CN113097486A - SnSe quantum dot/CFF compound and preparation method and application thereof - Google Patents
SnSe quantum dot/CFF compound and preparation method and application thereof Download PDFInfo
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- CN113097486A CN113097486A CN202110353783.1A CN202110353783A CN113097486A CN 113097486 A CN113097486 A CN 113097486A CN 202110353783 A CN202110353783 A CN 202110353783A CN 113097486 A CN113097486 A CN 113097486A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- -1 CFF compound Chemical class 0.000 title claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 66
- 239000004917 carbon fiber Substances 0.000 claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000004729 solvothermal method Methods 0.000 claims abstract description 13
- 229940071182 stannate Drugs 0.000 claims abstract description 10
- 125000005402 stannate group Chemical group 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 34
- 239000002131 composite material Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 18
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 14
- 239000005642 Oleic acid Substances 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910001414 potassium ion Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910020462 K2SnO3 Inorganic materials 0.000 claims description 3
- 229910020212 Na2SnO3 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 abstract description 9
- 239000010406 cathode material Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 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
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 4
- 239000006258 conductive agent Substances 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000007767 bonding agent Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- LYZMBUYUNBCSMW-UHFFFAOYSA-N selenium(2-);tin(2+) Chemical compound [Se-2].[Sn+2] LYZMBUYUNBCSMW-UHFFFAOYSA-N 0.000 description 47
- 239000012071 phase Substances 0.000 description 9
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical class [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The invention discloses an SnSe quantum dot/CFF compound and a preparation method and application thereof, wherein the preparation method takes a flexible matrix carbon fiber felt as a carbon matrix, stannate as a tin source and a reducing solvent as a reducing agent, and adopts a simple one-step solvothermal method to prepare the pure-phase SnSe quantum dot/CFF compound, the carbon fiber felt has a larger specific surface area as the matrix, and by preparing a self-supporting electrode, the addition of a bonding agent and a conductive agent is not needed in the process of synthesizing an electrode material, so that the proportion of active substances is large, and the existence of the carbon fiber felt can improve the conductivity of the cathode material and can be used as sodium and potassium for improving the conductivity of the cathode materialThe ionic electrode material has better electrochemical performance; addition of a reducing agent is effective with Sn2+Complexing, controlling the size of the product and being more effective for improving the electrochemical performance. The preparation method is simple, high in repeatability, short in preparation period and low in reaction temperature, reduces energy consumption and production cost, and is suitable for large-scale production and preparation.
Description
Technical Field
The invention belongs to the field of battery material preparation, and particularly relates to a SnSe quantum dot/CFF compound and a preparation method and application thereof.
Background
The lithium ion battery with high energy density becomes a research hotspot due to the rapid development of electric automobiles, smart power grids and the like, but simultaneously, the reserve of lithium resources is limited, so that sodium in the same main group with lithium becomes a secondary battery which can replace the lithium ion battery most possibly. However, sodium ion batteries have a problem of hindering the development thereof, and the energy density of electrode materials reported so far is lower than that of lithium ion batteries of the same kind of electrode materials, and therefore, it is very important to develop secondary battery electrode materials having high energy density.
The group IV-VI semiconductor compounds being tin selenides capable of forming compounds of various stoichiometric ratios, e.g. SnSe, SnSe2And Sn2Se3Wherein SnSe and SnSe2Has wider application prospect. Stannous selenide (SnSe) is an important semiconductor material, has a forbidden band width of about 0.9eV, has good electrical and optical properties, and is widely applied to infrared photoelectric instruments, memory change-over switches, solid-phase media of holograms, research on electrode materials of lithium ion/sodium ion batteries, absorption materials of thin-film solar cells and the like. Therefore, research on stannous selenide is a hot direction. In recent years, the lithium ion secondary battery has been used as a negative electrode of a sodium ion/potassium ion batteryThe material becomes the hot spot of research.
However, currently, stannous selenide as a cathode material of a secondary ion battery is less researched, mainly because the theoretical capacity of the stannous selenide as the cathode material of the sodium and potassium ion battery is 738mAh g-1Similar to other alloy materials, the alloy material also has large volume expansion during charge and discharge, so that the stability of the alloy material is poor. According to the literature, it is known that in order to improve the electronic conductivity of tin selenide and relieve the volume expansion, many researchers compound tin selenide and a carbon material, so that on one hand, the conductivity of the composite material is improved, and on the other hand, the carbon material serving as a matrix can relieve the volume expansion problem in the discharge process to a certain extent.
In recent years, studies on the preparation of battery negative electrode materials using carbon matrix materials such as carbon fiber cloth and carbon fiber felt have been increasing, for example: the method comprises the following steps of taking tin powder and selenium powder as raw materials, taking conductive carbon black as a carbon source, preparing a composite material of tin selenide and carbon by adopting a ball milling method to serve as a lithium/sodium ion battery cathode, and improving the conductivity of the composite material to a certain extent; long Zhang and the like enable tin selenide nano-particles to grow inside the carbon fibers by a ball-milling and electro-deposition method, greatly improve the structural stability of the composite material and relieve the volume expansion in the charging and discharging process. Therefore, the method is a means for effectively improving the electrochemical performance of the tin selenide by compounding with carbon. However, the preparation method disclosed at present is complicated in process and even uses large-scale expensive equipment. Therefore, it is very important to develop a method which is simple in preparation method and can effectively regulate and control the structure of the product.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the SnSe quantum dot/CFF compound and the preparation method and the application thereof, the preparation method is simple, the repeatability is high, the prepared SnSe quantum dot/CFF compound is granular, SnSe uniformly grows on the surface of a carbon fiber felt, and the SnSe quantum dot/CFF compound has better electrochemical performance as a sodium ion or potassium ion electrode material.
In order to achieve the above object, the present invention provides a method for preparing an SnSe quantum dot/CFF complex, comprising the steps of:
1) cleaning a carbon fiber felt and then soaking the carbon fiber felt in concentrated nitric acid;
2) adding 0.06836-6.836 g of stannate and 0.069-0.69 g of surfactant into 20-80 mL of solvent, and stirring until the stannate and the surfactant are completely dissolved to obtain a solution A;
3) adding 0.0237-2.37 g of selenium powder into 3-9 mL of reducing solvent, stirring until the selenium powder is completely dissolved to obtain a solution B, dropwise adding the solution B into the solution A, and uniformly stirring to obtain a mixed solution C;
4) and taking out the carbon fiber felt soaked in the concentrated nitric acid, immersing the carbon fiber felt in the mixed solution C, carrying out solvothermal reaction for 12-24 h at the temperature of 120-200 ℃, taking out the carbon fiber felt after the reaction is finished and cooling, and cleaning and drying the carbon fiber felt to obtain the SnSe quantum dot/CFF composite.
Further, the carbon fiber felt is sequentially placed into acetone, absolute ethyl alcohol and deionized water in the step 1) to be subjected to ultrasonic cleaning for 10-20 min respectively.
Further, the soaking time of the carbon fiber felt in concentrated nitric acid is 2-5 h.
Further, the stannate is K2SnO3Or Na2SnO3。
Further, the surfactant is oleic acid, and the solvent is ethylene glycol or glycerol.
Further, the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution.
Further, magnetic stirring is adopted for stirring, the stirring speed is 400-900 r/min, and the stirring time is 20-80 min.
Furthermore, the solvothermal reaction is carried out in a reaction kettle, and the filling degree of the hydrothermal kettle is controlled to be 30-70%.
The invention also provides an SnSe quantum dot/CFF compound which is prepared by the preparation method of the SnSe quantum dot/CFF compound, wherein the SnSe quantum dots are uniformly distributed in the carbon fiber felt, the SnSe quantum dots are pure phase SnSe particles, and the size of the pure phase SnSe particles is 8-10 nm.
The invention also provides application of the SnSe quantum dot/CFF composite as a negative electrode material in a sodium ion battery or a potassium ion battery.
Compared with the prior art, the pure-phase SnSe quantum dot/CFF composite is prepared by taking the flexible matrix carbon fiber felt as a carbon matrix, stannate as a tin source and a reducing solvent as a reducing agent through a simple one-step solvothermal method, and the size of the SnSe nano-particles is about 8-10 nm. The reducing agent can reduce the selenium powder to provide Se2-The carbon fiber felt replaces the traditional metal current collector to serve as a matrix and has larger specific surface area, and the addition of a bonding agent and a conductive agent is not needed in the process of synthesizing the electrode material by preparing the self-supporting electrode, so that the active substance accounts for a large proportion, and meanwhile, the conductivity of the cathode material can be improved due to the existence of the carbon fiber felt, and the carbon fiber felt has better electrochemical performance when serving as a sodium/potassium ion electrode material; on the other hand, addition of a reducing agent is effective with Sn2+Complexing, controlling the size of the product, and the nano material is more effective for improving the electrochemical performance. In addition, the preparation method adopted by the invention is simple, high in repeatability, short in preparation period and low in reaction temperature, reduces energy consumption and production cost, and is suitable for large-scale production and preparation.
The invention prepares a pure-phase SnSe quantum dot/CFF compound, the carbon fiber CFF is a uniformly distributed axial structure, the SnSe quantum dots are uniformly distributed on the surface of a carbon fiber felt, the SnSe quantum dots are pure-phase SnSe particles with the size of about 8-10 nm, the compound can be used as a sodium ion or potassium ion battery cathode material, the carbon fiber felt is directly used as a substrate, the sodium ion battery cathode material can be directly obtained through self-assembly, materials such as a metal current collector, an adhesive, a conductive agent and the like are not needed, the active substance accounts for a large proportion, the compound is not easy to be pulverized and fall off from the substrate in the charging and discharging process, the charging and discharging performance of the battery can be well improved, the excellent conductivity of the carbon fiber felt and the high sodium storage capacity of tin selenide are fully utilized, the energy density of the cathode material is greatly improved, and the capacity attenuation problem caused by volume expansion of the tin selenide under high cycle number is improved, has better cycling stability and larger research value.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a composite of example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the composite of example 1 of the present invention.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. 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 application.
The invention provides a preparation method of a SnSe quantum dot/CFF compound, which comprises the following steps:
1) firstly, sequentially adding carbon fiber felts into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic cleaning for 10-20 min, and soaking in concentrated nitric acid after cleaning; then 0.06836-6.836 g of stannate and 0.069-0.69 g of surfactant are added into 20-80 mL of solvent, and the mixture is stirred until the mixture is completely dissolved to form a solution A, wherein the stannate is K2SnO3Or Na2SnO3The surfactant is oleic acid, and the solvent is glycol or glycerol; adding 0.0237-2.37 g of selenium powder into 3-9 mL of reducing solvent, and uniformly stirring to obtain a solution B, wherein the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the concentrated nitric acid, and soaking the carbon fiber felt into the mixed solution C for 2-5 hours;
2) and transferring the mixed solution C and the carbon fiber felt into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor to react for 12-24 h at 120-200 ℃, cooling to room temperature along with the furnace after the reaction is finished, repeatedly washing with absolute ethyl alcohol to obtain a compound, and drying the separated product to obtain the SnSe quantum dot/CFF compound. Preferably, magnetic stirring is adopted for stirring, the stirring speed is 400-900 r/min, the stirring time is 20-80 min, and the filling degree of the hydrothermal kettle is controlled to be 30-70%.
The invention also provides the SnSe quantum dot/CFF composite prepared by the preparation method, wherein the CFF in the composite is in an evenly distributed axial structure, the SnSe quantum dots are evenly distributed on the surface of the CFF, the SnSe quantum dots are pure-phase SnSe particles, and the size of the particles is about 8-10 nm. The composite has better electrochemical performance when being used as a negative electrode material of a sodium or potassium ion battery, and also can be used as a photocatalytic material, thereby having better photocatalytic performance.
The present invention will be described with reference to specific examples.
Example 1:
the preparation method comprises the following steps: firstly, sequentially adding carbon fiber felts into acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning and then soaking in concentrated nitric acid; 0.06836g K will then be2SnO3And 0.069g of oleic acid into 20ml of ethylene glycol, and stirring until the oleic acid is completely dissolved to form a solution A; secondly, adding 0.0237g of selenium powder into 3ml of ethylenediamine, and stirring until the selenium powder is completely dissolved to obtain a solution B; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; and finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the mixed solution C, carrying out solvothermal reaction on the mixed solution C and the carbon fiber felt for 18 hours at 120 ℃, and separating a product to obtain the SnSe quantum dot/CFF composite.
The sample (SnSe quantum dot/CFF composite) was analyzed by a Japanese science D/max2000 PCX-ray diffractometer, and as a result, referring to FIG. 1, it was found to be consistent with the SnSe structure of JCPDS No. 48-1224, indicating that pure phase SnSe quantum dot particles were prepared. The sample is observed by a Field Emission Scanning Electron Microscope (FESEM), and the result is shown in figure 2, so that the prepared tin selenide quantum dots are uniformly dispersed on the surface of the shaft-shaped carbon fiber felt, and the SnSe particles in the SnSe quantum dot/CFF compound are nanoparticles with the size of about 8-10 nm.
Example 2:
the preparation method comprises the following steps: firstly, adding the carbon fiber felt into acetone, absolute ethyl alcohol and deionized water in sequenceRespectively ultrasonically cleaning and soaking in concentrated nitric acid; 0.6836g K will then be2SnO3And 0.6g of oleic acid into 40ml of ethylene glycol, and stirring until the oleic acid is completely dissolved to form a solution A; secondly, adding 0.237g of selenium powder into 5ml of hydrazine hydrate, and stirring until the selenium powder is completely dissolved to obtain a solution B; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; and finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the mixed solution C, carrying out solvothermal reaction on the mixed solution C and the carbon fiber felt for 15 hours at 160 ℃, and separating a product to obtain the SnSe quantum dot/CFF composite.
Example 3:
the preparation method comprises the following steps: firstly, sequentially adding carbon fiber felts into acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning and then soaking in concentrated nitric acid; 1.3672g of Na are then added2SnO3And 0.37g oleic acid to 60ml glycerol, stirred until completely dissolved to form solution A; secondly, adding 0.474g of selenium powder into 6ml of hydrazine hydrate, and stirring until the selenium powder is completely dissolved to obtain a solution B; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; and finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the mixed solution C, carrying out solvothermal reaction on the mixed solution C and the carbon fiber felt at 180 ℃ for 12h, and separating a product to obtain the SnSe quantum dot/CFF compound.
Example 4:
the preparation method comprises the following steps: firstly, sequentially adding carbon fiber felts into acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning and then soaking in concentrated nitric acid; 2.7344g of Na are then added2SnO3And 0.69g of oleic acid into 70ml of ethylene glycol, and stirring until the oleic acid is completely dissolved to form a solution A; secondly, adding 0.0237g of selenium powder into 3ml of sodium borohydride aqueous solution, and stirring until the selenium powder is completely dissolved to obtain solution B; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; and finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the mixed solution C, carrying out solvothermal reaction on the mixed solution C and the carbon fiber felt for 18 hours at 120 ℃, and separating a product to obtain the SnSe quantum dot/CFF compound.
Example 5:
preparation methodThe method comprises the following steps: firstly, sequentially adding carbon fiber felts into acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning and then soaking in concentrated nitric acid; 6.836g K will then be2SnO3And 0.69g of oleic acid into 70ml of ethylene glycol, and stirring until the oleic acid is completely dissolved to form a solution A; secondly, adding 2.37g of selenium powder into 8ml of triethanolamine, and stirring until the selenium powder is completely dissolved to obtain a solution B; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; and finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the mixed solution C, carrying out solvothermal reaction on the mixed solution C and the carbon fiber felt for 10 hours at 200 ℃, and separating a product to obtain the SnSe quantum dot/CFF compound.
Example 6:
the preparation method comprises the following steps: firstly, sequentially adding carbon fiber felts into acetone, absolute ethyl alcohol and deionized water to respectively carry out ultrasonic cleaning, and soaking in concentrated nitric acid after cleaning; 3.418g of Na are then added2SnO3And 0.2g of oleic acid into 80mL of glycerol, and stirring until the oleic acid and the glycerol are completely dissolved to form a solution A; secondly, adding 1.185g of selenium powder into 9mL of sodium borohydride aqueous solution, and uniformly stirring to obtain a solution B; dropwise adding the solution B into the solution A again to form a mixed solution C, and uniformly stirring; and finally, taking out the carbon fiber felt soaked in the concentrated nitric acid, adding the carbon fiber felt into the mixed solution C, immersing the mixed solution C and the carbon fiber felt into solvothermal reaction for 24 hours at the temperature of 140 ℃, and separating a product to obtain the SnSe quantum dot/CFF composite.
The invention takes ethylene glycol or glycerol as a solvent, and prepares a pure-phase SnSe quantum dot/CFF compound by adopting a one-step solvothermal method, wherein SnSe is a pure-phase nanoparticle with the size of about 8-10 nm and is uniformly dispersed on the surface of a carbon fiber felt. The preparation method is simple, the period is short, the carbon fiber felt replaces the traditional metal current collector to serve as a matrix to have a larger specific surface area by preparing the self-supporting electrode, an adhesive and a conductive agent are not needed to be added in the process of synthesizing the electrode material, the active substance accounts for a large proportion, meanwhile, due to the existence of the carbon fiber felt, the conductivity of the SnSe is improved, the structural stability of the composite material is improved, and the composite material has a larger research value when being used as a negative electrode material of a sodium-potassium ion battery. The composite material can be used as a photocatalytic material and an electrode material, and has better photocatalytic and electrochemical properties. The invention has simple process, high repeatability, short preparation period and low reaction temperature, reduces energy consumption and production cost, and is suitable for large-scale production and preparation.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of the SnSe quantum dot/CFF compound is characterized by comprising the following steps:
1) cleaning a carbon fiber felt and then soaking the carbon fiber felt in concentrated nitric acid;
2) adding 0.06836-6.836 g of stannate and 0.069-0.69 g of surfactant into 20-80 mL of solvent, and stirring until the stannate and the surfactant are completely dissolved to obtain a solution A;
3) adding 0.0237-2.37 g of selenium powder into 3-9 mL of reducing solvent, stirring until the selenium powder is completely dissolved to obtain a solution B, dropwise adding the solution B into the solution A, and uniformly stirring to obtain a mixed solution C;
4) and taking out the carbon fiber felt soaked in the concentrated nitric acid, immersing the carbon fiber felt in the mixed solution C, carrying out solvothermal reaction for 12-24 h at the temperature of 120-200 ℃, taking out the carbon fiber felt after the reaction is finished and cooling, and cleaning and drying the carbon fiber felt to obtain the SnSe quantum dot/CFF composite.
2. The SnSe quantum dot/CFF composite preparation method according to claim 1, wherein in the step 1), the carbon fiber felt is sequentially placed in acetone, absolute ethyl alcohol and deionized water to be subjected to ultrasonic cleaning for 10-20 min.
3. The method for preparing the SnSe quantum dot/CFF composite according to claim 1, wherein the carbon fiber felt is soaked in concentrated nitric acid for 2-5 h.
4. The method of claim 1, wherein the stannate is K2SnO3Or Na2SnO3。
5. The method of claim 1, wherein the surfactant is oleic acid and the solvent is ethylene glycol or glycerol.
6. The method of claim 1, wherein the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate, or aqueous sodium borohydride solution.
7. The method for preparing the SnSe quantum dot/CFF compound as claimed in claim 1, wherein the stirring is magnetic stirring, the stirring speed is 400-900 r/min, and the stirring time is 20-80 min.
8. The method for preparing the SnSe quantum dot/CFF composite according to claim 1, wherein the solvothermal reaction is carried out in a reaction kettle, and the filling degree of the hydrothermal kettle is controlled to be 30-70%.
9. The SnSe quantum dot/CFF composite is characterized by being prepared by the preparation method of the SnSe quantum dot/CFF composite according to any one of claims 1 to 8, wherein the SnSe quantum dots are uniformly distributed in the carbon fiber felt, the SnSe quantum dots are pure-phase SnSe particles, and the size of the pure-phase SnSe particles is 8-10 nm.
10. Use of the SnSe quantum dot/CFF composite of claim 9 as a negative electrode material in a sodium ion battery or a potassium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583160A (en) * | 2022-03-09 | 2022-06-03 | 广东工业大学 | Tin selenide nanosheet array/carbon cloth composite cathode material structure for sodium ion battery |
| CN114843464A (en) * | 2022-04-21 | 2022-08-02 | 陕西科技大学 | Three-dimensional cross-linked structure SnSe/3D r-GO composite material and preparation method and application thereof |
| CN114890392A (en) * | 2022-06-08 | 2022-08-12 | 陕西科技大学 | Carbon-coated tin selenide composite cross-linked three-dimensional graphene and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482201A (en) * | 2017-08-15 | 2017-12-15 | 三峡大学 | A kind of SnSe/ carbon cloths flexibility negative material and preparation method thereof |
| CN109742353A (en) * | 2018-12-29 | 2019-05-10 | 陕西科技大学 | A kind of SnSe quantum dot/r-GO compound and its preparation method and application |
| CN109786717A (en) * | 2019-01-30 | 2019-05-21 | 陕西科技大学 | A kind of sodium-ion battery cathode SnO2The preparation method of/carbon cloth composite material |
| CN109786716A (en) * | 2019-01-30 | 2019-05-21 | 陕西科技大学 | A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode |
| CN110190246A (en) * | 2019-06-24 | 2019-08-30 | 陕西科技大学 | A kind of Sb2O3The preparation method of/carbon felt flexibility anode material of lithium-ion battery |
-
2021
- 2021-04-01 CN CN202110353783.1A patent/CN113097486A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482201A (en) * | 2017-08-15 | 2017-12-15 | 三峡大学 | A kind of SnSe/ carbon cloths flexibility negative material and preparation method thereof |
| CN109742353A (en) * | 2018-12-29 | 2019-05-10 | 陕西科技大学 | A kind of SnSe quantum dot/r-GO compound and its preparation method and application |
| CN109786717A (en) * | 2019-01-30 | 2019-05-21 | 陕西科技大学 | A kind of sodium-ion battery cathode SnO2The preparation method of/carbon cloth composite material |
| CN109786716A (en) * | 2019-01-30 | 2019-05-21 | 陕西科技大学 | A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode |
| CN110190246A (en) * | 2019-06-24 | 2019-08-30 | 陕西科技大学 | A kind of Sb2O3The preparation method of/carbon felt flexibility anode material of lithium-ion battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583160A (en) * | 2022-03-09 | 2022-06-03 | 广东工业大学 | Tin selenide nanosheet array/carbon cloth composite cathode material structure for sodium ion battery |
| CN114583160B (en) * | 2022-03-09 | 2024-04-26 | 广东工业大学 | Tin selenide nano-sheet array/carbon cloth composite anode material structure for sodium ion battery |
| CN114843464A (en) * | 2022-04-21 | 2022-08-02 | 陕西科技大学 | Three-dimensional cross-linked structure SnSe/3D r-GO composite material and preparation method and application thereof |
| CN114890392A (en) * | 2022-06-08 | 2022-08-12 | 陕西科技大学 | Carbon-coated tin selenide composite cross-linked three-dimensional graphene and preparation method and application thereof |
| CN114890392B (en) * | 2022-06-08 | 2024-01-30 | 陕西科技大学 | Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof |
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