CN111874962A - Nickel-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof - Google Patents
Nickel-doped tungsten disulfide/graphene oxide 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 62
- 239000007772 electrode material Substances 0.000 title claims abstract description 55
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 36
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 27
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 19
- 239000002135 nanosheet Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 42
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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Abstract
The invention discloses a nickel-doped tungsten disulfide/graphene oxide composite electrode material and a preparation method and application thereof, and belongs to the technical field of tungsten disulfide nano material preparation. The preparation method is realized by a solvothermal reaction one-step method: growing tungsten disulfide nanosheets by taking graphene oxide as a matrix, and doping nickel at the same time to prepare the nickel-doped tungsten disulfide/graphene oxide composite electrode material. The preparation method has simple and controllable operation process and low cost, and can realize large-scale production. The invention also discloses the nickel-doped tungsten disulfide/graphene oxide composite electrode material prepared by the method, because the graphene oxide has larger specific surface area and better flexibility, the agglomeration of tungsten disulfide nanosheets is inhibited, the cycling stability of the material is improved, and because the nickel doping improves the conductivity of the material, increases the number of active positioning points and greatly improves the rate capability of the material, the nickel-doped tungsten disulfide/graphene oxide composite electrode material can be applied to a negative electrode material of a battery, and has wide research value and application value in the electrochemical field.
Description
Technical Field
The invention belongs to the technical field of preparation of tungsten disulfide nano materials, and relates to a nickel-doped tungsten disulfide/graphene oxide composite electrode material as well as a preparation method and application thereof.
Background
Tungsten disulfide (WS)2) The nano-sheet is a typical two-dimensional layered transition metal dichalcogenide, covalent bonds (S-W-S) with strong acting force are arranged in the layer, van der Waals force with weak acting force is arranged between the layers, the interlayer spacing is larger and about 0.62nm, the diffusion of metal ions with smaller size in a matrix is facilitated, and the special structure can promote the further reaction of lithium ions and sodium ions and the matrix material. WS2The structure of the nanoplatelets is similar to graphite, where 2D monolayers are 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 and lithium ions can be readily transported from WS2Insertion and extraction into the nanosheet, therefore WS2Also considered as a potential anode material.
Although WS2Has larger specific surface area, but has lower electron mobility and can provide smaller capacitance. And at the charge and discharge thereofThe large volume expansion during the process causes the collapse of the structure, resulting in poor cyclic stability.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nickel-doped tungsten disulfide/graphene oxide composite electrode material, and a preparation method and application thereof. The preparation method provided by the invention utilizes a solvothermal reaction one-step method to obtain the nickel-doped tungsten disulfide/graphene oxide composite electrode material. 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.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a nickel-doped tungsten disulfide/graphene oxide composite electrode material, which comprises the following steps:
1) uniformly dispersing sodium tungstate dihydrate, thiourea and nickel nitrate hexahydrate in an ethanol solution to obtain a suspension; carrying out solvothermal reaction on the suspension, and cooling to obtain a product; centrifugally washing the product, and then freeze-drying and collecting powder to obtain the nickel-doped tungsten disulfide/graphene oxide composite material;
2) and calcining and annealing the nickel-doped tungsten disulfide/graphene oxide composite material to obtain the nickel-doped tungsten disulfide/graphene oxide composite electrode material.
Preferably, in the step 1), the reaction feed ratio of the sodium tungstate dihydrate, the thiourea and the ethanol is 1mol (5-15) mol (30-60) mL, and the reaction feed ratio of the sodium tungstate dihydrate and the nickel nitrate hexahydrate is (5-15) 1.
Preferably, in the step 1), the temperature of the solvothermal reaction is 200-240 ℃ and the time is 12-48 h.
Preferably, in the step 1), the temperature of freeze drying is-40 to-70 ℃, the time is 8 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
Preferably, in step 2), the calcination annealing treatment operation specifically includes: the calcination temperature is 600-900 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-4 h.
The invention also discloses the nickel-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method.
Preferably, the composite electrode material is in the range of 1A-g-1After the current density of (1) is cycled for 100 circles, the capacity retention rate is 71%; at 20 A.g-1Has a capacity of 128mAh g at a current density of (1)-1When the current returns to a low current, the capacity of the capacitor returns to 354mAh g-1。
The invention also discloses an application of the nickel-doped tungsten disulfide/graphene oxide composite electrode material as a battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses nickel-doped tungsten disulfide/graphene oxide (WS)2The method for preparing the/GO) composite electrode material successfully prepares the nickel-doped WS by utilizing a one-step solvothermal method2the/GO composite material is then calcined to obtain the nickel-doped WS2a/GO composite electrode material. In the preparation method, Graphene Oxide (GO) is used as a matrix to grow tungsten disulfide (WS)2) Nanosheet, inhibiting WS2Due to the agglomeration among the nano sheets, the circulation stability of the material is effectively improved; by doping nickel into WS2the/GO composite material improves the conductivity of the material, increases the active positioning points and greatly improves the rate capability of the finally obtained material. The preparation method has the advantages of simple operation process, low raw material cost, easily controlled reaction temperature and short time consumption.
The invention also discloses nickel-doped tungsten disulfide/graphene oxide (WS) prepared by adopting the preparation method2/GO) composite electrode material. In the material, graphene oxide with large specific surface area and good flexibility is utilized and can be used as growth WS2An ideal substrate of the nano sheet, so that WS can be effectively inhibited by the composite graphene oxide2Due to the agglomeration among the nano sheets, the circulation stability of the nano sheets is effectively improved; meanwhile, through doping of the metal element nickel, the conductivity of the material is improved, the number of active positioning points is increased to improve the rate capability, and the problem that tungsten disulfide is used as a semi-product is solvedPoor conductivity of the conductor material, lagged electrochemical reaction in the process of charge-discharge reaction and poor rate capability. Therefore, the nickel-doped WS prepared by the invention2the/GO composite electrode material has excellent and stable electrochemical performance. Causing it. .
Furthermore, the cycle performance test proves that the nickel-doped tungsten disulfide/graphene oxide (WS) prepared by the invention2/GO) composite electrode material at 1A g-1After the current density of (1) is cycled for 100 circles, the capacity retention rate is 71%; at 20 A.g-1Has a capacity of 128mAh g at a current density of (1)-1When the current returns to a low current, the capacity of the capacitor returns to 354mAh g-1And has excellent rate performance.
The invention also discloses the nickel-doped tungsten disulfide/graphene oxide (WS)2The application of the/GO) composite electrode material as a battery negative electrode material. According to experimental characterization, the composite electrode material has excellent rate performance and capacity retention rate, so that the composite electrode material can be applied to a battery cathode material, and has wide research value and application value in the electrochemical field.
Drawings
FIG. 1 shows the preparation of nickel-doped WS prepared in example 3 of the present invention2An X-ray diffraction (XRD) pattern of the/GO composite electrode material;
FIG. 2 shows the preparation of Ni-doped WS prepared in example 3 of the present invention2Scanning Electron Microscope (SEM) pictures of the/GO composite electrode material; wherein, (a) is a low-power graph and (b) is a high-power graph;
FIG. 3 shows the preparation of Ni-doped WS prepared in example 3 of the present invention2Transmission Electron Microscope (TEM) photograph of the/GO composite electrode material; wherein, (a) is a low-power graph and (b) is a high-power graph;
FIG. 4 shows the preparation of nickel-doped WS according to the present invention2An energy spectrum of the/GO composite electrode material; (a) selecting the morphology; (b) c, S, W, Ni element distribution; (c) is element C; (d) is an S element; (e) is Ni element; (f) is a W element;
FIG. 5 shows the preparation of nickel-doped WS according to the present invention2Circulation of/GO composite electrode material as negative electrode material of sodium ion batteryA performance map;
FIG. 6 shows the preparation of nickel-doped WS according to the present invention2the/GO composite electrode material is used as a multiplying power performance diagram of a sodium ion battery cathode material.
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 sequences other 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 nickel-doped tungsten disulfide/graphene oxide (WS)2The preparation method of the/GO) composite electrode material comprises the following steps:
the method comprises the following steps: and adding a certain amount of sodium tungstate dihydrate and thiourea into 30-60 mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 500-800 r/min, and the stirring time is 30-120 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1 (5-15).
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be (5-15): 1, stirring at a speed of 500-800 r/min, and stirring for 10-30 min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the temperature of 200-240 ℃ for 12-48 h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4-6 times, and drying the product in a freeze dryer at the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for 8-12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 600-900 ℃, the heat preservation time is 1-4 h, and the heating rate is 5-20 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
The present invention is described in further detail below with reference to specific examples:
example 1
The method comprises the following steps: and adding a certain amount of sodium tungstate dihydrate and thiourea into 60mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 500-800 r/min, and the stirring time is 30-120 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 5.
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be 5:1, and stirring for 30min at a stirring speed of 500 r/min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 12h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4 times, and drying the product in a freeze dryer with the temperature of-40 ℃ and the vacuum degree of 40Pa for 8 hours.
Step five: taking the dried sample, and annealing in a low-temperature tube furnaceFire treatment, wherein the calcining temperature is 900 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
Example 2
The method comprises the following steps: adding a certain amount of sodium tungstate dihydrate and thiourea into 30mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 800r/min, and the stirring time is 120 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 8.
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be 10:1, and stirring for 30min at a stirring speed of 500 r/min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 240 ℃, the reaction time is 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 35Pa for 12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 600 ℃, the heat preservation time is 1h, and the heating rate is 10 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
Example 3
The method comprises the following steps: adding a certain amount of sodium tungstate dihydrate and thiourea into 60mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 800r/min, and the stirring time is 120 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 10.
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be 10:1, and stirring for 15min at a stirring speed of 700 r/min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 25Pa for 12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 800 ℃, the heat preservation time is 2h, and the heating rate is 10 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
Example 4
The method comprises the following steps: adding a certain amount of sodium tungstate dihydrate and thiourea into 45mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 600r/min, and the stirring time is 120 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 15.
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be 15:1, and stirring for 30min at a stirring speed of 800 r/min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at 240 ℃ for 48 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 10Pa for 12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 600 ℃, the heat preservation time is 4h, and the heating rate is 20 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
Example 5
The method comprises the following steps: adding a certain amount of sodium tungstate dihydrate and thiourea into 50mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 700r/min, and the stirring time is 60 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 12.
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be 9:1, and stirring for 25min at a stirring speed of 800 r/min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 36h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 10Pa for 12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 600 ℃, the heat preservation time is 1h, and the heating rate is 5 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
Example 6
The method comprises the following steps: adding a certain amount of sodium tungstate dihydrate and thiourea into 50mL of ethanol solution, and magnetically stirring until the sodium tungstate dihydrate and the thiourea are completely dissolved to form a blue-black suspension A, wherein the stirring speed is 700r/min, and the stirring time is 60 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 12.
Step two: adding nickel nitrate hexahydrate into the solution A, stirring until the nickel nitrate hexahydrate is completely dissolved, controlling the molar ratio of sodium tungstate dihydrate to nickel nitrate hexahydrate to be 9:1, and stirring for 25min at a stirring speed of 800 r/min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 36h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer with the temperature of-60 ℃ and the vacuum degree of 35Pa for 10 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 700 ℃, the heat preservation time is 1h, and the heating rate is 5 ℃/min. Obtaining nickel-doped WS2a/GO composite electrode material.
In conclusion, the invention utilizes a one-step solvothermal and high-temperature calcination method to obtain the nickel-doped WS2a/GO composite electrode material. The experimental operation process is simple, the raw material cost is low, the reaction temperature is easy to control, and the used time is short. GO is used as a substrate to grow tungsten disulfide nanosheets, and GO has a large specific surface area and good flexibility and can effectively inhibit WS2The agglomeration among the nano sheets effectively improves the circulation stability of the nano sheets. Doping of nickel into WS2the/GO composite electrode material improves the conductivity of the material, increases the active positioning points, greatly improves the rate capability of the material,
the invention is described in further detail below with reference to the accompanying drawings:
reference is made to FIG. 1 for nickel-doped WS prepared in example 32An X-ray diffraction (XRD) pattern of the/GO composite electrode material; sample and WS of hexagonal system having JCPDS number 08-02372The structures are consistent, which shows that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists.
FIG. 2 shows the nickel-doped WS prepared in example 32Scanning Electron Microscope (SEM) pictures of the/GO composite electrode material. The tungsten disulfide nanosheets uniformly grow on the surface of the graphene oxide.
FIG. 3 shows the preparation of nickel-doped WS prepared in example 32And (4) a Transmission Electron Microscope (TEM) picture of the/GO composite electrode material. The result thereof is consistent with the scanning result,
FIG. 4 shows the preparation of Ni-doped WS2The energy spectrum of the/GO composite electrode material can see that W, S, C, Ni and other elements are uniformly distributed, and the combination of the peaks of nickel or nickel compounds which are not obvious in XRD indicates that nickel exists in a doped form.
FIGS. 5 and 6 show the doping of WS with Ni2the/GO composite electrode material is used as a sodium ion battery cathode material and has cycle performance and rate capability. It can be seen that it is 1 A.g-1After 100 cycles at the current density of (3), the capacity retention rate is 71%. And it has excellent rate capability of 20 A.g-1Has a capacity of 128mAh g at a current density of (1)-1. When the current returns to a low current, the capacity of the capacitor is again raised to 354mAh g-1。
Analysis of the samples with a Japan science D/max2000 PCX-ray diffractometer (Nickel-doped WS)2/GO composite electrode material), found with hexagonal WS of JCPDS numbers 08-02372The structures are consistent, which shows that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists. The sample is observed by a Field Emission Scanning Electron Microscope (FESEM) and a transmission electron microscope, and the tungsten disulfide nanosheet can be uniformly grown on the graphene oxide. And the prepared product has better dispersibility and uniform size distribution. The observed appearance and scanning of the transmission are consistent, and the uniform distribution of W, S, C, Ni elements and the like can be seen from the energy spectrum test, which indicates that the nickel-doped WS is successfully synthesized2The electrochemical performance test of the/GO composite electrode material shows that the structure has good cycling stability and excellent rate performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of a nickel-doped tungsten disulfide/graphene oxide composite electrode material is characterized by comprising the following steps:
1) uniformly dispersing sodium tungstate dihydrate, thiourea and nickel nitrate hexahydrate in an ethanol solution to obtain a suspension; carrying out solvothermal reaction on the suspension, and cooling to obtain a product; centrifugally washing the product, and then freeze-drying and collecting powder to obtain the nickel-doped tungsten disulfide/graphene oxide composite material;
2) and calcining and annealing the nickel-doped tungsten disulfide/graphene oxide composite material to obtain the nickel-doped tungsten disulfide/graphene oxide composite electrode material.
2. The preparation method of the nickel-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the reaction charge ratio of sodium tungstate dihydrate, thiourea and ethanol is 1mol (5-15) mol (30-60) mL, and the reaction charge molar ratio of sodium tungstate dihydrate and nickel nitrate hexahydrate is (5-15) 1.
3. The preparation method of the nickel-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the temperature of the solvothermal reaction is 200-240 ℃ and the time is 12-48 h.
4. The preparation method of the nickel-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the temperature of freeze drying is-40 to-70 ℃, the time is 8 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
5. The method for preparing the nickel-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 2), the calcination annealing treatment operation specifically comprises: the calcination temperature is 600-900 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-4 h.
6. The nickel-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method of any one of claims 1 to 5.
7. The nickel-doped tungsten disulfide/graphene oxide composite electrode material as claimed in claim 6, wherein the composite electrode material is between 1A-g-1After the current density of (1) is cycled for 100 circles, the capacity retention rate is 71%; at 20 A.g-1Has a capacity of 128mAh g at a current density of (1)-1When the current returns to a low current, the capacity of the capacitor returns to 354mAh g-1。
8. Use of the nickel-doped tungsten disulfide/graphene oxide composite electrode material of claim 6 or 7 as a battery negative electrode material.
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