearance and large size span, so that the electron ion transmission speeds of different parts of the electrode are inconsistent in the charging and discharging processes, and the local concentration of charges is caused to generate polarization, therefore, in order to ensure stable electrochemical performance, a high-conductivity carbon-based material and the prepared SnS must be added0.5Se0.5The powder is compounded, but the carbon microspheres generated by pyrolysis of a large amount of glucose are overlarge in size, sodium ions and electrons are difficult to enter the microspheres in the charging and discharging process, so that corresponding charging and discharging capacity cannot be generated, the carbon microspheres can occupy certain mass and volume, the integral specific capacity of the electrode material can be reduced, and the material can be used as the cathode of a sodium ion battery at 200mA g-1The sodium storage capacity of the circulating 100 circles under the current density is 430mAh g-1。
In summary, the nano-scale SnSe for the sodium ion battery with uniform distribution and controllable shape and size is provided0.5S0.5The ternary alloy and the preparation method thereof are very necessary and have scientific research value.
Disclosure of Invention
In order to achieve the purpose, the invention provides a tin-selenium-sulfur ternary alloy cathode material for a sodium ion battery, and a preparation method and application thereof, and provides nano-scale SnSe for the sodium ion battery, which is uniform in distribution and controllable in shape and size0.5S0.5The ternary alloy and the preparation method thereof can buffer the volume change of the SnSe material in the sodium storage process and effectively solve the problem of Sn/Na2Se is continuously coarsened, the electron ion transmission speed of each part of the electrode is consistent in the charging and discharging process, the electrochemical property and the cycling stability are effectively improved, the Se can be independently used as a negative electrode material of a sodium ion battery, and the problem of sodium ion battery in the prior art is solvedMeter-level SnS0.5Se0.5The preparation of the material is difficult, and the product has the problems of uneven distribution, uncontrollable micro-appearance and uncontrollable size.
The technical scheme adopted by the invention is that the preparation method of the tin-selenium-sulfur ternary alloy cathode material for the sodium ion battery comprises the following steps:
step 1: the SnSe nanocrystalline preform is prepared by adopting an oil bath method, and the specific process is as follows:
step 1.1: adding a certain amount of selenium powder into a container containing a reducing solvent, wherein the concentration of the selenium powder in the reducing solvent is 0.2 mol.L-1～1.0mol·L-1Placing the container which is added with the selenium powder and is filled with the reducing solvent in an oil bath, and preserving the heat for 30-90 min at the temperature of 80-150 ℃ to form a wine red uniform solution in the container (since the selenium powder is not easy to be reduced into selenium ions, the long-time reduction ensures that all the selenium powder is completely reduced, and no impurity is introduced into the final product);
step 1.2: adding ethylene glycol into the container, stirring until the mixture is completely mixed, adding a certain amount of inorganic tin salt, continuously stirring and keeping the temperature for 60-360 min at the temperature of 80-150 ℃, and after the reaction is finished, centrifugally drying the product and collecting powder to obtain an SnSe nanocrystalline preform; the inorganic tin salt in the step is easy to dissolve in the solution to quickly form tin ions;
the preparation method of the SnSe nanocrystalline preform in the step 1 is simple and novel, the required temperature is low, the time is short, the energy consumption is saved, and Se powder is reduced into Se by a reducing solvent in a liquid phase environment2-Ion, and Se powder is treated in oil bath at certain temperature for a long time in a reducing solvent2-The ions are distributed evenly under the condition of liquid phase, and then are stirred by glycol until the ions are completely mixed, Se2-The ions still keep a very uniform distribution in the liquid phase, at this time, a certain amount of inorganic tin salt is added, and the inorganic tin salt is dissolved in the solution by Sn2+In the form of (A), (B) Se2-And Sn2+The SnSe nanocrystalline preform with uniform distribution and controllable shape and size is generated through the combination of ions, the reaction is realized in a liquid phase environment, so the required reaction temperature is lower, and an oil bath method is adoptedThe prepared SnSe nanocrystalline preform is nano-particles which are uniformly distributed and controllable in shape and size, and the distribution condition and shape and size of the SnSe nanocrystalline preform directly influence SnS in the step 20.5Se0.5The distribution condition and the size appearance are used as a prefabricated body to quickly obtain the nano-scale SnS with controllable appearance and size0.5Se0.5A material;
step 2: and (3) mixing the SnSe nanocrystalline preform prepared in the step (1.2) with sublimed sulfur according to the weight ratio of 1: mixing according to the mass ratio of 0.08, grinding until the mixture is uniformly mixed, pouring the mixture into a porcelain boat (preferably an alumina porcelain boat), quickly heating to 90-160 ℃ in a vacuum atmosphere tube furnace, preserving heat for 30-180 min, quickly heating to 400-600 ℃, preserving heat for 30-60 min, quickly cooling to room temperature after the heat preservation is finished, taking out a product, washing by using an organic solvent to remove a sulfur source solidified on the surface of the product, and freeze-drying to obtain the tin-selenium-sulfur ternary alloy. If other sulfur sources are adopted as the sulfur source in the step 2, impurity elements can be introduced.
The prepared SnSe nanocrystal and sublimed sulfur are mixed according to the weight ratio of 1: the reason why the mass ratio of 0.08 is mixed is that: ensuring that half of Se atoms in the SnSe are replaced by S atoms without residue to obtain pure phase of SnS0.5Se0.5The mass ratio is 1: 0.08 ratio of SnSe to the amount of substance subliming sulphur was 2: 1, subliming sulphur in this way replacing half of the Se atoms, obtaining SnS in pure phase0.5Se0.5For example, the amount of 1g of SnSe is 0.005mol, the amount of Se atom-corresponding substance is also 0.005mol, and in order to substitute half of Se atoms by S atoms, the amount of S atom-corresponding substance should be 0.0025mol, and the corresponding mass should be 0.08 g.
SnS0.5Se0.5The generation of (A) is that half of Se in SnSe undergoes an interatomic substitution reaction with S. Theoretically, the bond energy of Sn-Se bond is smaller than that of Sn-S bond, and the radius difference between S and Se atoms is smaller (0.01nm), so that S atoms can easily replace Se atoms; in technical terms, the sublimation temperature of sublimed sulfur<The difference between the melting point (816 ℃) of 100 ℃ and the melting point (816 ℃) of SnSe is larger, so that the adoption of a temperature gradient and rapid heating vulcanization process can ensure that the SnSe fully reacts with a gas-phase sulfur source before being melted, sulfur powder is firstly gasified to form a high-concentration gas-phase sulfur source under the condition of low temperature, and the sulfur source moves under the condition of high temperatureAggravated, the contact with the small-sized SnSe multi-surface can ensure that S atoms can fully permeate and replace Se atoms, and the in-situ conversion into SnS is realized0.5Se0.5。
The final product obtained in the step 2 is pure-phase nano-grade tin-selenium-sulfur ternary alloy, namely SnS0.5Se0.5Ternary alloys, because SnSe and sublimed sulphur are present in a ratio of 1: 0.08, just to cause the replacement reaction of half Se atoms and S atoms in the SnSe, without the residual of the SnSe which is not completely reacted.
The principle of preparing the tin-selenium-sulfur ternary alloy cathode material for the sodium ion battery in the specific embodiment of the invention is as follows: firstly, obtaining an SnSe nanocrystalline preform by adopting an oil bath method, innovatively mixing the prefabricated SnSe nanocrystalline preform with sublimed sulfur according to a certain mass ratio, grinding the mixture until the mixture is uniformly mixed, placing the mixture in a vacuum tube furnace, adopting a segmented rapid heating mode to gasify a sulfur source at a low temperature (90-160 ℃) to form a high-concentration gas-phase sulfur source, keeping the original microstructure of the SnSe nanocrystalline unchanged at the temperature, keeping the temperature for 30-180 min to ensure that all the sulfur sources are completely gasified, enabling the SnSe and the gas-phase sulfur source to react according to the given mass ratio of the raw materials, then intensifying the movement of the sulfur source under a high temperature condition (400-600 ℃), ensuring that S atoms are fully and rapidly permeated into crystal lattices of the SnSe nanocrystalline to generate multi-site interatomic displacement reaction (S displacement Se), and avoiding the precipitation of SnS crystals due to overhigh local concentration of the sulfur source (rapidly heating to 400-600 ℃) to ensure that the movement of the gas-phase sulfur molecules is intensified and the SnSe are rapidly precipitated Reaction, if the temperature rise rate is too slow or the temperature is too low, the gas-phase sulfur molecules move slowly and are distributed unevenly on the surface of the SnSe, part of sulfur molecules with too high local concentration can completely replace Se atoms in the SnSe to precipitate SnS crystals), no by-products are generated, rapid cooling can be realized by opening the cover of the high-temperature tubular furnace, and SnS is prevented from being cooled0.5Se0.5By-products such as SnS or SnSe crystal are precipitated, and the nano-scale SnS is finally obtained0.5Se0.5A ternary alloy.
The nano-scale SnS prepared by the invention0.5Se0.5Ternary alloys exhibit nanoparticle assemblyThe length of the nano rod is not more than 500nm, because the raw materials for preparing the SnSe nanocrystalline preform participate in the reaction in the form of ions in the solution of a tin source and a selenium source, the formed product is uniform in distribution and controllable in shape and size, the in-situ exchange reaction between S atoms and Se is realized in the later stage in a gas phase vulcanization mode, and the generated nano-scale SnS0.5Se0.5The micro-morphology of the ternary alloy is still relatively uniform.
The nano-scale SnS prepared by the invention0.5Se0.5The ternary alloy is used as a negative electrode material of the sodium-ion button cell, and shows higher reversible capacity and cycling stability. In addition, the preparation method is simple and easy to operate, and can realize SnS0.5Se0.5Controllable synthesis of nano material and SnS0.5Se0.5The preparation of the material provides a new method, and also provides a new idea for the preparation of other similar ternary materials (the existing preparation method of the ternary material mostly focuses on taking three alloy simple substances as raw materials and adopting a physical ball milling method, a physical vapor deposition method, a chemical vapor deposition method and a chemical vapor transmission method).
Further, in step 1.1, the reducing solvent comprises any one of ethylenediamine, hydrazine hydrate and dimethylformamide.
Further, in step 1.2, the volume ratio of the ethylene glycol to the reducing solvent in step 1.1 is: 3: 4-13.5.
Further, in step 1.2, adding a certain amount of inorganic tin salt specifically comprises: the molar ratio of the added inorganic tin salt to the selenium powder in step 1.1 is 1: 1.
Further, in step 1.2, the inorganic tin salt comprises SnCl2·2H2O or Na2SnO3·3H2O。
Further, in the step 2, the temperature is rapidly raised to 90-160 ℃ at a rapid heating rate of 15-30 ℃/min.
Further, in the step 2, the rapid heating rate of rapidly heating to 400-600 ℃ is 15-30 ℃/min.
Further, in step 2, the organic solvent includes any one of carbon disulfide, carbon tetrachloride, toluene and benzene.
The invention also aims to provide a tin-selenium-sulfur ternary alloy cathode material for a sodium ion battery, which is prepared according to the preparation method.
The invention also aims to provide application of the tin-selenium-sulfur ternary alloy negative electrode material for the sodium ion battery in the field of battery negative electrode materials.
The specific embodiment of the invention has the beneficial effects that:
(1) the specific embodiment of the invention provides the SnSe with the nano-scale size, uniform distribution and controllable appearance and size0.5S0.5Ternary alloy as negative pole material of sodium ion battery with excellent performance and nano grade SnSe0.5S0.5The preparation method is completely different from the prior art, is simple and novel to prepare and easy to operate, and can accurately regulate and control the distribution degree and the grain shape and size of the product.
(2) The specific embodiment of the invention innovatively adopts gas-phase vulcanization reaction to prepare nano-scale SnS0.5Se0.5The ternary alloy is prepared by firstly preparing a SnSe nanocrystalline preform by an oil bath method, then mixing the SnSe nanocrystalline preform with sublimed sulfur according to a certain mass ratio, and then treating the mixture in a nitrogen-filled vacuum atmosphere tube furnace by adopting a rapid heating and segmented heat preservation mode to ensure that gas-phase sulfur atoms replace half Se atoms in the SnSe nanocrystalline to obtain pure-phase nanoscale SnS0.5Se0.5Ternary alloys, in pure phase, of nano-scale SnS0.5Se0.5The ternary alloy as the negative electrode material of the sodium-ion battery shows good electrochemical performance, the preparation method provided by the invention is simple and novel, and is nano-scale SnS0.5Se0.5The preparation of the ternary alloy provides a new method, and has obvious scientific significance for promoting the application of the electrode material of the sodium-ion battery.
(3) The nano-scale SnS prepared by the specific embodiment of the invention has uniform distribution and controllable appearance and size0.5Se0.5Intermediate phase S of conversion reaction of ternary alloy in sodium storage processn、Na2S、Na2Se can form a multiphase interface without introducing other new species, Sn and Na2S、Na2The multiphase interface formed by Se can be Sn and Na2The single crystal domains formed by Se are isolated to prevent Sn and Na2Se is transferred to the same crystal domain nearby to generate aggregation and coarsening growth, so that the volume change and Sn/Na in the sodium storage process of the SnSe material can be effectively solved2Se is continuously coarsened, and the electrochemical performance with good performance is achieved, the stable and efficient electrochemical performance can be obtained without adding a high-conductivity carbon-based material for compounding, the preparation procedure is greatly simplified, and the resources are saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of SnSe prepared in example 3.
FIG. 2 shows SnS prepared in example 30.5Se0.5The X-ray diffraction pattern of the ternary alloy.
FIG. 3 is SnS prepared in example 30.5Se0.5Scanning electron microscope photograph of the ternary alloy.
FIG. 4 shows SnS prepared in example 30.5Se0.5Cycle performance diagram of ternary alloy.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The tin-selenium-sulfur ternary alloy, namely SnSe0.5S0.5A ternary alloy.
Example 1
(1) Adding 0.315g of selenium powder into a round-bottom flask containing 20mL of ethylenediamine solvent, wherein the concentration of the selenium powder in the ethylenediamine solvent is 0.2 mol.L-1Placing the round-bottom flask in an oil bath, keeping the temperature at 80 ℃ for 90min to form a wine-red uniform solution, adding 40mL of ethylene glycol into the round-bottom flask, stirring the mixture by using a glass rod until the mixture is completely mixed, and adding 0.9g of SnCl2·2H2And O, continuously stirring and keeping the temperature for 360min, and centrifugally drying and collecting powder after the reaction is finished to obtain the SnSe nanocrystal.
(2) Mixing 1g of the prepared SnSe nanocrystalline with 0.08g of sublimed sulfur, grinding the mixture until the mixture is uniformly mixed, then pouring the mixture into an alumina porcelain boat, heating the mixture to 90 ℃ at the speed of 15 ℃/min in a vacuum atmosphere tube furnace filled with nitrogen, and preserving the heat for 180 min; rapidly heating to 400 deg.C at a rate of 30 deg.C/min, maintaining for 60min, rapidly cooling to room temperature, repeatedly washing solidified sulfur source on powder surface with carbon disulfide, and freeze drying to obtain nano-scale SnS0.5Se0.5Ternary alloy used as negative electrode material of sodium ion battery.
Example 2
(1) Adding 0.787g of selenium powder into a round-bottom flask containing 25mL of hydrazine hydrate solvent, wherein the concentration of the selenium powder in the hydrazine hydrate solvent is 0.4 mol.L-1Placing the round-bottom flask in an oil bath, keeping the temperature at 100 ℃ for 80min to form a wine-red uniform solution, adding 50mL of ethylene glycol into the round-bottom flask, stirring the mixture with a glass rod until the mixture is completely mixed, and adding 2.257g of SnCl2·2H2And O, continuously stirring and preserving the temperature for 240min, and centrifugally drying and collecting powder after the reaction is finished to obtain the SnSe nanocrystal.
(2) Mixing 1.5g of the prepared SnSe nanocrystalline with 0.12g of sublimed sulfur, grinding until the mixture is uniformly mixed, then pouring the mixture into an alumina porcelain boat, heating to 120 ℃ at the speed of 20 ℃/min in a vacuum atmosphere tube furnace filled with nitrogen, and preserving the temperature for 120 min; rapidly heating to 500 deg.C at a speed of 25 deg.C/min, maintaining for 50min, rapidly cooling to room temperature, and repeatedly using carbon disulfideWashing the solidified sulfur source on the surface of the powder, and freeze-drying to obtain nano-grade SnS0.5Se0.5Ternary alloy used as negative electrode material of sodium ion battery.
Example 3
(1) Adding 1.417g selenium powder into a round-bottom flask containing 30mL hydrazine hydrate solvent, wherein the concentration of the selenium powder in the hydrazine hydrate solvent is 0.6 mol.L-1Placing the round-bottom flask in an oil bath, keeping the temperature at 120 ℃ for 60min to form a wine-red uniform solution, adding 60mL of ethylene glycol into the round-bottom flask, stirring the mixture by using a glass rod until the mixture is completely mixed, and adding 4.062g of SnCl2·2H2And O, continuously stirring and preserving the temperature for 120min, and centrifugally drying and collecting powder after the reaction is finished to obtain the SnSe nanocrystal.
(2) 1.5g of the SnSe nanocrystalline prepared by the method is mixed with 0.12g of sublimed sulfur, then ground to be uniformly mixed, then poured into an alumina porcelain boat, heated to 150 ℃ at the speed of 25 ℃/min in a vacuum atmosphere tube furnace filled with nitrogen, and kept for 60 min; rapidly heating to 600 deg.C at a rate of 20 deg.C/min, maintaining for 30min, rapidly cooling to room temperature, repeatedly washing solidified sulfur source on powder surface with carbon disulfide, and freeze drying to obtain nano-scale SnS0.5Se0.5Ternary alloy used as negative electrode material of sodium ion battery.
Referring to fig. 1, a field emission scanning electron microscope with a model number of S4800 is used to observe that the SnSe nanocrystals prepared in step (1) are nanoparticles with small morphology and uniform distribution; referring to FIG. 2, the nano-sized SnS obtained in the step (2) is analyzed by using a Japanese XRD Rigaku Ultima IV X-ray diffractometer0.5Se0.5Ternary alloy, and finding the SnS of the sample and the orthorhombic system with the JCPDS number of 48-12250.5Se0.5The structures are consistent; referring to FIG. 3, the nano-sized SnS prepared in step (2) is observed by a field emission Scanning Electron Microscope (SEM) model Zeiss Sigma3000.5Se0.5Ternary alloy, which is shown as a nanorod assembled by nanoparticles, and has a length not exceeding 500nm and is uniformly distributed.
Example 4
(1) To a round bottom flask containing 20mL Dimethylformamide (DMF) solvent was added 1.259g seleniumThe concentration of the powder and the selenium powder in the dimethylformamide solvent is 0.8 mol.L-1Placing round-bottom flask in oil bath, keeping temperature at 150 deg.C for 30min to obtain wine red homogeneous solution, adding 80mL ethylene glycol into round-bottom flask, stirring with glass rod to completely mix, adding 4.272g Na2SnO3·3H2And O, continuously stirring and preserving the temperature for 60min, and centrifugally drying and collecting powder after the reaction is finished to obtain the SnSe nanocrystal.
(2) 2.0g of the prepared SnSe nanocrystalline and 0.16g of sublimed sulfur are mixed and ground to be uniformly mixed, then the mixture is poured into an alumina porcelain boat, the temperature is raised to 160 ℃ at the speed of 20 ℃/min in a vacuum atmosphere tube furnace filled with nitrogen, and the temperature is kept for 60 min; rapidly heating to 600 deg.C at a rate of 15 deg.C/min, maintaining for 40min, rapidly cooling to room temperature, repeatedly washing sulfur source solidified on powder surface with carbon tetrachloride, and freeze drying to obtain nano-grade SnS0.5Se0.5Ternary alloy used as negative electrode material of sodium ion battery.
Example 5
(1) Adding 2.361g of selenium powder into a round-bottom flask containing 30mL of ethylenediamine solvent, wherein the concentration of the selenium powder in the ethylenediamine solvent is 1.0 mol.L-1Placing round-bottom flask in oil bath, keeping temperature at 160 deg.C for 50min to obtain wine red homogeneous solution, adding 90mL ethylene glycol into round-bottom flask, stirring with glass rod to completely mix, adding 8.01g Na2SnO3·3H2And O, continuously stirring and preserving the temperature for 120min, and centrifugally drying and collecting powder after the reaction is finished to obtain the SnSe nanocrystal.
(2) Mixing 1.0g of the prepared SnSe nanocrystalline with 0.08g of sublimed sulfur, grinding until the mixture is uniformly mixed, then pouring the mixture into an alumina porcelain boat, heating to 120 ℃ at the speed of 30 ℃/min in a vacuum atmosphere tube furnace filled with nitrogen, and preserving the temperature for 120 min; rapidly heating to 500 deg.C at a rate of 30 deg.C/min, maintaining for 60min, rapidly cooling to room temperature, repeatedly washing with toluene to obtain solidified sulfur source on the surface of the powder, and freeze drying to obtain nano-grade SnS0.5Se0.5Ternary alloy used as negative electrode material of sodium ion battery.
Example 6
The adding amount of the selenium powder in the step (1) is 0.708g, and the concentration of the selenium powder in a hydrazine hydrate solvent is 0.3 mol.L-1，SnCl2·2H2The adding amount of O is 2.03 g;
(2) the adding amount of the SnSe nanocrystal and the sublimed sulfur is 0.75g and 0.06 g;
the rest is the same as in example 3.
Example 7
The adding amount of the selenium powder in the step (1) is 1.18g, and the concentration of the selenium powder in a hydrazine hydrate solvent is 0.5 mol.L-1，SnCl2·2H2The adding amount of O is 3.385 g;
(2) the adding amount of the SnSe nanocrystal and the sublimed sulfur is 1.3g and 0.104 g;
the rest is the same as in example 3.
Example 8
The adding amount of the selenium powder in the step (1) is 1.65g, and the concentration of the selenium powder in a hydrazine hydrate solvent is 0.7 mol.L-1，SnCl2·2H2The addition of O is 4.73 g;
(2) the adding amount of the SnSe nanocrystal and the sublimed sulfur is 1.7g and 0.136 g;
the rest is the same as in example 3.
Example 9
The adding amount of the selenium powder in the step (1) is 2.125g, and the concentration of the selenium powder in a hydrazine hydrate solvent is 0.9 mol.L-1，SnCl2·2H2The adding amount of O is 6.09 g;
(2) the adding amount of the SnSe nanocrystal and the sublimed sulfur is 2g and 0.16 g;
the rest is the same as in example 3.
Example 10
In the step (2), heating to 150 ℃ at the speed of 30 ℃/min in a vacuum atmosphere tube furnace filled with nitrogen, and preserving heat for 180 min; rapidly heating to 600 ℃ at the speed of 30 ℃/min and preserving the heat for 60 min; the organic solvent adopts benzene;
the rest is the same as in example 3.
Examples of the experiments
The nano-scale SnS prepared in the embodiment 1 to 100.5Se0.5Ternary elementThe alloy is mixed with a conductive agent and a binder to prepare a negative plate, and the negative plate and the treated sodium plate are assembled to form the CR2032 button type sodium ion battery for testing the cycle performance at 200 mA.g-1After 50 cycles at the current density of (a), the respective reversible capacity values are shown in table 1.
TABLE 1 nanoscale SnS prepared in examples 1-100.5Se0.5The ternary alloy is 200mA g-1Table of values of reversible capacity after 50 cycles at current density
As shown in Table 1, the nano-sized SnS prepared in examples 1 to 100.5Se0.5The ternary alloy is 200mA g-1The reversible capacity after circulating for 50 circles under the current density is kept between 400 and 510 mAh.g-1In range, as shown in FIG. 4, the nano-sized SnS prepared in example 30.5Se0.5The ternary alloy is 200mA g-1After circulating for 50 circles under the current density, the reversible capacity is still kept at 500mAh g-1The electrochemical performance of the SnS is similar to that of the prior SnS0.5Se0.5The electrochemical performance of the/C is equivalent, the battery can be independently used as a negative electrode material of a sodium-ion battery, and the cycling stability of the battery can basically meet the requirement.
As is well known in the field of the industry, the electrochemical performance of the electrode material added with carbon material is improved, if the nano-scale SnS prepared by the method is used0.5Se0.5The ternary alloy is further compounded with carbon materials and the like, so that the electrochemical performance is more excellent, and the nano-scale SnS prepared by the method is0.5Se0.5Ternary alloys as SnS0.5Se0.5The material is applied to the front-edge research of the battery cathode material and is expected to promote SnS0.5Se0.5The rapid development of the subsequent continuous modification and composite doping technologies of the material has obvious scientific significance.
It is noted that, in the present application, relational terms such as first, second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of a tin-selenium-sulfur ternary alloy cathode material for a sodium ion battery is characterized by comprising the following steps of:
step 1: the SnSe nanocrystalline preform is prepared by adopting an oil bath method, and the specific process is as follows:
step 1.1: adding a certain amount of selenium powder into a container containing a reducing solvent, wherein the concentration of the selenium powder in the reducing solvent is 0.2 mol.L-1~1.0mol·L-1Placing the container which is added with the selenium powder and contains the reducing solvent in an oil bath, and preserving the heat for 30-90 min at the temperature of 80-150 ℃ to form a wine red uniform solution in the container;
step 1.2: adding ethylene glycol into the container, stirring until the ethylene glycol is completely mixed, adding a certain amount of inorganic tin salt, continuously stirring and preserving the temperature for 60-360 min at the temperature of 80-150 ℃, and after the reaction is finished, centrifugally drying the product and collecting powder to obtain an SnSe nanocrystalline preform; the molar ratio of the added inorganic tin salt to the selenium powder in the step 1.1 is 1: 1;
step 2: and (3) mixing the SnSe nanocrystalline preform prepared in the step (1.2) with sublimed sulfur according to the weight ratio of 1: mixing according to the mass ratio of 0.08, grinding until the mixture is uniformly mixed, pouring the mixture into a porcelain boat, quickly heating to 90-160 ℃ in a vacuum atmosphere tube furnace, preserving heat for 30-180 min, quickly heating to 400-600 ℃, preserving heat for 30-60 min, quickly cooling to room temperature after heat preservation, taking out a product, washing by using an organic solvent to remove a sulfur source solidified on the surface of the product, and freeze-drying to obtain the tin-selenium-sulfur ternary alloy.
2. The method for preparing the tin-selenium-sulfur ternary alloy anode material for the sodium-ion battery according to claim 1, wherein in step 1.1, the reducing solvent comprises any one of ethylenediamine, hydrazine hydrate and dimethylformamide.
3. The method for preparing the ternary tin-selenium-sulfur alloy anode material for the sodium-ion battery as claimed in claim 1, wherein in step 1.2, the volume ratio of the ethylene glycol to the reducing solvent in step 1.1 is as follows: 3: 4-13.5.
4. The method for preparing the ternary tin-selenium-sulfur alloy anode material for the sodium-ion battery as claimed in claim 1, wherein in step 1.2, the inorganic tin salt comprises SnCl2·2H2O or Na2SnO3·3H2O。
5. The preparation method of the tin-selenium-sulfur ternary alloy negative electrode material for the sodium ion battery according to claim 1, wherein in the step 2, the rapid temperature rise rate of the first rapid temperature rise to 90-160 ℃ is 15-30 ℃/min.
6. The preparation method of the tin-selenium-sulfur ternary alloy negative electrode material for the sodium ion battery according to claim 1, wherein in the step 2, the rapid temperature rise rate of the rapid temperature rise to 400-600 ℃ is 15-30 ℃/min.
7. The method for preparing the ternary tin-selenium-sulfur alloy anode material for the sodium-ion battery according to claim 1, wherein in the step 2, the organic solvent comprises any one of carbon disulfide, carbon tetrachloride, toluene and benzene.
8. A tin-selenium-sulfur ternary alloy negative electrode material for a sodium ion battery is characterized by being prepared according to the preparation method of any one of claims 1 to 7.
9. The application of the tin-selenium-sulfur ternary alloy negative electrode material for the sodium-ion battery as defined in claim 8 in the field of battery negative electrode materials.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214932A (en) * | 2008-01-08 | 2008-07-09 | 上海大学 | Method for preparing nanometer tin selenide |
| JP2015002054A (en) * | 2013-06-14 | 2015-01-05 | 出光興産株式会社 | Negative electrode mixture, electrode, and lithium ion battery |
| CN106654261A (en) * | 2016-12-19 | 2017-05-10 | 陕西科技大学 | Preparation method for three-dimensional flower-shaped SnSe<2> nanocrystalline for negative electrode of sodium ion battery |
| CN106744728A (en) * | 2016-12-19 | 2017-05-31 | 陕西科技大学 | A kind of method that room temperature liquid phase method prepares SnSe micron balls |
| CN106784598A (en) * | 2016-12-19 | 2017-05-31 | 陕西科技大学 | A kind of used as negative electrode of Li-ion battery flake SnSe2Nanocrystalline preparation method |
| CN107017403A (en) * | 2017-06-07 | 2017-08-04 | 东莞市迈科新能源有限公司 | A kind of cell negative electrode material and preparation method thereof and its application |
-
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- 2021-02-23 CN CN202110203064.1A patent/CN113005328B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214932A (en) * | 2008-01-08 | 2008-07-09 | 上海大学 | Method for preparing nanometer tin selenide |
| JP2015002054A (en) * | 2013-06-14 | 2015-01-05 | 出光興産株式会社 | Negative electrode mixture, electrode, and lithium ion battery |
| CN106654261A (en) * | 2016-12-19 | 2017-05-10 | 陕西科技大学 | Preparation method for three-dimensional flower-shaped SnSe<2> nanocrystalline for negative electrode of sodium ion battery |
| CN106744728A (en) * | 2016-12-19 | 2017-05-31 | 陕西科技大学 | A kind of method that room temperature liquid phase method prepares SnSe micron balls |
| CN106784598A (en) * | 2016-12-19 | 2017-05-31 | 陕西科技大学 | A kind of used as negative electrode of Li-ion battery flake SnSe2Nanocrystalline preparation method |
| CN107017403A (en) * | 2017-06-07 | 2017-08-04 | 东莞市迈科新能源有限公司 | A kind of cell negative electrode material and preparation method thereof and its application |
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