CN112186182A - One-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and preparation method thereof - Google Patents
One-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and preparation method thereof Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 41
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 29
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000013225 prussian blue Substances 0.000 claims abstract description 23
- 229960003351 prussian blue Drugs 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
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- 239000000463 material Substances 0.000 abstract description 25
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- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 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 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to the technical field of electrode material preparation, and particularly relates to a one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and a preparation method thereof. Synthesizing a white Prussian blue matrix by a self-template method, and then carbonizing and selenizing to obtain the carbon-coated iron selenide nanotube composite electrode material. The composite nano-tube structure can effectively improve various electrochemical properties of the electrode material; and the pores in the middle of the material provide buffer space for the volume expansion of the iron selenide, so that the material can freely expand without pulverization, and the cycling stability of the electrode material is further improved.
Description
The technical field is as follows:
the invention belongs to the technical field of electrode material preparation, and particularly relates to a one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and a preparation method thereof.
Background art:
a large number of studies have shown that graphite negative electrode materials widely used in lithium ion batteries exhibit extremely low capacity in sodium ion batteries because they cannot form stable high-order compounds with sodium ions, which makes graphite-based materials with lower cost unsuitable for use as sodium ion batteries. Therefore, it is very important to develop a negative electrode material of a sodium ion battery with low cost and excellent performance. The negative electrode material with metal base alloy or conversion reaction has higher theoretical specific capacity due to multi-electron reaction in the energy storage process, and has attracted extensive attention in recent years. Among many metal conversion materials, iron-based materials are favored by researchers because of their high specific capacity, low cost, and simple synthesis methods. However, the iron-based material often undergoes large volume expansion in the process of sodium intercalation, and stress generated by the volume change can cause the material to undergo pulverization phenomenon, so that the material falls off from a current collector, loss of active substances and damage of an electrode material structure are caused, and finally the cycle life and actual specific capacity of the electrode material are reduced. In addition, the iron-based material has poor conductivity, which results in a reduction in rate capability of the electrode material.
The invention content is as follows:
the technical problem to be solved by the invention is that the iron-based material can generate large volume expansion in the process of sodium intercalation, and then the material is pulverized, so that the material falls off from a current collector, the loss of active substances and the damage of an electrode material structure are caused, and finally the cycle life and the actual specific capacity of the electrode material are reduced; the iron-based material has poor conductivity, so that the rate capability of the electrode material is reduced.
In order to solve the problems, the carbon-coated iron selenide nanotube composite electrode material is obtained by carrying out the strategies of optimizing the nano structure of the iron-based material and compounding the iron-based material with the carbon material, and the composite nano tubular structure can effectively improve various electrochemical properties of the electrode material; and the pores in the middle of the material provide buffer space for the volume expansion of the iron selenide, so that the material can freely expand without pulverization, and the cycling stability of the electrode material is further improved.
In order to achieve the purpose, the invention is realized by the following technical scheme that the preparation method of the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material comprises the steps of synthesizing a white Prussian blue matrix by a self-template method, and then carbonizing and selenizing to obtain the carbon-coated iron selenide nanotube composite electrode material.
Further, the self-template method for synthesizing the white Prussian blue matrix comprises the following steps:
(1-1) mixing ascorbic acid aqueous solution A with Na4Fe(CN)6·10H2Mixing and stirring the O-glycol solution B until the O-glycol solution B is completely dissolved, pouring the solution into a high-pressure autoclave in polytetrafluoroethylene village, and keeping the solution in an oven at 70 ℃ for 24 hours; wherein, the solution A is a reducing agent and provides an acid environment; the solution B is an iron source and is in an acidic environment [ Fe (CN)6]4-Will decompose into Fe2+Ascorbic acid (reducing agent) inhibits Fe2+Oxidation in air (but with some Fe)2+Oxidized). At 70 ℃ Fe2+/Fe3+With undecomposed [ Fe (CN)6]4-React to form "insoluble" Fe4[Fe(CN)6]3Crystal nuclei, which constitute the white prussian blue skeleton. According to the ostwald ripening mechanism, the internal metastable part dissolves in the solution and regenerates at the outer surface, eventually forming a tubular morphology.
(1-2) washing the white precipitate obtained in (1-1) with deionized water and alcohol for several times, centrifuging, collecting, removing impurities dissolved in water or alcohol, drying at 80 deg.C for 12h, and removing excessive water in the material to obtain matrix white Prussian blue nanotube.
Further, in step (1-1), 8mmol of ascorbic acid was added to 6mL of deionized water, and stirred for 20min to obtain a clear solution A.
Further, in the step (1-1), 0.4mmol of Na was added4Fe(CN)6·10H2O was added to 74mL of ethylene glycol and stirred for 20min to obtain solution B.
Further, the carbonization comprises the following steps:
(2-1) dispersing the matrix prussian blue nanotube into tris buffer solution, performing ultrasonic treatment, performing magnetic stirring, adding dopamine hydrochloride in the stirring process, wherein the dopamine hydrochloride can be coated on the surface of the matrix prussian blue nanotube to form a Polydopamine (PDA) -coated prussian blue nanotube; after stirring, washing the mixture for several times by using deionized water and alcohol, and then centrifugally collecting the mixture to obtain a polydopamine-coated white Prussian blue nanotube;
(2-2) calcining the product obtained in the step (2-1) for 3h at 500 ℃ in an argon atmosphere, wherein the coated polydopamine can be converted into carbon, and the matrix white Prussian blue nanotube can be converted into Fe3O4(ii) a Then naturally cooling to room temperature to obtain Fe3O4@ C nanotubes.
Further, in the step (2-1), the matrix white Prussian blue nanotubes are dispersed in 150mL of tris buffer solution, ultrasonic treatment is carried out for 20min, then the solution is placed on a magnetic stirrer, and 50mg of dopamine hydrochloride is added during stirring.
Further, the temperature rise rate during the calcination in the step (2-2) is 2 ℃/min. The heating rate is slow under the condition, so that the phenomenon that the shape of the material is damaged due to large stress generated by the material due to the fact that the heating rate is too fast is avoided.
Further, the selenizing step comprises: mixing Fe3O4Mixing the @ C nanotube and selenium powder, grinding, keeping the mixture at 450 ℃ for 5h under the argon atmosphere, then keeping the mixture at 600 ℃ for 5h, naturally cooling to room temperature, and finally obtaining the target product, namely the one-dimensional hollow iron selenide and carbon composite nanotube.
Further, the temperature rise rate of the two-stage temperature rise is 2 ℃/min. The iron selenide is formed at 450 ℃ and then is raised to 600 ℃ so as to remove the redundant selenium powder and further improve the crystallinity of the iron selenide.
Further, Fe3O4The mixing ratio of the @ C nanotube and the selenium powder is 1: 7. To make Fe3O4The @ C nanotube is fully selenized, so that the excessive selenium powder is ensured, and meanwhile, the selenium powder cannot have too much residue after the reaction is finished, and the best effect can be achieved by selecting the mixing proportion.
The one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material prepared by the method has a one-dimensional hollow tubular structure, the composite nano tubular structure has the advantages of large pore, large specific surface area, high active site, high specific capacity and the like, and the coated carbon layer can improve the whole conductivity of the electrode material, is favorable for forming a stable SEI film and improves the whole structural stability of the electrode material; the nanotube-shaped morphology can not only increase the contact area of the active material and the electrolyte, but also reduce the transmission path of electrons and ions, and improve the reaction kinetics of the material. The advantages can effectively improve various electrochemical properties of the electrode material. In addition, the middle pore space provides a buffer space for the volume expansion of the iron selenide, so that the material can freely expand without pulverization, and the cycling stability of the electrode material is further improved.
The invention has the beneficial effects that:
(1) the one-dimensional tubular structure of the precursor of the white Prussian blue can be completely maintained after selenization, the structural stability of the electrode material in the charging and discharging processes can be maintained, meanwhile, the middle pore space provides a buffer space for the volume expansion of the iron selenide, so that the material can freely expand without pulverization, and the cycling stability of the electrode material is further improved.
(2) The composite structure of the iron selenide nanotube fully exerts the advantages of large pore, large specific surface area, high active site, high specific capacity and the like of the composite nanotube material, the coated carbon layer can well relieve the problem of large volume expansion of the iron selenide in the charging and discharging processes, and the integral conductivity of the electrode material is improved. The nanotube-shaped morphology can not only increase the contact area of the active material and the electrolyte, but also reduce the transmission path of electrons and ions, and the advantages can effectively improve various electrochemical properties of the electrode material.
Description of the drawings:
FIG. 1 is a scanning electron micrograph of a composition of the present invention;
wherein a and b are precursor white Prussian blue; c is the cross section of the precursor white Prussian blue; d is a one-dimensional hollow carbon-coated iron selenide nanotube.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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.
Example 1:
the preparation method of the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material comprises the following steps:
s1: firstly, adding 8mmol of ascorbic acid into 6mL of deionized water (DIW), and stirring for 20min to obtain a clear solution A; then 0.4mmol of Na4Fe(CN)6·10H2O was added to 74mL of ethylene glycol and stirred for 20min to obtain solution B. And pouring the solution A into the solution B, and continuously stirring until the solution A is completely dissolved to obtain a clear yellow solution. The solution was poured into a 100mL Teflon Enmural autoclave and held in an oven at 70 ℃ for 24h (the oven was previously heated to 70 ℃).
S2: and washing the white precipitate with DIW and alcohol for several times, centrifuging, collecting, and drying at 80 ℃ for 12h to obtain matrix white Prussian blue nanotubes.
S3: dispersing the product obtained in S2 into 150mL of tris buffer solution, performing ultrasonic treatment for 20min, then placing the solution on a magnetic stirrer, and adding 50mg of dopamine hydrochloride in the stirring process (wherein the ratio of the white Prussian blue nanotube to the dopamine hydrochloride can be adjusted according to the thickness of a carbon layer to be obtained, but the material coating is incomplete when the dopamine hydrochloride is too little, and carbon microspheres are formed when the dopamine hydrochloride is too much). The solution is continuously stirred for 4 hours, washed by DIW and alcohol for several times and then centrifugally collected to obtain the Polydopamine (PDA) -coated white Prussian blue nano-tubes.
S4: calcining the product obtained in the step S3 at 500 ℃ for 3h in an argon atmosphere (the heating rate is 2 ℃/min), naturally cooling to room temperature to obtain Fe3O4@ C nanotubes.
S5: and (3) mixing the product obtained in the step (S4) with selenium powder (the ratio is 1:7), and grinding for 20 min. Keeping the mixture at 450 ℃ for 5h (the heating rate is 2 ℃/min) under the argon atmosphere, then keeping the mixture at 600 ℃ for 5h (the heating rate is 2 ℃/min), and naturally cooling to room temperature to finally obtain the target product, namely the one-dimensional hollow composite nanotube of iron selenide and carbon.
Claims (10)
1. The preparation method of the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material is characterized by comprising the following steps of: synthesizing a white Prussian blue matrix by a self-template method, and then carbonizing and selenizing to obtain the carbon-coated iron selenide nanotube composite electrode material.
2. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 1, wherein the method comprises the following steps: the self-template method for synthesizing the white Prussian blue matrix comprises the following steps:
(1-1) mixing ascorbic acid aqueous solution A with Na4Fe(CN)6·10H2Mixing and stirring the O-glycol solution B until the O-glycol solution B is completely dissolved, pouring the solution into a high-pressure autoclave in polytetrafluoroethylene village, and keeping the solution in an oven at 70 ℃ for 24 hours;
(1-2) washing the white precipitate obtained in (1-1) with deionized water and alcohol for several times, centrifuging, collecting, and drying at 80 ℃ for 12h to obtain the matrix white Prussian blue nanotube.
3. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 2, wherein the method comprises the following steps: in the step (1-1), 8mmol of ascorbic acid is added into 6mL of deionized water, and the mixture is stirred for 20min to obtain a clear solution A.
4. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 2, wherein the method comprises the following steps: in step (1-1), 0.4mmol of Na4Fe(CN)6·10H2O was added to 74mL of ethylene glycol and stirred for 20min to obtain solution B.
5. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 1, wherein the method comprises the following steps: the carbonization comprises the following steps:
(2-1) dispersing the matrix prussian blue nano-tube into tris buffer solution, performing ultrasonic treatment, then performing magnetic stirring, and adding dopamine hydrochloride in the stirring process; after stirring, washing the mixture for several times by using deionized water and alcohol, and then centrifugally collecting the mixture to obtain a polydopamine-coated white Prussian blue nanotube;
(2-2) calcining the product obtained in the step (2-1) at 500 ℃ for 3h in an argon atmosphere, naturally cooling to room temperature to obtain Fe3O4@ C nanotubes.
6. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 5, wherein the method comprises the following steps: and (2-1) dispersing the matrix white Prussian blue nanotubes into 150mL of tris buffer solution, carrying out ultrasonic treatment for 20min, then placing the solution on a magnetic stirrer, and adding 50mg of dopamine hydrochloride during stirring.
7. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 1, wherein the method comprises the following steps: the selenizing step comprises: mixing Fe3O4Mixing the @ C nanotube and selenium powder, grinding, keeping the mixture at 450 ℃ for 5h under the argon atmosphere, then keeping the mixture at 600 ℃ for 5h, naturally cooling to room temperature, and finally obtaining the target product, namely the one-dimensional hollow iron selenide and carbon composite nanotube.
8. The method of claim 7The preparation method of the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material is characterized by comprising the following steps of: fe3O4The mixing ratio of the @ C nanotube and the selenium powder is 1: 7.
9. The method for preparing the one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material as claimed in claim 5 or 7, wherein the method comprises the following steps: the rate of temperature rise was 2 ℃/min.
10. A one-dimensional hollow carbon-coated iron selenide nanotube composite electrode material obtained by the preparation method of claims 1-9, which is characterized in that: has a one-dimensional hollow tubular structure.
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