CN114784244A - Three-dimensional hollow WS2/C composite electrode material and preparation method and application thereof - Google Patents
Three-dimensional hollow WS2/C composite electrode material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000007772 electrode material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 238000004729 solvothermal method Methods 0.000 claims abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 35
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 31
- 239000012498 ultrapure water Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 27
- 239000012046 mixed solvent Substances 0.000 claims description 19
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004246 zinc acetate Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000003575 carbonaceous material Substances 0.000 claims description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 10
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 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 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- -1 transition metal sulfides Chemical class 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
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- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—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
- H01M4/5815—Sulfides
-
- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
Abstract
The invention discloses a three-dimensional hollow WS2A three-dimensional hollow carbon structure is constructed by utilizing a hard template method and ZIF-8 derived carbon, and then a three-dimensional hollow WS is synthesized by a solvothermal method2a/C composite material. WS obtainable by this process2The phase purity of the/C composite electrode material is high, and no other impurity phase exists; WS (WS)2the/C composite electrode material has a three-dimensional hollow composite structure,and prepared WS2the/C composite electrode material has good dispersibility and uniform size distribution; let WS be2the/C composite electrode material is applied to a sodium ion battery, on one hand, the volume expansion of the electrode in the charging and discharging process can be effectively improved through the three-dimensional hollow structure, and in addition, the high-speed migration of charges can be ensured through the three-dimensional hollow carbon layer structure and the nano structure, so that the excellent sodium storage performance is shown. The invention discloses a three-dimensional hollow WS2The preparation method of the/C composite electrode material has the advantages of simple experimental operation process, low raw material cost, easily controlled reaction temperature, short used time and large-scale preparation in a short time.
Description
Technical Field
The invention belongs to WS2The technical field of nano material preparation, in particular to a three-dimensional hollow WS2a/C composite electrode material, a preparation method and application thereof.
Background
WS2The nano-sheets are typical layered transition metal sulfides, covalent bonds (S-W-S) with strong acting force are arranged in the layers, van der Waals force with weak acting force is arranged between the layers, the interlayer spacing is larger by about 0.62nm, and the diffusion of sodium ions with larger ionic radius is facilitated. WS2The structure of the nanoplatelets is similar to graphite with 2D monolayers stacked by weak van der waals interactions, and the 2D structure can provide large surface area and 2D percolation channels to facilitate rapid transport of electrons within a monolayer, so sodium ions can be readily transported from WS2Insertion and extraction in the nanosheet, therefore WS2Is also considered to be a potential sodium ion battery cathode material.
Due to WS2The inherent semiconductor characteristics result in poor conductivity, low electron mobility, and poor rate performance. In addition, the large volume expansion during the charge and discharge process can cause the destruction and collapse of the structure, resulting in poor cycle stability. Constructing hollow structuresThe volume change of the material caused by volume expansion can be effectively relieved, and the stability of the structure is ensured. But WS2The sodium storage performance of a single hollow structure after multiple charging and discharging is not ideal enough, and the interweaving network of the three-dimensional structure has a better charge transmission channel, so that the charge transfer efficiency in the electrochemical reaction process can be promoted. Therefore, it is very important to construct a three-dimensional hollow composite structure.
Disclosure of Invention
To overcome the above disadvantages of the prior art, it is an object of the present invention to provide a three-dimensional hollow WS2The preparation method and application of the/C composite electrode material to solve the problem of WS2Poor cycle stability due to volume expansion during charging and discharging, and WS2The single hollow structure has the problem of unsatisfactory sodium storage performance after multiple charging and discharging.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a three-dimensional hollow WS2The preparation method of the/C composite electrode material comprises the following steps:
the method comprises the following steps: dissolving zinc acetate in ultrapure water, stirring until the zinc acetate is dissolved to obtain a clear and transparent solution, dropwise adding ammonia water into the transparent solution, stirring, adding ultrapure water, continuously stirring to obtain a uniform transparent solution, then carrying out hydrothermal reaction, cooling, washing and drying to obtain a ZnO material;
step two: adding ZnO and 2-methylimidazole into a mixed solvent of ultrapure water and NMP, fully stirring to obtain a mixed solution, then carrying out heating reaction on the mixed solution, and after the reaction is finished, washing and drying to obtain a ZnO @ ZIF-8 material;
step three: carrying out heat treatment on the ZnO @ ZIF-8 material to obtain a ZnO @ C composite material, adding the ZnO @ C composite material into an HCl solution, heating, stirring, carrying out suction filtration, and drying to obtain a hollow carbon material;
step four: adding a hollow carbon material into an ethanol solution, and stirring to obtain a black suspension; adding tungsten hexachloride and thioacetamide into the suspension, stirring, carrying out solvothermal reaction, cooling, washing, drying, and heatingObtaining the three-dimensional hollow WS2a/C composite electrode material.
Preferably, in the step one, the dosage ratio of the zinc acetate to the ultrapure water is (0.1-1) g: (5-30) mL; the volume ratio of the ammonia water to the ultrapure water is (0.1-5): (5-30).
Preferably, in the step one, stirring is carried out for 5-15min until the solution is dissolved, ammonia water is dripped to stir for 10-30min, and ultrapure water is added to continue stirring for 20 min.
Preferably, in the first step, the hydrothermal reaction temperature is 160-220 ℃, and the reaction time is 12-36 h.
Preferably, in the first step, the ZnO material is obtained after washing with ethanol and deionized water three times respectively and drying in vacuum at 60 ℃ for 12 hours.
Preferably, in the second step, the mass ratio of ZnO to 2-methylimidazole is (0.1-0.5): (0.2-1); the volume ratio of ultrapure water to NMP in the mixed solvent was 1: 1.
Preferably, in the second step, the stirring time is 10-30min, the heating temperature is 60-80 ℃, and the reaction time is 12-48 h.
Preferably, in the second step, the ZnO @ ZIF-8 material is obtained after the ZnO @ ZIF-8 material is dried in vacuum at 70 ℃ for 12 hours after the ethanol and the deionized water are respectively washed for three times.
Preferably, in the third step, the heat treatment is heating to 500-800 ℃ at a heating rate of 5-15 ℃/min and preserving heat for 1-4 h; the concentration of the HCl solution is 0.5-3mol/L, and the HCl solution is stirred for 12-36h at the temperature of 30-60 ℃.
Preferably, in step three, the hollow carbon material is obtained after drying for 12h in vacuum at 70 ℃.
Preferably, in the fourth step, stirring for 10-30min to obtain a black suspension, magnetically stirring for 2h, then carrying out a solvothermal reaction, washing with ethanol and deionized water respectively after the reaction, and drying in vacuum at 60 ℃ for 12 h.
Preferably, in the fourth step, the dosage ratio of the hollow carbon material to the ethanol is (30-60) mg: (30-60) mL, wherein the mass ratio of the tungsten hexachloride to the thioacetamide is (0.55-1.19): (0.75-2.25).
Preferably, in the fourth step, the solvothermal reaction temperature is 180-; the heat treatment is performed in Ar gas atmosphereKeeping the temperature at 500-800 ℃ for 1-3h at the heating rate of 5-15 ℃ for min-1。
The invention also discloses the three-dimensional hollow WS prepared by the preparation method2a/C composite electrode material.
The invention also discloses a three-dimensional hollow WS2The application of the/C composite electrode material in the preparation of a sodium-ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a three-dimensional hollow WS2The preparation method of the/C composite electrode material comprises the steps of constructing a three-dimensional hollow carbon structure by using a hard template method and ZIF-8 derived carbon, and synthesizing the three-dimensional hollow WS by a solvothermal method2Composite electrode material/C, WS produced by the method2The phase purity of the/C composite electrode material is high, and no other impurity phase exists; the invention discloses a three-dimensional hollow WS2The preparation method of the/C composite electrode material has the advantages of simple experimental operation process, low raw material cost, easily controlled reaction temperature, short used time and large-scale preparation in a short time.
Further, under the conditions that the hydrothermal reaction temperature is 160-220 ℃ and the reaction time is 12-36h, the three-dimensional self-assembled ZnO structure can be obtained.
Furthermore, three-dimensional self-assembled ZnO is used as a template and a precursor to be coordinated with 2-methylimidazole, so that the ZnO @ ZIF-8 composite structure can be obtained.
Further, carrying out heat treatment on the ZnO @ ZIF-8 material to further carbonize the ZnO @ ZIF-8 material to obtain a ZnO @ C composite structure, adding the ZnO @ C composite material into an HCl solution, and removing a ZnO template through acid washing to obtain the three-dimensional hollow carbon structure.
Further, the temperature of the solvothermal reaction is 180-220 ℃, the reaction time is 12-48h, and the three-dimensional hollow WS can be obtained under the solvothermal reaction condition2the/C composite material further improves the crystallinity of the material by using an annealing process.
The invention also discloses a three-dimensional hollow WS2Composite electrode material/C, WS2the/C composite electrode material is a three-dimensional hollow composite structure, and WS2the/C composite electrode material has good dispersibility and uniform size distribution; the three-dimensional hollow structure can effectively improve the volume expansion of the electrode in the charging and discharging process and shows good structural stability and cycle performance when applied to the sodium ion battery. In addition, the three-dimensional nanostructure can ensure high-speed charge migration and improve the rate capability of the material, thereby synergistically realizing excellent sodium storage performance and having wide research value and application value in the electrochemical field.
Drawings
FIG. 1 is a schematic representation of a three-dimensional hollow WS prepared in example 3 of the present invention2Composite material/C and phase-pure WS2XRD pattern of the nano material;
FIG. 2 shows phase-pure WS prepared in example 3 of the present invention2Nanomaterial and hollow WS2SEM image of/C composite material; wherein (a) pure phase WS2Nano material, (b) is an enlarged view of (a), (c) hollow WS2a/C composite material, wherein (d) is an enlarged view of (C);
FIG. 3 shows phase-pure WS prepared in example 3 of the present invention2Nanomaterial (a-c) and hollow WS2TEM, HRTEM and elemental distribution plots of the/C composite (d-f); wherein (a) pure phase WS2TEM of the nanomaterial, (b) is an enlargement of (a), (c) phase-pure WS2HRTEM of nanomaterial, (d) hollow WS2TEM of the/C composite, (e) is an enlargement of (d), (f) hollow WS2HRTEM of/C composite material, (g) hollow WS2Element distribution diagram of the/C composite material;
FIG. 4 shows phase-pure WS prepared in example 3 of the present invention2Nanomaterials and hollow WS2XPS plots of/C composites; wherein, (a) W4 f, (b) S2 p, (c) N1S;
FIG. 5 shows phase-pure WS prepared in example 3 of the present invention2Nanomaterial and hollow WS2the/C composite material is used as the cathode material of the sodium-ion battery and has cycle performance and rate capability; wherein, (a) cycle performance, (b) rate performance, and (c) capacity retention rate.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a three-dimensional hollow WS2The preparation method of the/C composite electrode material comprises the following steps:
the method comprises the following steps: dissolving 0.1-1g of zinc acetate in 5-30mL of ultrapure water, and stirring for 5-15min until the zinc acetate is dissolved to obtain a clear and transparent solution. Then 0.1-5mL of ammonia water is dripped into the transparent solution, stirring is continued for 10-30min, and 5-30mL of ultrapure water is added and stirred for 20min, so as to obtain uniform transparent solution. Transferring the solution into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, wherein the reaction temperature is 160-220 ℃, and the heat preservation time is 12-36 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted white turbid liquid with ethanol and deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnO material.
Step two: adding 0.1-0.5g of ZnO and 0.2-1g of 2-methylimidazole into 10-60mL of ultrapure water and 10-60mL of NMP mixed solvent, ensuring the volume ratio of the mixed solvent to be 1:1, stirring for 10-30min to fully mix, transferring the mixture into a silk-mouth bottle, and preserving heat for 12-48h at the temperature of 60-80 ℃. After the reaction is finished, washing the reacted white turbid liquid with ethanol and deionized water for three times respectively, and drying in vacuum at 70 ℃ for 12 hours to obtain the ZnO @ ZIF-8 material.
Step three: the ZnO @ ZIF-8 material is put into a porcelain boat and heated to 500 ℃ and 800 ℃ for heat preservation for 1-4h at the heating rate of 5-15 ℃/min in the vacuum atmosphere of a tubular furnace to obtain a ZnO @ C sample. Adding the ZnO @ C composite material into 0.5-3mol/L HCl solution, stirring at 30-60 ℃ for 12-36h, carrying out suction filtration to obtain black powder, and drying at 70 ℃ in vacuum for 12h to obtain the hollow carbon material.
Step four: adding 30-60mg of the hollow carbon-carbon material into 30-60mL of ethanol solution to ensure that the concentration of the solution is 1mg/mL, and stirring for 10-30min to disperse the hollow carbon-carbon material in a solvent to obtain black suspension. 0.55-1.19g of tungsten hexachloride and 0.75-2.25g of thioacetamide were added to the above suspension and stirred magnetically for 2 h. Then, the solution is transferred into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, the reaction temperature is 180-220 ℃, and the temperature is kept for 12-48 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted turbid solution with ethanol and deionized water, and drying in vacuum at 60 ℃ for 12 h. Heat treating the dried powder in a vacuum tube furnace filled with Ar at 500-800 deg.C for 1-3h with a heating rate of 5-15 deg.C for min-1Obtaining WS2a/C composite material.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
The method comprises the following steps: 0.1g of zinc acetate is dissolved in 10mL of ultrapure water, and the solution is stirred for 5min until the zinc acetate is dissolved to obtain a clear and transparent solution. Then, 0.1mL of ammonia water was added dropwise to the transparent solution, and after stirring was continued for 10min, 20mL of ultrapure water was added thereto and stirred for 20min to obtain a uniform transparent solution. The solution was transferred to a 100mL stainless steel autoclave lined with Teflon at 180 ℃ for 12 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted white turbid liquid with ethanol and deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnO material.
Step two: adding 0.1g of ZnO and 0.2g of 2-methylimidazole into a mixed solvent of 10mL of ultrapure water and 10mL of NMP, ensuring that the volume ratio of the mixed solvent is 1:1, stirring for 10min to fully mix the mixed solvent, transferring the mixed solvent into a silk-mouth bottle, and preserving the heat at the temperature of 60 ℃ for 12 h. After the reaction is finished, washing the reacted white turbid liquid with ethanol and deionized water for three times respectively, and drying in vacuum at 70 ℃ for 12 hours to obtain the ZnO @ ZIF-8 material.
Step three: and (2) putting the ZnO @ ZIF-8 material into a porcelain boat, heating to 500 ℃ at a heating rate of 5 ℃/min in a vacuum atmosphere of a tube furnace, and preserving heat for 1h to obtain a ZnO @ C sample. Adding the ZnO @ C composite material into 0.5mol/L HCl solution, stirring for 12h at 30 ℃, carrying out suction filtration to obtain black powder, and drying for 12h in vacuum at 70 ℃ to obtain the hollow carbon material.
Step four: and (3) adding 30mg of the hollow carbon-carbon material into 30mL of ethanol solution to ensure that the concentration of the solution is 1mg/mL, and stirring for 10min to disperse the hollow carbon-carbon material in the solvent to obtain black suspension. 0.55g of tungsten hexachloride and 0.75g of thioacetamide are added to the suspension and stirred magnetically for 2 h. Next, the above solution was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, the reaction temperature was 180 ℃ and the temperature was maintained for 12 hours. After the reaction is finished, cooling to room temperature, respectively washing the reacted turbid solution with ethanol and deionized water, and drying in vacuum at 60 ℃ for 12 hours. Heat treating the dried powder in a vacuum tube furnace filled with Ar at 500 deg.C for 1h with a heating rate of 5 deg.C for min-1Obtaining WS2a/C composite electrode material.
Example 2
The method comprises the following steps: 0.2g of zinc acetate is dissolved in 15mL of ultrapure water and stirred for 15min until the zinc acetate is dissolved to obtain a clear and transparent solution. Then, 2mL of ammonia water was added dropwise to the transparent solution, and after stirring for 30min, 15mL of ultrapure water was added thereto and stirred for 20min to obtain a uniform transparent solution. The solution was transferred to a 100mL stainless steel autoclave lined with Teflon at 180 ℃ for 12 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted white turbid liquid with ethanol and deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnO material.
Step two: 0.2g of ZnO and 0.4g of 2-methylimidazole were added to a mixed solvent of 30mL of ultrapure water and 30mL of NMP, and the volume ratio of the mixed solvent was kept at 1: 1. Stirring for 10min to mix thoroughly, transferring to a silk-mouth bottle, and keeping the temperature at 80 deg.C for 48 h. After the reaction is finished, washing the reacted white turbid liquid with ethanol and deionized water for three times respectively, and drying in vacuum at 70 ℃ for 12 hours to obtain the ZnO @ ZIF-8 material.
Step three: and (2) putting the ZnO @ ZIF-8 material into a porcelain boat, heating to 500 ℃ at a heating rate of 5 ℃/min in a vacuum atmosphere of a tube furnace, and preserving heat for 1h to obtain a ZnO @ C sample. Adding the ZnO @ C composite material into 3mol/L HCl solution, stirring for 12 hours at 60 ℃, carrying out suction filtration to obtain black powder, and drying for 12 hours in vacuum at 70 ℃ to obtain the hollow carbon material.
Step four: 60mg of the hollow carbon-carbon material is added into 60mL of ethanol solution, the concentration of the solution is ensured to be 1mg/mL, and the mixture is stirred for 30min to be dispersed in the solvent to obtain black suspension. 1.19g of tungsten hexachloride and 2.25g of thioacetamide were added to the above suspension and stirred magnetically for 2 h. Next, the above solution was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, the reaction temperature was 220 ℃ and the temperature was maintained for 48 hours. After the reaction is finished, cooling to room temperature, respectively washing the reacted turbid solution with ethanol and deionized water, and drying in vacuum at 60 ℃ for 12 hours. Heat treating the dried powder in a vacuum tube furnace filled with Ar at 800 deg.C for 2h with a heating rate of 10 deg.C for min-1Obtaining WS2a/C composite electrode material.
Example 3
The method comprises the following steps: 0.4g of zinc acetate is dissolved in 20mL of ultrapure water, and the solution is stirred for 5min until the zinc acetate is dissolved to obtain a clear and transparent solution. Then, 0.5mL of ammonia water was added dropwise to the transparent solution, and after stirring was continued for 30min, 20mL of ultrapure water was added thereto and stirred for 20min to obtain a uniform transparent solution. The solution was transferred to a 100mL stainless steel autoclave lined with Teflon at 200 ℃ for 24 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted white turbid liquid with ethanol and deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnO material.
Step two: 0.2g of ZnO and 0.4g of 2-methylimidazole were added to a mixed solvent of 30mL of ultrapure water and 30mL of NMP, and after stirring for 20min to mix them thoroughly, they were transferred to a wire-neck flask and kept at 70 ℃ for 24 hours. After the reaction is finished, washing the reacted white turbid liquid with ethanol and deionized water for three times respectively, and drying in vacuum at 70 ℃ for 12 hours to obtain the ZnO @ ZIF-8 material.
Step three: and (2) putting the ZnO @ ZIF-8 material into a porcelain boat, heating to 700 ℃ at a heating rate of 10 ℃/min in a vacuum atmosphere of a tubular furnace, and preserving heat for 2 hours to obtain a ZnO @ C sample. Adding the ZnO @ C composite material into 1mol/L HCl solution, stirring for 24h at 50 ℃, carrying out suction filtration to obtain black powder, and drying for 12h in vacuum at 70 ℃ to obtain the hollow carbon material.
Step four: 30mg of the hollow carbon material is added into 30mL of ethanol solution, and the mixture is stirred for 15min to be dispersed in the solvent to obtain black suspension. 0.55g of tungsten hexachloride and 0.75g of thioacetamide are added to the suspension and stirred magnetically for 2 h. Next, the above solution was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, the reaction temperature was 200 ℃ and the temperature was maintained for 24 hours. After the reaction is finished, cooling to room temperature, respectively washing the reacted turbid solution with ethanol and deionized water, and drying in vacuum at 60 ℃ for 12 h. Heat treating the dried powder in a vacuum tube furnace filled with Ar at 500 deg.C for 2h with a heating rate of 10 deg.C for min-1Obtaining WS2a/C composite electrode material. Pure phase WS2The preparation of the nano material is that the hollow carbon-carbon material is not added in the fourth step, and the other processes are the same.
Three-dimensional hollow WS prepared in this example2Composite electrode material/C and phase-pure WS2The performance test analysis results of the nano material are as follows:
referring to FIG. 1, from three-dimensional hollow WS2Composite electrode material/C and phase-pure WS2The X-ray diffraction (XRD) pattern of the nano material can show that two samples are combined with WS of a hexagonal system with JCPDS serial numbers of 08-02372Consistent structure, sayHollow WS that can be made by the method2The phase purity of the/C product is higher, and no other mixed phase exists. In addition, since WS2the/C composite electrode material has the carbon material, so the diffraction peak intensity of XRD is reduced.
Referring to FIG. 2, FIG. 2 shows pure phase WS2Nanomaterial and hollow WS2Scanning Electron Microscope (SEM) images of the/C composite electrode material. It can be seen that the morphologies of the two are both nanosheet structure and pure phase WS2The nanomaterial is represented as a solid spherical structure self-assembled by nanosheets, and WS2the/C composite electrode material has a divergent three-dimensional hollow composite structure, and the prepared product has good dispersibility and uniform size distribution.
Referring to FIG. 3, FIG. 3 shows phase-pure WS prepared in example 32Nanomaterial and hollow WS2The results of scanning electron microscopy (TEM) and HRTEM images of the/C composite electrode material are consistent with those of the scanning electron microscopy, and WS can be seen2The nanomaterial is of a solid structure, and WS2the/C composite exhibited a divergent hollow structure, indicating that we succeeded in synthesizing a three-dimensional hollow composite structure. Otherwise from hollow WS2The element distribution of the/C composite electrode material shows a uniform distribution of W, S, C, N elements, wherein the N element is derived from N-doped carbon.
Referring to FIG. 4, FIG. 4 shows the preparation of pure phase WS2Nanomaterials and hollow WS2XPS test of/C composite electrode materials, in which W4 f and S2 p correspond to W, respectively4+And S2-. In the hollow WS2The signal of N1s was detected in the/C composite electrode material, consistent with the results obtained in the energy spectrum.
Referring to FIG. 5, FIG. 5 shows pure phase WS2Nanomaterials and hollow WS2the/C composite material is used as the cathode material of the sodium ion battery and has cycle performance and rate capability. All sodium ion batteries assembled by the invention are CR2032 type button batteries with the diameter of 20mm, a sodium sheet is used as a counter electrode, and the electrolyte used by the sodium ion batteries is EC/DEC (volume ratio of 1:1) + 5% of FEC + NaClO4. From the figure, one can see the hollow WS2the/C composite electrode material has excellent cycle performance and rate capability, and is applied to high currentThe long-cycle performance test can also show better capacity retention rate. WS (WS)2After the/C composite electrode material circulates for 150 circles, the reversible capacity is 384mAh g-1And WS2Electrode, capacity decayed rapidly to 86mAh g only after 60 cycles-1This shows that the three-dimensional hollow composite structure can effectively improve the cycle stability of the material. WS (WS)2the/C composite electrode material is 0.1, 0.2, 0.5, 1, 2, 5 and 10Ag-1Has a reversible capacity of 487, 450, 385, 345, 303, 247, and 191mAh g, respectively-1. When the current density returns to 200mA g-1When the capacity of the material is still 472mAh g-1And excellent rate performance is shown.
Example 4
The method comprises the following steps: dissolving 1g of zinc acetate in 30mL of ultrapure water, and stirring for 15min until the zinc acetate is dissolved to obtain a clear and transparent solution. Then, 5mL of ammonia water was added dropwise to the transparent solution, and after stirring was continued for 30min, 30mL of ultrapure water was added thereto and stirred for 20min to obtain a uniform transparent solution. The solution was transferred to a 100mL stainless steel autoclave lined with Teflon at 220 deg.C for 36 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted white turbid liquid with ethanol and deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnO material.
Step two: 0.5g of ZnO and 1g of 2-methylimidazole are added into a mixed solvent of 60mL of ultrapure water and 60mL of NMP, the volume ratio of the mixed solvent is ensured to be 1:1, the mixed solvent is stirred for 30min to be fully mixed, and then the mixed solvent is transferred into a wire-mouth bottle to be insulated for 48h at the temperature of 80 ℃. After the reaction is finished, washing the reacted white turbid liquid with ethanol and deionized water for three times respectively, and drying in vacuum at 70 ℃ for 12 hours to obtain the ZnO @ ZIF-8 material.
Step three: and (3) putting the ZnO @ ZIF-8 material into a porcelain boat, heating to 800 ℃ at a heating rate of 15 ℃/min in a vacuum atmosphere of a tubular furnace, and preserving heat for 4 hours to obtain a ZnO @ C sample. Adding the ZnO @ C composite material into 3mol/L HCl solution, stirring at 60 ℃ for 36 hours, carrying out suction filtration to obtain black powder, and drying in vacuum at 70 ℃ for 12 hours to obtain the hollow carbon material.
Step four: 60mg of the hollow carbon-carbon material is added into 60mL of ethanol solution, the concentration of the solution is ensured to be 1mg/mL, and the mixture is stirred for 30min to be dispersed in the solvent to obtain black suspension. 1.19g of tungsten hexachloride and 2.25g of thioacetamide were added to the above suspension and stirred magnetically for 2 h. Next, the above solution was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, the reaction temperature was 220 ℃ and the temperature was maintained for 48 hours. After the reaction is finished, cooling to room temperature, respectively washing the reacted turbid solution with ethanol and deionized water, and drying in vacuum at 60 ℃ for 12 h. Heat-treating the dried powder in a vacuum tube furnace filled with Ar at 800 deg.C for 3h at a temperature rise rate of 15 deg.C for 15min-1Obtaining WS2a/C composite electrode material.
Example 5
The method comprises the following steps: 0.6g of zinc acetate is dissolved in 20mL of ultrapure water, and the solution is stirred for 12min until the zinc acetate is dissolved to obtain a clear and transparent solution. Then, 3mL of ammonia water was added dropwise to the transparent solution, and after stirring for 25min, 20mL of ultrapure water was added thereto and stirred for 20min to obtain a uniform transparent solution. The solution was transferred to a 100mL stainless steel autoclave lined with Teflon at 180 ℃ for 24 h. After the reaction is finished, cooling to room temperature, respectively washing the reacted white turbid liquid with ethanol and deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnO material.
Step two: 0.25g of ZnO and 0.5g of 2-methylimidazole are added into a mixed solvent of 40mL of ultrapure water and 40mL of NMP, the volume ratio of the mixed solvent is ensured to be 1:1, the mixture is stirred for 20min to be fully mixed, and then the mixture is transferred into a wire-mouth bottle and is subjected to heat preservation at the temperature of 70 ℃ for 36 h. After the reaction is finished, washing the reacted white turbid liquid with ethanol and deionized water for three times respectively, and drying in vacuum at 70 ℃ for 12 hours to obtain the ZnO @ ZIF-8 material.
Step three: and (2) putting the ZnO @ ZIF-8 material into a porcelain boat, heating to 600 ℃ at a heating rate of 10 ℃/min in a vacuum atmosphere of a tube furnace, and preserving heat for 3h to obtain a ZnO @ C sample. Adding the ZnO @ C composite material into 2mol/L HCl solution, stirring for 24h at 50 ℃, carrying out suction filtration to obtain black powder, and drying for 12h in vacuum at 70 ℃ to obtain the hollow carbon material.
Step four: and (3) adding 45mg of the hollow carbon-carbon material into 45mL of ethanol solution to ensure that the concentration of the solution is 1mg/mL, and stirring for 20min to disperse the hollow carbon-carbon material in the solvent to obtain black suspension. 1.1g of tungsten hexachloride and 1.5g of thioacetamide were added to the above suspension and stirred magnetically for 2 h. Next, the above solution was transferred to a 100mL stainless steel autoclave lined with Teflon at 200 ℃ and held for 24 hours. After the reaction is finished, cooling to room temperature, respectively washing the reacted turbid solution with ethanol and deionized water, and drying in vacuum at 60 ℃ for 12 hours. Heat treating the dried powder in a vacuum tube furnace filled with Ar at 700 deg.C for 1.5h with a heating rate of 10 deg.C for min-1Obtaining WS2a/C composite electrode material.
In a word, the invention constructs a three-dimensional hollow carbon structure by using a hard template method and ZIF-8 derived carbon, and synthesizes the three-dimensional hollow WS by a solvothermal method2a/C composite electrode material. The three-dimensional hollow carbon layer structure and the nano structure can ensure high-speed migration of charges, thereby showing excellent sodium storage performance. The experimental operation process is simple, the raw material cost is low, the reaction temperature is easy to control, the used time is short, and the large-scale preparation can be realized in a short time.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. Three-dimensional hollow WS2The preparation method of the/C composite electrode material is characterized by comprising the following steps of:
the method comprises the following steps: dissolving zinc acetate in ultrapure water, stirring until the zinc acetate is dissolved to obtain a clear and transparent solution, dropwise adding ammonia water into the transparent solution, stirring, adding ultrapure water, continuously stirring to obtain a uniform transparent solution, then carrying out hydrothermal reaction, cooling, washing and drying to obtain a ZnO material;
step two: adding ZnO and 2-methylimidazole into a mixed solvent of ultrapure water and NMP, fully stirring to obtain a mixed solution, then heating the mixed solution for reaction, and after the reaction is finished, washing and drying to obtain a ZnO @ ZIF-8 material;
step three: carrying out heat treatment on the ZnO @ ZIF-8 material to obtain a ZnO @ C composite material, adding the ZnO @ C composite material into an HCl solution, heating, stirring, carrying out suction filtration, and drying to obtain a hollow carbon material;
step four: adding a hollow carbon material into an ethanol solution, and stirring to obtain a black suspension; adding tungsten hexachloride and thioacetamide into the suspension, stirring, carrying out solvothermal reaction, cooling, washing, drying and carrying out heat treatment to obtain the three-dimensional hollow WS2a/C composite electrode material.
2. The three-dimensional hollow WS according to claim 12The preparation method of the/C composite electrode material is characterized in that in the first step, the dosage ratio of zinc acetate to ultrapure water is (0.1-1) g: (5-30) mL; the volume ratio of the ammonia water to the ultrapure water is (0.1-5): (5-30).
3. The three-dimensional hollow WS according to claim 12The preparation method of the/C composite electrode material is characterized in that in the step one, the hydrothermal reaction temperature is 160-220 ℃, and the reaction time is 12-36 h.
4. The three-dimensional hollow WS of claim 12The preparation method of the/C composite electrode material is characterized in that in the second step, the mass ratio of ZnO to 2-methylimidazole is (0.1-0.5): (0.2-1); the volume ratio of ultrapure water to NMP in the mixed solvent was 1: 1.
5. The three-dimensional hollow WS of claim 12The preparation method of the/C composite electrode material is characterized in that in the second step, the heating temperature is 60-80 ℃, and the reaction time is 12-48 h.
6. The three-dimensional hollow WS of claim 12The preparation method of the/C composite electrode material is characterized in that in the third step, the heat treatment is heating to 500-800 ℃ at the heating rate of 5-15 ℃/min and keeping the temperature for 1-4 h; the concentration of the HCl solution is 0.5-3mol/L, and the HCl solution is stirred for 12-36h at the temperature of 30-60 ℃.
7. The three-dimensional hollow WS of claim 12The preparation method of the/C composite electrode material is characterized in that in the fourth step, the dosage ratio of the hollow carbon material to the ethanol is (30-60) mg: (30-60) mL, wherein the mass ratio of the tungsten hexachloride to the thioacetamide is (0.55-1.19): (0.75-2.25).
8. The three-dimensional hollow WS of claim 12The preparation method of the/C composite electrode material is characterized in that in the fourth step, the solvothermal reaction temperature is 180-220 ℃, and the reaction time is 12-48 h; the heat treatment is carried out for 1-3h at the temperature of 500-800 ℃ under the Ar gas atmosphere, and the heating rate is 5-15 ℃ for min-1。
9. Three-dimensional hollow WS prepared by the preparation method according to any one of claims 1 to 82a/C composite electrode material.
10. The three-dimensional hollow WS of claim 92The application of the/C composite electrode material in the preparation of a sodium-ion battery.
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