CN114937760B - Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material - Google Patents
Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 63
- SQPMBIVYYZVHKZ-UHFFFAOYSA-N [N].[S].[Se] Chemical compound [N].[S].[Se] SQPMBIVYYZVHKZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000006258 conductive agent Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 14
- 239000002121 nanofiber Substances 0.000 claims description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 37
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 17
- 239000004917 carbon fiber Substances 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 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
- 239000011734 sodium Substances 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 229910052711 selenium Inorganic materials 0.000 abstract description 9
- 229910052718 tin Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 12
- 208000028659 discharge Diseases 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- DIGQNXIGRZPYDK-WKSCXVIASA-N (2R)-6-amino-2-[[2-[[(2S)-2-[[2-[[(2R)-2-[[(2S)-2-[[(2R,3S)-2-[[2-[[(2S)-2-[[2-[[(2S)-2-[[(2S)-2-[[(2R)-2-[[(2S,3S)-2-[[(2R)-2-[[(2S)-2-[[(2S)-2-[[(2S)-2-[[2-[[(2S)-2-[[(2R)-2-[[2-[[2-[[2-[(2-amino-1-hydroxyethylidene)amino]-3-carboxy-1-hydroxypropylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1-hydroxyethylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxyethylidene]amino]-1-hydroxypropylidene]amino]-1,3-dihydroxypropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxybutylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1-hydroxypropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxyethylidene]amino]-1,5-dihydroxy-5-iminopentylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxybutylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxyethylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1-hydroxyethylidene]amino]hexanoic acid Chemical compound C[C@@H]([C@@H](C(=N[C@@H](CS)C(=N[C@@H](C)C(=N[C@@H](CO)C(=NCC(=N[C@@H](CCC(=N)O)C(=NC(CS)C(=N[C@H]([C@H](C)O)C(=N[C@H](CS)C(=N[C@H](CO)C(=NCC(=N[C@H](CS)C(=NCC(=N[C@H](CCCCN)C(=O)O)O)O)O)O)O)O)O)O)O)O)O)O)O)N=C([C@H](CS)N=C([C@H](CO)N=C([C@H](CO)N=C([C@H](C)N=C(CN=C([C@H](CO)N=C([C@H](CS)N=C(CN=C(C(CS)N=C(C(CC(=O)O)N=C(CN)O)O)O)O)O)O)O)O)O)O)O)O DIGQNXIGRZPYDK-WKSCXVIASA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 102000003792 Metallothionein Human genes 0.000 description 1
- 108090000157 Metallothionein Proteins 0.000 description 1
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The preparation method of the @ CNF self-supporting electrode material comprises the following steps: (1) preparing spinning solution; (2) high-voltage electrostatic spinning; (3) high temperature calcination; (4) Battery assembly and testing. The invention synthesizes the high-quality nitrogen-sulfur-selenium co-doped SnS by regulating and controlling the element proportion of Sn, S and Se and synthesizing in situ sulfur/selenium 0.5 Se 0.5 Carbon fiber composite. The composite material effectively converts SnS 0.5 Se 0.5 Is combined with high specific capacity and high conductivity and stability of carbon fiber, effectively improves SnS 0.5 Se 0.5 Lower conductivity and lower sodium storage capacity of the carbon fiber. The nitrogen-sulfur-selenium co-doped carbon fiber can provide abundant active sites and relieve SnS 0.5 Se 0.5 And prevents side reactions of the electrode material with the electrolyte, causing dissolution of the active material, thereby improving the cycling stability of the electrode material. The negative electrode material has a three-dimensional self-supporting structure, can be directly used as an electrode, has no binder or conductive agent, has low cost and simple operation, is suitable for large-scale production, and has application potential.
Description
Technical Field
The invention relates to a preparation method of a negative electrode material of a sodium ion battery, in particular to a nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 A preparation method of a CNF self-supporting electrode material.
Background
The large-scale application of lithium ion batteries causes continuous rise of battery cost and shortage of lithium resources, greatly limits further development thereof, and becomes a challenge for industry. Sodium ion batteries are a promising energy technology due to their low cost, abundant reserves, chemical properties similar to lithium. However, a larger ionic radius of sodium ions results in a larger volume change and slow kinetics during reaction with the electrode material. Commercial graphites do not form effective sodium intercalation compounds and exhibit poor electrochemical performance. Therefore, the development of the high-performance sodium ion battery anode material becomes a research hot spot.
Metallic sulfur selenium compound SnS 0.5 Se 0.5 Has unique layered structure and higher theoretical capacity, and has potential of becoming negative electrode material of sodium ion battery. SnS (SnS) 0.5 Se 0.5 The sodium storage mechanism of (a) is a conversion reaction and an alloying reaction, which causes a large structural phase change and dissolution of polysulfide/selenide, resulting in a decrease in the active material of the electrode material and a deterioration in the cycle performance. Carbon material compounding is a common and effective method to solve the above problems. The carbon material can not only improve the conductivity of the electrode material, but also relieve the internal stress of the electrode material and shorten the diffusion distance of ions.
In the traditional sodium ion electrode preparation process, active substances, conductive agents and binders are uniformly mixed in an organic solution according to a certain proportion and coated on a current collector. The process takes a long time, and in order to avoid pollution to the environment, the organic solvent must be recovered, resulting in an increase in cost. In addition, the presence of the conductive agent may lower the loading of the active material and the energy density of the battery. The binder may undergo some uncontrolled side reactions with the electrode material. The current collector occupies a certain proportion of mass, which is unfavorable for the lightweight of the battery.
Disclosure of Invention
The invention aims at a metallothionein SnS compound 0.5 Se 0.5 As the problems of poor conductivity, large structural phase change and dissolution of reaction products in the sodium ion battery anode material, the preparation method of the high-performance sodium ion battery anode material with a self-supporting structure is provided.
The invention provides a nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The preparation method of the @ CNF self-supporting electrode material comprises the following steps of:
a. dispersing polyacrylonitrile, tin dichloride, sulfur powder and selenium powder with certain mass into N, N-dimethylformamide organic solvent under the condition of continuous stirring at a certain temperature to obtain spinning solution;
b. extracting the spinning solution, and carrying out electrostatic spinning to prepare nano fibers;
c. calcining the nanofiber in an inert atmosphere to obtain the nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Carbon fiber (SnS) 0.5 Se 0.5 @ CNF) composite material.
Preferably, in step a, polyacrylonitrile (PAN) is dissolved under heating and continuous stirring into N, N-Dimethylformamide (DMF), and tin chloride (SnCl) 2 ) Dissolving into PAN-DMF solution, dispersing sulfur powder and selenium powder into tin-containing PAN-DMF solution, and stirring for 12 hr to obtain spinning solution.
Preferably, in step a, stirring is continued at 60.+ -. 10 ℃.
Preferably, in step a, the ratio of polyacrylonitrile to N, N-dimethylformamide organic solvent is 0.8g to 10mL; the mol ratio of tin dichloride, sulfur powder and selenium powder is 4:6:6.
Preferably, in step b, the electrospinning parameters are as follows: the inner diameter of the needle head of the injector is 1.4mm, the outer diameter is 1.8mm, the positive voltage is 14kV, the negative voltage is 1.5kV, the distance between the needle head and the aluminum foil collector is 13-17 cm, the rotation speed of the aluminum foil roller collector is 40-60 circles/min, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃.
Preferably, in the step c, the protective atmosphere is one of nitrogen, argon-hydrogen mixture and the like.
Preferably, in step c, the calcination temperature is 600-800 ℃; the calcination time is 1-3 h.
Compared with the prior art, the invention has the following beneficial effects: the invention adopts the electrostatic spinning technology with simple operation to successfully synthesize the nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 @CNF composite material effectively uses SnS 0.5 Se 0.5 Is combined with high specific capacity and high conductivity and stability of carbon fiber, effectively improves SnS 0.5 Se 0.5 Lower conductivity and lower sodium storage capacity of the carbon fiber. In the synthesis process, excessive sulfur powder and selenium powder are not only SnS 0.5 Se 0.5 Can form defects in carbon fibers, and is convenient for adsorbing sodiumIons accelerate the transfer of sodium ions. Nitrogen-sulfur-selenium co-doped carbon fiber effectively avoids SnS 0.5 Se 0.5 Side reactions with the electrolyte occur, causing dissolution of the active material, thereby improving the stability of the electrode material. In addition, the synthesized nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The @ CNF composite material has a self-supporting structure, can be directly used as an electrode, and solves the defect that the conventional electrode material is introduced with a binder and a conductive additive.
Drawings
FIG. 1 is an XRD pattern of the nitrogen-sulfur-selenium co-doped Sn@CNF composite material prepared in example 1.
FIG. 2 shows the nitrogen-sulfur-selenium co-doped Sn@SnS prepared in example 2 0.5 Se 0.5 XRD pattern of @ CNF composite.
FIG. 3 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 XRD pattern of @ CNF composite.
FIG. 4 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Scanning electron microscope image of @ CNF composite.
FIG. 5 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Self-supporting structure of CNF composite.
FIG. 6 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 XPS full graph of @ CNF composite.
FIG. 7 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Element profile of CNF composite.
FIG. 8 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 C1 s fitting map of @ CNF composite.
FIG. 9 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Cycle performance graph of @ CNF composite.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the present invention easier to understand, the present invention is further described below with reference to examples.
The self-supporting electrode can be straightThe electrode is used as an electrode, has good mechanical flexibility, does not need additional conductive agent, binder and current collector, and can provide higher specific capacity and energy density. The invention is implemented by using SnS 0.5 Se 0.5 And the composite material is compounded with carbon fibers, so that the overall conductivity of the electrode material is improved. The nitrogen-sulfur-selenium co-doped carbon fiber can provide abundant active sites and relieve SnS 0.5 Se 0.5 And prevents side reactions of the electrode material with the electrolyte.
The invention uses nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The @ carbon fiber composite material is a negative plate, a metal sodium plate is used as a counter electrode, whatman glass fiber (GF/D) is used as a diaphragm, and an electrolyte is NaClO of 1 mol/L 4 Pc+5% fec solution a CR2032 type coin cell was assembled in a glove box filled with argon protection. Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The @ CNF composite is a self-supporting structure that does not require conductive agents and binders in the assembly of the battery.
Example 1
0.8g of Polyacrylonitrile (PAN) was dissolved in 10ml of N, N-Dimethylformamide (DMF) with heating and continuous stirring at 60℃and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving into PAN-DMF solution, dispersing 2 mmol of sulfur powder and 2 mmol of selenium powder into the tin-containing PAN-DMF solution, and continuously stirring for 12 hours to obtain spinning solution.
Extracting spinning solution by using a needle (with an inner diameter of 1.4mm and an outer diameter of 1.8 mm) injector, collecting by using aluminum foil wrapped on a roller, wherein the rotating speed of a roller collector is 50 circles/min, the positive voltage of electrostatic spinning is 14kV, the negative voltage is 1.5kV, the distance between the electrostatic spinning needle and the aluminum foil collector is 15cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so as to prepare the nanofiber.
Calcining the nanofiber at 700 ℃ for 2 hours in a nitrogen atmosphere, and heating at a speed of 5 ℃/min to obtain the nitrogen-sulfur-selenium co-doped Sn@CNF composite material (figure 1).
The nitrogen-sulfur-selenium co-doped Sn@CNF composite material is used as a negative electrode sheet, a metal sodium sheet is used as a counter electrode, whatman glass fiber (GF/D) is used as a diaphragm, and the electrolyte is NaClO with the concentration of 1 mol/L 4 PC+5% FEC solutionThe CR2032 type coin cell was assembled in a glove box filled with argon gas. Sodium-electricity negative electrode circulation test is carried out under the constant temperature environment of 25 ℃ and with the current density of 0.1A/g and the cut-off voltage of 0.01-3.0V. The primary discharge specific capacity of the nitrogen-sulfur-selenium co-doped Sn@CNF composite material is 791.9mAh/g, and the discharge specific capacity is still kept at 279.4mAh/g after 100 circles of circulation.
Example 2
0.8g of Polyacrylonitrile (PAN) was dissolved in 10ml of N, N-Dimethylformamide (DMF) with heating and continuous stirring at 60℃and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving into PAN-DMF solution, dispersing 4 mmol of sulfur powder and 4 mmol of selenium powder into the tin-containing PAN-DMF solution, and continuously stirring for 12 hours to obtain spinning solution.
Extracting spinning solution by using a needle (with an inner diameter of 1.4mm and an outer diameter of 1.8 mm) injector, collecting by using aluminum foil wrapped on a roller, wherein the rotating speed of a roller collector is 50 circles/min, the positive voltage of electrostatic spinning is 14kV, the negative voltage is 1.5kV, the distance between the electrostatic spinning needle and the aluminum foil collector is 15cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so as to prepare the nanofiber.
Calcining the nanofiber at 700 ℃ for 2 hours in a nitrogen atmosphere, and obtaining the nitrogen-sulfur-selenium co-doped Sn@SnS at a heating rate of 5 ℃/min 0.5 Se 0.5 @ CNF composite (fig. 2).
Co-doping Sn@SnS with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is a negative plate, a metal sodium plate is used as a counter electrode, whatman glass fiber (GF/D) is used as a diaphragm, and an electrolyte is NaClO of 1 mol/L 4 Pc+5% fec solution a CR2032 type coin cell was assembled in a glove box filled with argon protection. Sodium-electricity negative electrode circulation test is carried out under the constant temperature environment of 25 ℃ and with the current density of 0.1A/g and the cut-off voltage of 0.01-3.0V. Nitrogen-sulfur-selenium co-doped Sn@SnS 0.5 Se 0.5 The initial discharge specific capacity of the @ CNF composite material is 847.4mAh/g, and the discharge specific capacity is still 339.4mAh/g after 100 circles of circulation.
Example 3
0.8. 0.8g Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF) with heating and continuous stirring at 60℃and the mixture was then subjected to a stirring treatment4 mmol tin dichloride (SnCl) 2 ) Dissolving into PAN-DMF solution, dispersing 6 mmol of sulfur powder and 6 mmol of selenium powder into the tin-containing PAN-DMF solution, and continuously stirring for 12 hours to obtain spinning solution.
Extracting spinning solution by using a needle (with an inner diameter of 1.4mm and an outer diameter of 1.8 mm) injector, collecting by using aluminum foil wrapped on a roller, wherein the rotating speed of a roller collector is 50 circles/min, the positive voltage of electrostatic spinning is 14kV, the negative voltage is 1.5kV, the distance between the electrostatic spinning needle and the aluminum foil collector is 15cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so as to prepare the nanofiber
Calcining the nanofiber at 700 ℃ for 2 hours in a nitrogen atmosphere, and obtaining the nitrogen-sulfur-selenium co-doped SnS at a heating rate of 5 ℃/min 0.5 Se 0.5 @ CNF composite. By combining the XRD patterns of example 1 and example 2, only when the molar ratio of tin dichloride, sulfur powder and selenium powder is 4:6:6, nitrogen-sulfur-selenium co-doped SnS free of other impurities can be prepared 0.5 Se 0.5 @ CNF composite (fig. 3). As shown in fig. 4 and 5, the nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The @ CNF composite material has a three-dimensional continuous self-supporting structure and can be directly used as an electrode. As shown in fig. 6 and 7, the composite material contains N, S, se, sn element and is uniformly distributed. After fitting, fig. 8 shows that the carbon fiber contains three elements of doping of nitrogen, sulfur and selenium.
Co-doping SnS with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is a negative plate, a metal sodium plate is used as a counter electrode, whatman glass fiber (GF/D) is used as a diaphragm, and an electrolyte is NaClO of 1 mol/L 4 Pc+5% fec solution a CR2032 type coin cell was assembled in a glove box filled with argon protection. Sodium-electricity negative electrode circulation test is carried out under the constant temperature environment of 25 ℃ and with the current density of 0.1A/g and the cut-off voltage of 0.01-3.0V. As shown in FIG. 9, the nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The initial discharge specific capacity of the @ CNF composite material is 1061.5mAh/g, and the discharge specific capacity is still 471.0mAh/g after 100 circles of circulation.
Example 4
0.8. 0.8g Polyacrylonitrile (PAN) was dissolved to 10mL N with heating and continuous stirring at 60 ℃,N-Dimethylformamide (DMF), 4 mmol of tin dichloride (SnCl) 2 ) Dissolving in PAN-DMF solution, dispersing 6 mmol sulfur powder and 6 mmol selenium powder into tin-containing PAN-DMF solution, and continuously stirring for 12h to obtain spinning solution.
Extracting spinning solution by using a needle (with an inner diameter of 1.4mm and an outer diameter of 1.8 mm) injector, collecting by using aluminum foil wrapped on a roller, wherein the rotating speed of a roller collector is 30 circles/min, the positive voltage of electrostatic spinning is 14kV, the negative voltage is 1.5kV, the distance between the electrostatic spinning needle and the aluminum foil collector is 13 cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so as to prepare the nanofiber.
Calcining the nanofiber at 600 ℃ for 1h in a nitrogen atmosphere, and obtaining the nitrogen-sulfur-selenium co-doped SnS at a heating rate of 5 ℃/min 0.5 Se 0.5 @ CNF composite.
Co-doping SnS with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is a negative plate, a metal sodium plate is used as a counter electrode, whatman glass fiber (GF/D) is used as a diaphragm, and an electrolyte is NaClO of 1 mol/L 4 Pc+5% fec solution a CR2032 type coin cell was assembled in a glove box filled with argon protection. Sodium-electricity negative electrode circulation test is carried out under the constant temperature environment of 25 ℃ and with the current density of 0.1A/g and the cut-off voltage of 0.01-3.0V. Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The initial discharge specific capacity of the @ CNF composite material is 970.8mAh/g, and the discharge specific capacity is still kept at 340.7mAh/g after 100 circles of circulation.
Example 5
0.8g of Polyacrylonitrile (PAN) was dissolved in 10ml of N, N-Dimethylformamide (DMF) with heating and continuous stirring at 60℃and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving into PAN-DMF solution, dispersing 6 mmol of sulfur powder and 6 mmol of selenium powder into the tin-containing PAN-DMF solution, and continuously stirring for 12 hours to obtain spinning solution.
The spinning solution is extracted by a needle (with the inner diameter of 1.4mm and the outer diameter of 1.8 mm) injector, the spinning solution is collected by an aluminum foil wrapped on a roller, the rotating speed of a roller collector is 50 circles/min, the positive voltage of electrostatic spinning is 14kV, the negative voltage is 1.5kV, the distance between the electrostatic spinning needle and the aluminum foil collector is 17cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so that the nanofiber is prepared.
Calcining the nanofiber at 800 ℃ in nitrogen atmosphere for 3h at a heating rate of 5 ℃/min to obtain the nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 @ CNF composite.
Co-doping SnS with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is a negative plate, a metal sodium plate is used as a counter electrode, whatman glass fiber (GF/D) is used as a diaphragm, and an electrolyte is NaClO of 1 mol/L 4 Pc+5% fec solution a CR2032 type coin cell was assembled in a glove box filled with argon protection. Sodium-electricity negative electrode circulation test is carried out under the constant temperature environment of 25 ℃ and with the current density of 0.1A/g and the cut-off voltage of 0.01-3.0V. Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The initial discharge specific capacity of the @ CNF composite material is 980.8mAh/g, and the discharge specific capacity is still 405.8mAh/g after 100 circles of circulation.
Example 6
0.8. 0.8g Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF) with heating and continuous stirring at 60℃and 4 mmol of tin dichloride (SnCl) 2 ) 6 mmol of sulfur powder and 6 mmol of selenium powder are dispersed into PAN-DMF solution together, and stirring is continued for 12 hours to obtain spinning solution. During electrostatic spinning, the solution can agglomerate at the needle to block the needle, so that the equipment cannot spin normally. Therefore, when preparing the spinning solution, 4 mmol of tin dichloride (SnCl) needs to be added in the following order 2 ) Completely dissolved in PAN-DMF solution, and 6 mmol of sulfur powder and 6 mmol of selenium powder are dispersed in the tin-containing PAN-DMF solution.
In conclusion, the invention synthesizes the high-quality nitrogen-sulfur-selenium co-doped SnS by regulating the element proportion of Sn, S and Se and synthesizing in situ sulfur/selenium 0.5 Se 0.5 Carbon fiber composite. The composite material effectively converts SnS 0.5 Se 0.5 Is combined with high specific capacity and high conductivity and stability of carbon fiber, effectively improves SnS 0.5 Se 0.5 Lower conductivity and lower sodium storage capacity of the carbon fiber. The nitrogen-sulfur-selenium co-doped carbon fiber can provide abundant active sites and relieve SnS 0.5 Se 0.5 Is of the body of (2)The product change and the side reaction of the electrode material and the electrolyte are prevented, and the dissolution of active substances is caused, so that the cycling stability of the electrode material is improved. The negative electrode material has a three-dimensional self-supporting structure, can be directly used as an electrode, has no binder or conductive agent, has low cost and simple operation, is suitable for large-scale production, and has application potential.
Claims (6)
1. Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 The preparation method of the @ CNF self-supporting electrode material is characterized by comprising the following steps of:
a. dissolving polyacrylonitrile into N, N-dimethylformamide organic solvent under continuous stirring at 60+/-10 ℃, adding tin dichloride for dissolving, finally adding sulfur powder and selenium powder, and continuously stirring for 12 hours to obtain spinning solution;
b. extracting the spinning solution, and carrying out electrostatic spinning to prepare nano fibers;
c. calcining the nanofiber in an inert atmosphere to obtain SnS 0.5 Se 0.5 CNF self-supporting electrode material;
wherein in the step a, the ratio of the polyacrylonitrile to the N, N-dimethylformamide organic solvent is 0.8 g/10 mL; the mol ratio of tin dichloride, sulfur powder and selenium powder is 4:6:6.
2. The method of claim 1, wherein in step b, the electrospinning parameters are as follows: the inner diameter of the needle head of the injector is 1.4mm, the outer diameter is 1.8mm, the positive voltage is 14kV, the negative voltage is 1.5kV, the distance between the needle head and the aluminum foil collector is 13-17 cm, the rotation speed of the aluminum foil roller collector is 40-60 circles/min, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃.
3. The method of claim 1, wherein in step c, the protective atmosphere is one of nitrogen, argon, and argon-hydrogen mixture.
4. The method of claim 1, wherein in step c, the calcination temperature is 600 to 800 ℃; the calcination time is 1-3 h.
5. The nitrogen-sulfur-selenium co-doped SnS prepared by the method of any one of claims 1 to 4 0.5 Se 0.5 CNF self-supporting electrode material.
6. The nitrogen-sulfur-selenium co-doped SnS prepared by the method of any one of claims 1 to 4 0.5 Se 0.5 The use of a CNF self-supporting electrode material as an electrode for a sodium ion battery, characterized in that no binder or conductive agent is needed.
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| CN106784834A (en) * | 2017-02-03 | 2017-05-31 | 北京化工大学 | A kind of stannic selenide@carbon nano-fiber composite materials and its preparation method and application |
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| CN113823783A (en) * | 2021-08-25 | 2021-12-21 | 福建师范大学 | Preparation method and application of few-layer tin sulfide-sulfur-doped polyacrylonitrile compound potassium ion battery negative electrode material |
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| CN106784834A (en) * | 2017-02-03 | 2017-05-31 | 北京化工大学 | A kind of stannic selenide@carbon nano-fiber composite materials and its preparation method and application |
| CN113005328A (en) * | 2021-02-23 | 2021-06-22 | 西安航空学院 | Tin-selenium-sulfur ternary alloy cathode material for sodium ion battery and preparation method and application thereof |
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