CN114937760A - Nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material - Google Patents
Nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material Download PDFInfo
- Publication number
- CN114937760A CN114937760A CN202210380232.9A CN202210380232A CN114937760A CN 114937760 A CN114937760 A CN 114937760A CN 202210380232 A CN202210380232 A CN 202210380232A CN 114937760 A CN114937760 A CN 114937760A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- selenium
- sns
- nitrogen
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011669 selenium Substances 0.000 title claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 23
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 239000011593 sulfur Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 40
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 23
- SQPMBIVYYZVHKZ-UHFFFAOYSA-N [N].[S].[Se] Chemical compound [N].[S].[Se] SQPMBIVYYZVHKZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 50
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 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 13
- 235000011150 stannous chloride Nutrition 0.000 claims description 13
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 238000000034 method 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
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 18
- 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 16
- 229910052708 sodium Inorganic materials 0.000 abstract description 16
- 239000011734 sodium Substances 0.000 abstract description 16
- 239000004917 carbon fiber Substances 0.000 abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 229910052718 tin Inorganic materials 0.000 abstract description 10
- 239000010406 cathode material Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 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
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [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
- 239000011149 active material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007423 decrease Effects 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
- 230000008569 process Effects 0.000 description 2
- 229940065287 selenium compound Drugs 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 230000007246 mechanism Effects 0.000 description 1
- 239000007773 negative electrode material Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 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
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses 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 a spinning solution; (2) high-voltage electrostatic spinning; (3) high-temperature calcination; (4) and (5) assembling and testing the battery. The invention synthesizes high-quality nitrogen-sulfur-selenium co-doped SnS through in-situ sulfur/selenylation by regulating the element proportion of Sn, S and Se 0.5 Se 0.5 @ carbon fiber composite material. Composite material effectively converts SnS 0.5 Se 0.5 The high specific capacity of the carbon fiber is combined with the high conductivity and the stability of the carbon fiber, so that the SnS is effectively improved 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 rich active sites and relieve SnS 0.5 Se 0.5 And prevent the electrode material from generating side reaction with the electrolyte to cause activityThe dissolution of the substance, thereby improving the cycling stability of the electrode material. The cathode material has a three-dimensional self-supporting structure, can be directly used as an electrode, is free of an adhesive and a conductive agent, is low in cost, simple to operate, suitable for large-scale production and has application potential.
Description
Technical Field
The invention relates to a preparation method of a sodium ion battery cathode material, in particular to a nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 A preparation method of the @ CNF self-supporting electrode material.
Background
The large-scale application of lithium ion batteries leads to the continuous rise of battery cost and the shortage of lithium resources, greatly limits the further development of the batteries and becomes a challenge for the industry. Sodium ion batteries are a promising energy technology due to their low cost, abundant reserves, and chemical properties similar to lithium. However, the larger ionic radius of sodium ions leads to larger volume changes and slower 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 high-performance sodium-ion battery negative electrode materials becomes a research hotspot.
Metallic sulfur selenium compound SnS 0.5 Se 0.5 Has unique layered structure and higher theoretical capacity and has the potential of becoming the cathode material of the sodium-ion battery. SnS 0.5 Se 0.5 The sodium storage mechanism of (a) is a transformation reaction and an alloying reaction, which causes a large structural phase transition and dissolution of polysulfide/selenide, resulting in a decrease in the active material of the electrode material and a decline in cycle performance. Carbon material compounding is a common and effective method for solving 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.
The traditional preparation process of the sodium ion electrode is to uniformly mix active substances, conductive agents and binders in organic solution according to a certain proportion and coat the mixture on a current collector. The process is long in time, and the organic solvent must be recovered to avoid environmental pollution, which leads to 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 not beneficial to the light weight of the battery.
Disclosure of Invention
The invention aims at the SnS of the metal sulfur selenium compound 0.5 Se 0.5 The preparation method of the high-performance sodium ion battery cathode material with the self-supporting structure is provided, which has the problems of poor conductivity, larger structural phase change and dissolution of reaction products when being used as the cathode material of the sodium ion battery.
The invention provides a nitrogen sulfur selenium codoped SnS 0.5 Se 0.5 The preparation method of the @ CNF self-supporting electrode material comprises the following steps of:
a. under the condition of continuous stirring at a certain temperature, dispersing polyacrylonitrile, tin dichloride, sulfur powder and selenium powder with certain mass into an N, N-dimethylformamide organic solvent to obtain a spinning solution;
b. extracting the spinning solution, and carrying out electrostatic spinning to prepare nano fibers;
c. calcining the nano-fiber in inert atmosphere to obtain 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 in N, N-Dimethylformamide (DMF) under heating and continuous stirring, and then tin chloride (SnCl) 2 ) Dissolving into PAN-DMF solution, finally dispersing sulfur powder and selenium powder into PAN-DMF solution containing tin, and continuously stirring for 12h to obtain spinning solution.
Preferably, in step a, the stirring is continued at 60. + -. 10 ℃.
Preferably, in the step a, the ratio of polyacrylonitrile to N, N-dimethylformamide organic solvent is 0.8g: 10 mL; the molar ratio of the tin dichloride to the sulfur powder to the selenium powder is 4: 6: 6.
Preferably, in step b, the electrostatic spinning parameters are as follows: the inner diameter of a 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 an aluminum foil collector is 13-17 cm, the rotating 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 step c, the protective atmosphere is one of nitrogen, argon-hydrogen mixture, and the like.
Preferably, in the step c, the calcination temperature is 600-; the calcination time is 1-3 h.
Compared with the prior art, the invention has the following beneficial effects: the invention successfully synthesizes the nitrogen-sulfur-selenium co-doped SnS by adopting the electrostatic spinning technology with simple operation 0.5 Se 0.5 @ CNF composite material, effective in reducing SnS 0.5 Se 0.5 The high specific capacity and the high conductivity and the stability of the carbon fiber are combined together, and the SnS is effectively improved 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 The preparation raw material can form defects in the carbon fiber, so that sodium ions can be conveniently adsorbed and the transfer of the sodium ions is accelerated. The nitrogen-sulfur-selenium co-doped carbon fiber can effectively avoid SnS 0.5 Se 0.5 And side reaction with the electrolyte occurs, resulting in dissolution of the active material, thereby improving the stability of the electrode material. In addition, the synthesized nitrogen, sulfur and selenium codoped SnS 0.5 Se 0.5 The @ CNF composite material has a self-supporting structure, can be directly used as an electrode, and overcomes the defect that a binder and a conductive additive are introduced into the traditional electrode material.
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 that nitrogen, sulfur and selenium codoped Sn @ SnS prepared in example 2 0.5 Se 0.5 The XRD pattern of the @ CNF composite.
FIG. 3 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 The XRD pattern of the @ CNF composite.
FIG. 4 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Scanning electron microscope picture of @ CNF composite material.
FIG. 5 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Structure of 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 The elemental profile of the @ CNF composite.
FIG. 8 shows that the nitrogen, sulfur and selenium co-doped SnS prepared in example 3 0.5 Se 0.5 C1 s fit plot for @ CNF composites.
FIG. 9 shows the nitrogen-sulfur-selenium co-doped SnS prepared in example 3 0.5 Se 0.5 Graph of the cycling performance of @ CNF composites.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention is further described below with reference to the following embodiments.
The self-supporting electrode can be directly 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 realized by adding SnS 0.5 Se 0.5 The carbon fiber is compounded, so that the overall conductivity of the electrode material is improved. The nitrogen-sulfur-selenium co-doped carbon fiber can provide rich active sites and relieve SnS 0.5 Se 0.5 And preventing side reactions of the electrode material with the electrolyte.
The invention uses nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 @ carbon fiber composite material is taken as a negative plate, a metal sodium plate is taken as a counter electrode, Whatman glass fiber (GF/D) is taken as a diaphragm, and electrolyte is 1 mol/L NaClO 4 PC + 5% FEC solution, assembling CR2032 coin cells in a glove box filled with argon protection. Nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 The @ CNF composite is a self-supporting structure, and requires no conductive agent and adhesive when assembling the battery.
Example 1
0.8g of Polyacrylonitrile (PAN) is dissolved at 60 ℃ with heating and continuous stirring in 10mL of N, N-Dimethylformamide (DMF), and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving in PAN-DMF solution, dispersing 2 mmol of sulfur powder and 2 mmol of selenium powder in PAN-DMF solution containing tin, and stirring for 12 hr to obtain spinningAnd (3) solution.
The spinning solution is extracted by a syringe needle (the inner diameter is 1.4mm and the outer diameter is 1.8 mm), and 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 needle of the electrostatic spinning and the aluminum foil collector is 15cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so that the nano-fiber is prepared.
And calcining the nanofiber at 700 ℃ for 2h in a nitrogen atmosphere at the heating speed of 5 ℃/min to obtain the nitrogen-sulfur-selenium co-doped Sn @ CNF composite material (shown in figure 1).
The nitrogen-sulfur-selenium co-doped Sn @ CNF composite material is used as a negative plate, a metal sodium plate is used as a counter electrode, Whatman glass fiber (GF/D) is used as a diaphragm, and 1 mol/L of electrolyte is NaClO 4 the/PC + 5% FEC solution was used to assemble CR2032 coin cells in a glove box filled with argon protection. And carrying out sodium electric negative electrode cycle test at a constant temperature of 25 ℃ and with a current density of 0.1A/g and a cut-off voltage of 0.01-3.0V. The initial 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 cycles of circulation.
Example 2
0.8g of Polyacrylonitrile (PAN) is dissolved at 60 ℃ with heating and continuous stirring in 10mL of N, N-Dimethylformamide (DMF), and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving the solution into PAN-DMF solution, dispersing 4 mmol of sulfur powder and 4 mmol of selenium powder into the PAN-DMF solution containing tin, and continuously stirring for 12h to obtain spinning solution.
The spinning solution is extracted by a syringe with a needle (the inner diameter is 1.4mm and the outer diameter is 1.8 mm), and 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 needle of the electrostatic spinning and the aluminum foil collector is 15cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so that the nanofiber is prepared.
Calcining the nanofiber at 700 ℃ for 2h in nitrogen atmosphere at the heating speed of 5 ℃/min to obtain nitrogen-sulfur-selenium co-doped Sn @ SnS 0.5 Se 0.5 @ CNF composite (FIG. 2).
Nitrogen, sulfur and selenium co-doped Sn @ SnS 0.5 Se 0.5 The @ CNF composite material is taken as a negative plate, a metal sodium plate is taken as a counter electrode, Whatman glass fiber (GF/D) is taken as a diaphragm, and the electrolyte is 1 mol/L NaClO 4 the/PC + 5% FEC solution was used to assemble CR2032 coin cells in a glove box filled with argon protection. And carrying out sodium electric negative electrode cycle test at a constant temperature of 25 ℃ and with a current density of 0.1A/g and a cut-off voltage of 0.01-3.0V. Nitrogen, sulfur and 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 kept at 339.4mAh/g after 100 cycles of circulation.
Example 3
0.8g of Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF) with heating at 60 ℃ and continuous stirring, and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving the solution into PAN-DMF solution, dispersing 6 mmol of sulfur powder and 6 mmol of selenium powder into the PAN-DMF solution containing tin, and continuously stirring for 12h to obtain spinning solution.
Extracting spinning solution with syringe needle (inner diameter 1.4mm and outer diameter 1.8 mm), collecting with aluminum foil wrapped on roller, rotating at speed of roller collector of 50 circles/min, electrostatic spinning positive voltage of 14kV and negative voltage of 1.5kV, distance between electrostatic spinning needle and aluminum foil collector of 15cm, injection flow rate of 0.1mL/min, temperature of 25 deg.C, and preparing into nanofiber
Calcining the nano-fiber for 2h at 700 ℃ in nitrogen atmosphere, and heating at the speed of 5 ℃/min to obtain nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 @ CNF composite. Combining the XRD patterns of example 1 and example 2, only when the molar ratio of the tin dichloride, the sulfur powder and the selenium powder is 4: 6: 6, the nitrogen-sulfur-selenium co-doped SnS without other impurities can be prepared 0.5 Se 0.5 @ CNF composite (FIG. 3). As shown in FIGS. 4 and 5, SnS co-doped with N, S and Se 0.5 Se 0.5 The @ CNF composite 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, and Sn elements and is uniformly distributed. After fitting, fig. 8 shows that the carbon fiber contains three element dopings of nitrogen, sulfur and selenium.
SnS co-doped with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is taken as a negative plate, a metal sodium plate is taken as a counter electrode, Whatman glass fiber (GF/D) is taken as a diaphragm, and the electrolyte is 1 mol/L of NaClO 4 the/PC + 5% FEC solution was used to assemble CR2032 coin cells in a glove box filled with argon protection. And carrying out sodium electric negative electrode cycle test at a constant temperature of 25 ℃ and with a current density of 0.1A/g and a cut-off voltage of 0.01-3.0V. As shown in FIG. 9, SnS co-doped with N, S and Se 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 kept at 471.0mAh/g after 100 cycles of circulation.
Example 4
0.8g of Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF) with heating at 60 ℃ and continuous stirring, and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving the solution into PAN-DMF solution, dispersing 6 mmol of sulfur powder and 6 mmol of selenium powder into the PAN-DMF solution containing tin, and continuously stirring for 12h to obtain spinning solution.
The spinning solution is extracted by a syringe needle (the inner diameter is 1.4mm and the outer diameter is 1.8 mm), and the spinning solution is collected by an aluminum foil wrapped on a roller, 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 needle of the electrostatic spinning and the aluminum foil collector is 13 cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so that the nano-fiber is prepared.
Calcining the nano-fiber in nitrogen atmosphere at 600 ℃ for 1h at the heating rate of 5 ℃/min to obtain nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 @ CNF composite.
SnS co-doped with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is taken as a negative plate, a metal sodium plate is taken as a counter electrode, Whatman glass fiber (GF/D) is taken as a diaphragm, and the electrolyte is 1 mol/L NaClO 4 the/PC + 5% FEC solution was used to assemble CR2032 coin cells in a glove box filled with argon protection. And carrying out sodium electric negative electrode cycle test at a constant temperature of 25 ℃ and with a current density of 0.1A/g and a cut-off voltage of 0.01-3.0V. Nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 First discharge of @ CNF compositeThe specific capacity is 970.8mAh/g, and the discharge specific capacity is still maintained at 340.7mAh/g after 100 cycles of circulation.
Example 5
0.8g of Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF) with heating at 60 ℃ and continuous stirring, and 4 mmol of tin dichloride (SnCl) 2 ) Dissolving the solution into PAN-DMF solution, dispersing 6 mmol of sulfur powder and 6 mmol of selenium powder into the PAN-DMF solution containing tin, and continuously stirring for 12h to obtain spinning solution.
The spinning solution is extracted by a syringe needle (the inner diameter is 1.4mm and the outer diameter is 1.8 mm), and 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 needle of the electrostatic spinning and the aluminum foil collector is 17cm, the injection flow rate is 0.1mL/min, and the temperature is 25 ℃, so that the nano-fiber is prepared.
Calcining the nano-fiber for 3h at 800 ℃ in nitrogen atmosphere at the heating rate of 5 ℃/min to obtain nitrogen, sulfur and selenium co-doped SnS 0.5 Se 0.5 @ CNF composite.
SnS co-doped with nitrogen, sulfur and selenium 0.5 Se 0.5 The @ CNF composite material is taken as a negative plate, a metal sodium plate is taken as a counter electrode, Whatman glass fiber (GF/D) is taken as a diaphragm, and the electrolyte is 1 mol/L of NaClO 4 the/PC + 5% FEC solution was used to assemble CR2032 coin cells in a glove box filled with argon protection. And carrying out sodium electric negative electrode cycle test at a constant temperature of 25 ℃ and with a current density of 0.1A/g and a cut-off voltage of 0.01-3.0V. Nitrogen, sulfur and 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 kept at 405.8mAh/g after 100 cycles of circulation.
Example 6
0.8g of Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF) with heating at 60 ℃ and continuous stirring, and 4 mmol of tin dichloride (SnCl) 2 ) And 6 mmol of sulfur powder and 6 mmol of selenium powder are dispersed in PAN-DMF solution together, and the mixture is continuously stirred for 12 hours to obtain the spinning solution. During electrostatic spinning, the solution can be agglomerated at the needle head to block the needle head, so that the equipment cannot spin normally. Thus, it is possible to provideWhen preparing the spinning solution, 4 mmol of tin dichloride (SnCl) was added in the following order 2 ) Completely dissolving the solution in PAN-DMF solution, and then dispersing 6 mmol of sulfur powder and 6 mmol of selenium powder in the PAN-DMF solution containing tin.
In a word, the invention synthesizes high-quality nitrogen-sulfur-selenium co-doped SnS through in-situ sulfur/selenization by regulating the element proportion of Sn, S and Se 0.5 Se 0.5 @ carbon fiber composite material. Composite material effectively converts SnS 0.5 Se 0.5 The high specific capacity and the high conductivity and the stability of the carbon fiber are combined together, and the SnS is effectively improved 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 rich active sites and relieve SnS 0.5 Se 0.5 And prevents the electrode material from side reaction with the electrolyte, resulting in dissolution of the active material, thereby improving the cycle stability of the electrode material. The cathode material has a three-dimensional self-supporting structure, can be directly used as an electrode, is free of an adhesive and a conductive agent, is low in cost, simple to operate, suitable for large-scale production and has application potential.
Claims (10)
1. Nitrogen, sulfur and 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. under the condition of continuous stirring at a certain temperature, dispersing polyacrylonitrile, tin dichloride, sulfur powder and selenium powder with certain mass into an N, N-dimethylformamide organic solvent to obtain a spinning solution;
b. extracting the spinning solution, and carrying out electrostatic spinning to prepare nano fibers;
c. calcining the nano-fiber in inert atmosphere to obtain SnS 0.5 Se 0.5 @ CNF self-supporting electrode material.
2. The method of claim 1, wherein in the step a, polyacrylonitrile is dissolved in an N, N-dimethylformamide organic solvent under continuous stirring at a certain temperature, then tin dichloride is added for dissolution, and finally sulfur powder and selenium powder are added, and stirring is continued for 12 hours to obtain the spinning solution.
3. The method of claim 1, wherein in step a, the stirring is continued at 60 ± 10 ℃.
4. The method of claim 1, wherein in step a, the ratio of polyacrylonitrile to N, N-dimethylformamide organic solvent is 0.8g: 10 mL; the molar ratio of the tin dichloride to the sulfur powder to the selenium powder is 4: 6: 6.
5. The method of claim 1, wherein in step b, the electrospinning parameters are as follows: the inner diameter of a 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 an aluminum foil collector is 13-17 cm, the rotating 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 ℃.
6. The method of claim 1, wherein in step c, the protective atmosphere is one of nitrogen, argon-hydrogen mixture.
7. The method as claimed in claim 1, wherein in step c, the calcination temperature is 600-800 ℃; the calcination time is 1-3 h.
8. Nitrogen sulfur selenium co-doped SnS prepared by the method of any one of claims 1-7 0.5 Se 0.5 @ CNF self-supporting electrode material.
9. Nitrogen sulfur selenium co-doped SnS prepared by the method of any one of claims 1-7 0.5 Se 0.5 Use of a @ CNF self-supporting electrode material as a sodium-ion battery electrode.
10. Use according to claim 9, wherein no binders or conductive agents are required.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210380232.9A CN114937760B (en) | 2022-04-12 | 2022-04-12 | Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210380232.9A CN114937760B (en) | 2022-04-12 | 2022-04-12 | Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114937760A true CN114937760A (en) | 2022-08-23 |
| CN114937760B CN114937760B (en) | 2024-04-05 |
Family
ID=82862773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210380232.9A Active CN114937760B (en) | 2022-04-12 | 2022-04-12 | Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114937760B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113823784A (en) * | 2021-08-25 | 2021-12-21 | 福建师范大学 | Preparation method and application of tin selenide-selenium-doped polyacrylonitrile compound sodium ion battery cathode material with long cycle life |
-
2022
- 2022-04-12 CN CN202210380232.9A patent/CN114937760B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113823784A (en) * | 2021-08-25 | 2021-12-21 | 福建师范大学 | Preparation method and application of tin selenide-selenium-doped polyacrylonitrile compound sodium ion battery cathode material with long cycle life |
Non-Patent Citations (1)
| Title |
|---|
| QIMING TANG等: "Ternary tin selenium sulfide (SnSe0.5S0.5) nano alloy as the high-performance anode for lithium-ion and sodium-ion batteries", 《NANO ENERGY》, vol. 41, pages 377 - 386 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114937760B (en) | 2024-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106058212B (en) | A kind of sodium-ion battery composite positive pole and preparation method thereof | |
| Wang et al. | The effect of tin content to the morphology of Sn/carbon nanofiber and the electrochemical performance as anode material for lithium batteries | |
| US10950866B2 (en) | Battery with active materials stored on or in carbon nanosheets | |
| CN107248569B (en) | Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof | |
| CN105514369A (en) | Hollow SnO2/Co3O4 hybrid nanotube as well as preparation method and application thereof | |
| CN108461734A (en) | A kind of preparation method and application of titanium phosphate sodium/carbon composite | |
| CN110042503B (en) | MoSe2@ C electrospun hollow nanofiber and preparation method and application thereof | |
| Li et al. | Architecture and performance of Si/C microspheres assembled by nano-Si via electro-spray technology as stability-enhanced anodes for lithium-ion batteries | |
| CN111769272A (en) | Bi @ C hollow nanosphere composite material and preparation method and application thereof | |
| Liu et al. | Facile preparation of a V 2 O 3/carbon fiber composite and its application for long-term performance lithium-ion batteries | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN110190261A (en) | SnSb nanoparticle/three-dimensional nitrogen-doped nanometer porous carbon composite preparation method and applications | |
| Ji et al. | Electrospinning preparation of one-dimensional Co 2+-doped Li 4 Ti 5 O 12 nanofibers for high-performance lithium ion battery | |
| CN114944476A (en) | MoS 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof | |
| CN108899499A (en) | Based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery | |
| Su et al. | Electrospun Na doped Li2TiSiO5/C nanofibers with outstanding lithium-storage performance | |
| Yao et al. | SnSe2 encapsuled in N-doped carbon nanofibers as self-supporting anode for lithium-ion storage | |
| Han et al. | Enhanced electrochemical properties of N-doped carbon nanofibers by Co9S8 nanoparticles derived from ZIF-67 | |
| CN111416124B (en) | Self-standing Sn-SnS/CNTs @ C flexible film and preparation and application thereof | |
| Xie et al. | Complementary two-phase anode improving stability and conductivity for lithium storage performance | |
| Wang et al. | Boosting lithium storage performance of Co-Sn double hydroxide nanocubes in-situ grown in mesoporous hollow carbon nanospheres | |
| Xiao et al. | Synthesis and electrochemical properties of ZnFe 2 O 4/C as novel anode material for lithium ion battery | |
| CN104009232A (en) | Preparation method of lithium iron phosphate composite anode material | |
| Shi et al. | Bi@ C fibre synthesized by electrostatic spinning as high-performance anode material for Li-ion batteries | |
| CN114937760B (en) | Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |