CN114920283B - Zinc-tin binary sulfide/carbon nano-cube composite material and preparation method thereof - Google Patents
Zinc-tin binary sulfide/carbon nano-cube composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 37
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004073 vulcanization Methods 0.000 claims abstract description 10
- 239000007983 Tris buffer Substances 0.000 claims abstract description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 3
- 150000003751 zinc Chemical class 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229910007717 ZnSnO Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 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 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 5
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 20
- 239000000843 powder Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 229910052573 porcelain Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/58—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
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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
- H01M4/62—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a zinc-tin binary sulfide/carbon nano-cube composite material and a preparation method thereof, wherein the zinc-tin binary sulfide/carbon nano-cube composite material has a cube microstructure, the grain size is about 200-250 nm, and the surface is coated with a carbon material with the thickness of about 5-10 nm, and is prepared by water-soluble zinc salt, water-soluble tin salt and polyethylene glycol under alkaline condition 6 Precipitation, dispersing in Tris buffer solution, reacting with dopamine hydrochloride to obtain ZnSn (OH) 6 And (3) carrying out high-temperature vulcanization reaction on the carbon fiber and sublimated sulfur in an inert environment after high-temperature carbonization reaction in the inert environment. The zinc-tin binary sulfide/carbon nano-cube composite material has excellent sodium storage performance, can be used as a negative electrode material of a sodium ion battery, and is applied to the preparation of the sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of nano composite material preparation, and particularly relates to a zinc-tin binary sulfide/carbon nano cubic composite material and preparation and application thereof.
Background
Under the global requirement of realizing the carbon neutralization target, the requirements of people on clean energy sources such as wind energy, solar energy and the like are rising year by year, and the development of large-scale energy storage technology has become the research focus in the current world.
Lithium ion batteries have been widely used in life due to their stable cycle, high capacity, and no memory effect. However, the low reserve and uneven distribution of lithium in the crust of earth have prompted research into novel energy storage devices other than lithium ion batteries.
Sodium ion batteries are considered to be one of the ideal alternatives to lithium ion batteries thanks to the abundant reserves of metallic sodium in the earth. Moreover, the reaction mechanism of the sodium ion battery and the lithium ion battery is similar, and the development difficulty is relatively low. However, the electrochemical performance of current sodium ion batteries is not ideal, subject to the larger radius of sodium ions.
The qualified negative electrode material is one of the main factors restricting the development of the sodium ion battery. The requirement for becoming a qualified negative electrode material of a sodium ion battery needs to have considerable sodium storage capacity, good circulation and multiplying power characteristics. For example, snS x The single metal sulfides such as ZnS and the like have higher theoretical specific capacity and are important points for developing negative electrode materials of sodium ion batteries.
Even though the operation principle of the sodium ion battery is similar to that of the lithium ion battery, the larger ion radius of the sodium ion still causes great trouble to the development work of the negative electrode material of the sodium ion battery. The different ionic radii cause a change in the kinetics of the electrode reaction and a difference in the internal reaction potential, e.g. Zhang et al (Hierarchical assembly and superio)r lithium/sodium storage properties of a flowerlike C/SnS@C nanocomposite[J]. Electrochimica Acta, 296: 891-900, 2019.；3D spongy CoS 2 nanoparticles/carbon composite as high-performance anode material for lithium/sodium ion batteries[J]Chemical Engineering Journal, 332:370-376, 2018.) it was found that the lithium and sodium storage properties of the same metal sulfide negative electrode material differ greatly. Therefore, the development of the negative electrode material of the sodium ion battery cannot fully follow the development experience of the negative electrode material of the lithium ion battery.
As a negative electrode material of the sodium ion battery, the low ion diffusivity of the metal sulfide leads to poor rate performance of the battery; dissolution of the intermediate product in the electrolyte during charge and discharge causes degradation of cycle performance. Therefore, it is necessary to develop a metal sulfide having both of cycle property and rate capability.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc-tin binary sulfide/carbon nano-cube composite material, which is characterized in that gaps with different sizes are formed in the material by combining in-situ assembly and a high-temperature vulcanization process, so that electrolyte infiltration is facilitated, ion diffusion distance is shortened, and overall conductivity of the material is improved by coating of a carbon material.
It is another object of the present invention to provide a zinc tin binary sulfide/carbon nanocube composite material with excellent cycle performance and rate performance based on the above preparation method, which is used as a negative electrode material of a sodium ion battery.
The preparation method of the zinc-tin binary sulfide/carbon nano cubic composite material comprises the following steps:
adding an ethanol solution of water-soluble tin salt into a mixed aqueous solution of water-soluble zinc salt and polyethylene glycol, and dropwise adding an alkali solution to react to prepare ZnSn (OH) 6 Precipitating the precursor;
ZnSn (OH) 6 Dispersing the precipitate in Tris buffer solution, adding dopamine hydrochloride to react to obtain ZnSn (OH) 6 An intermediate @ C;
under inert environment to ZnSn (OH) 6 Performing high-temperature carbonization reaction on @ C to prepare ZnSnO 3 @C；
By ZnSnO 3 Carrying out high-temperature vulcanization reaction on @ C and sublimed sulfur in an inert environment to prepare zinc-tin binary sulfide/carbon nano cubic composite material ZnS/SnS 2 @C。
Wherein, polyethylene glycol-4000 is preferably used as the polyethylene glycol, and sodium hydroxide aqueous solution is preferably used as the alkali solution.
Further, in the preparation method, after the alkali solution is added dropwise, stirring is continuously carried out for reaction for 12-24 hours so as to fully prepare ZnSn (OH) 6 Precipitating the precursor.
Specifically, the Tris buffer preferably uses 0.01M Tris buffer, and the preparation ZnSn (OH) 6 The reaction time of the @ C intermediate is 12-24 h.
Further, the present invention is to mix ZnSn (OH) 6 Heating @ C to 400-600 ℃ in an inert environment to carry out high-temperature carbonization reaction for 2-8 h to obtain ZnSnO 3 @C。
Further, znSn (OH) is preferably added at a heating rate of 2 to 5 ℃/min 6 Heating to 400-600 ℃.
Specifically, the invention uses ZnSnO 3 Heating the @ C and sublimed sulfur to 400-600 ℃ in an inert environment to carry out high-temperature vulcanization reaction for 3-6 h.
More specifically, the ZnSnO 3 The mass ratio of @ C to sublimed sulfur is preferably (1-3) to 5, and heating is carried out at a heating rate of 2-5 ℃/min.
The zinc-tin binary sulfide/carbon nano-cube composite material prepared by the method has a cube microstructure, and the surface of the zinc-tin binary sulfide/carbon nano-cube composite material is coated with a carbon material. The grain size of the cubic microstructure is about 200-250 nm, and the thickness of the carbon material layer is about 5-10 nm.
The zinc-tin binary sulfide/carbon nano-cube composite material can be used as a negative electrode material of a sodium ion battery and applied to preparation of the sodium ion battery.
The invention further provides a sodium ion battery which is composed of a positive electrode, a negative electrode, a diaphragm and electrolyte and is of a conventional sodium ion battery structure, wherein the negative electrode is formed by taking copper foil as a negative electrode current collector and coating a negative electrode material layer on the surface, and the negative electrode material layer is prepared by taking the zinc-tin binary sulfide/carbon nano cubic composite material as a negative electrode active substance and mixing the zinc-tin binary sulfide/carbon nano cubic composite material with a conductive agent and a binder.
According to the invention, the zinc-tin binary sulfide/carbon nano-cube composite material with a three-dimensional cube structure is simply, effectively and relatively high in mass production through the PEG in-situ assembly and high-temperature vulcanization process. Wherein the polyethylene glycol used in the in-situ assembly process is a polymer commonly used in production and life, is nontoxic and harmless, and is used as a high polymer to promote ZnSn (OH) in the reaction process of participation of the polyethylene glycol 6 Formation of nanocubes, in turn, against ZnSn (OH) 6 After the high-temperature carbonization and high-temperature vulcanization treatment, the obtained zinc-tin binary sulfide/nanocube composite material with a three-dimensional cube structure has excellent sodium storage performance.
The invention utilizes an in-situ growth method to effectively improve the binding force of the zinc-tin binary sulfide nano particles and the carbon nano cubic skeleton in the zinc-tin binary sulfide/carbon nano cubic composite material, so that the zinc-tin binary sulfide nano particles are firmly anchored on the carbon skeleton, and the collapse of the structure and the polymerization of the nano particles in the charge and discharge process are prevented.
The zinc-tin binary sulfide/carbon nano cubic composite material prepared by the method is used as a negative electrode material of a sodium ion battery, the first-cycle charge-discharge efficiency under high current density reaches 80%, the charge-discharge efficiency is kept above 90% in the process of 1000 cycles, and the final specific capacity is not lower than 500mA ∙ h ∙ g -1 。
Drawings
FIG. 1 is an SEM image and a TEM image of the products prepared in example 1.
FIG. 2 is a ZnS/SnS 2 (r) C-1 as a negative electrode material of a sodium ion battery in an amount of 2A ∙ g -1 Cycle performance at current density.
FIG. 3 is ZnS/SnS 2 (r) C-2 as a negative electrode material of sodium ion battery in 2A ∙ g -1 Cycle performance at current density.
FIG. 4 is a ZnS/SnS 2 (r) C-3 as a negative electrode material for sodium ion battery in 2A ∙ g -1 Cycle performance at current density.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are presented only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention, the names and abbreviations thereof are all conventional in the art, and are clearly understood and defined in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names, and perform the operations according to the conventional conditions or the conditions suggested by the manufacturer.
The various raw materials or reagents used in the examples and comparative examples of the present invention are not particularly limited in source, and are conventional products commercially available. The preparation may also be carried out according to conventional methods known to the person skilled in the art.
The zinc-tin binary sulfide/carbon nano-cube composite material can be prepared by three steps of precursor preparation, precursor carbon coating and high-temperature reaction.
Specifically, firstly, adding 2-6 mmol of zinc chloride and 0.4-0.8 g of polyethylene glycol-4000 into 30-90 ml of deionized water, and fully stirring and dissolving to obtain solution A; adding 2-6 mmol of anhydrous tin tetrachloride into 10-20 ml of absolute ethyl alcohol, and fully stirring and dissolving to obtain a solution B; then, the solution B is added into the solution A in a dropwise manner, and the mixed solution is obtained after the solution A is fully stirred for 1 h.
Sodium hydroxide is dissolved in deionized water to obtain solution C with the concentration of 0.4-0.6M.
Dropwise adding the solution C into the mixed solution, continuously stirring at room temperature for reaction for 12-24 hours, filtering, collecting reaction precipitate, washing with deionized water and absolute ethyl alcohol in sequence, and drying at 60-100 ℃ for 12-24 hours to obtain ZnSn (OH) 6 White colorAnd (3) powder.
Weighing 0.2-0.4 g ZnSn (OH) 6 Dispersing the powder in 100-200 ml of 0.01M Tris buffer solution by ultrasonic, stirring for 0.5h, adding 100-150 mg of dopamine hydrochloride, continuously stirring for reacting for 12-24 h, filtering, collecting precipitate, washing with deionized water and absolute ethyl alcohol in sequence, and drying at 60-80 ℃ for 12-24 h to obtain ZnSn (OH) 6 Black powder @ C.
ZnSn (OH) 6 Placing the black powder @ C into a porcelain boat, then placing the porcelain boat into a tube furnace under the protection of nitrogen atmosphere, heating to 400-600 ℃ according to the heating rate of 2-5 ℃/min, reacting for 2-8 h, and naturally cooling to obtain ZnSnO 3 Black powder @ C.
ZnSnO (zinc sulfide) 3 Placing black powder @ C and sublimed sulfur powder in a mass ratio of (1-3) to 5 in a porcelain boat respectively, wherein sublimed sulfur is positioned at the upstream of the porcelain boat, then placing the porcelain boat in a tube furnace protected by nitrogen atmosphere, heating to 400-600 ℃ at a heating rate of 2-5 ℃/min for reaction for 3-6 h, and naturally cooling to obtain the zinc-tin binary sulfide/carbon nano cubic composite ZnS/SnS 2 @C。
Example 1.
0.2726g (2 mmol) of zinc chloride and 0.4g of polyethylene glycol-4000 are weighed and added together into 30ml of deionized water, and the solution A is obtained by fully stirring and dissolving.
0.521g (2 mmol) of anhydrous tin tetrachloride was dissolved in 10ml of absolute ethanol, and the solution was dissolved by stirring thoroughly.
To 50ml of deionized water was added 0.82g (20.5 mmol) of sodium hydroxide, and the mixture was dissolved uniformly to give a 0.41M aqueous sodium hydroxide solution, designated as solution C.
And (3) dropwise adding the solution B into the solution A, and fully stirring for 1h to obtain a mixed solution. Dropwise adding the solution C into the mixed solution, continuously stirring at room temperature for 24 hours, filtering, collecting reaction precipitate, washing with deionized water and absolute ethyl alcohol in sequence, and drying at 60-100 ℃ for 12-24 hours to obtain ZnSn (OH) 6 White powder.
FIG. 1 (a) shows ZnSn (OH) 6 SEM pictures of white powder, as can be seen in the apparent cube structure, the cube side lengths were about 200-300 nm. Thus (2)Polyethylene glycol-4000 acts as a high polymer, which promotes the formation of a cubic structure.
Weighing 0.2g ZnSn (OH) 6 Adding the white powder into 100ml of 0.01M Tris buffer solution, stirring for 0.5h to uniformly disperse, adding 150mg of dopamine hydrochloride, stirring for 24h, filtering, collecting reaction product, washing, and drying to obtain ZnSn (OH) 6 Black powder @ C.
ZnSn (OH) 6 Placing the @ C black powder into a porcelain boat, placing into a tube furnace protected by nitrogen atmosphere, heating to 400 ℃ at a heating rate of 2 ℃/min for reaction for 2 hours, and naturally cooling to obtain ZnSnO 3 Black powder @ C.
ZnSnO 3 As shown in fig. 1 (b), the SEM image of the black powder @ C still has a cubic structure with a side length of about 200 to 300nm, and the surface structure is rough compared to fig. 1 (a), which is the cause of the carbon material coating.
ZnSnO (zinc sulfide) 3 Placing @ C black powder into a porcelain boat, placing sublimed sulfur powder (the mass ratio of the two is 1:5) at the upstream, placing into a tube furnace protected by nitrogen atmosphere, heating to 600 ℃ at a heating rate of 2 ℃/min for reaction for 3h, and naturally cooling to obtain the composite material ZnS/SnS 2 @C-1。
FIG. 1 (c) is a SEM image showing ZnS/SnS after high temperature vulcanization 2 Morphology of @ C-1 and ZnSnO 3 The @ C is kept substantially identical. Furthermore, from the TEM image of FIG. 1 (d), znS/SnS can be seen 2 The thickness of the carbon layer in @ C-1 is about 5 to 10nm.
Example 2.
0.4g of ZnSn (OH) prepared in example 1 was reacted with 6 Adding the white powder into 200ml of 0.01M Tris buffer solution, stirring for 0.5h to uniformly disperse, adding 150mg of dopamine hydrochloride, stirring for 24h, filtering, collecting reaction product, washing, and drying to obtain ZnSn (OH) 6 Black powder @ C.
ZnSn (OH) 6 Placing the @ C black powder into a porcelain boat, placing into a tube furnace protected by nitrogen atmosphere, heating to 400 ℃ at a heating rate of 5 ℃/min for reaction for 4 hours, and naturally cooling to obtain ZnSnO 3 Black powder @ C.
ZnSnO (zinc sulfide) 3 Black @ CPlacing the powder in a porcelain boat, placing sublimated sulfur powder (the mass ratio of the powder to the porcelain boat is 1:5) at the upstream, placing the porcelain boat in a tube furnace protected by nitrogen atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min for reaction for 3 hours, and naturally cooling to obtain the composite material ZnS/SnS 2 @C-2。
Example 3.
0.2g of ZnSn (OH) prepared in example 1 was reacted with 6 Adding the white powder into 100ml of 0.01M Tris buffer solution, stirring for 0.5h to uniformly disperse, adding 100mg of dopamine hydrochloride, stirring for 24h, filtering, collecting reaction product, washing, and drying to obtain ZnSn (OH) 6 Black powder @ C.
ZnSn (OH) 6 Placing the @ C black powder into a porcelain boat, placing into a tube furnace protected by nitrogen atmosphere, heating to 400 ℃ at a heating rate of 5 ℃/min for reaction for 6 hours, and naturally cooling to obtain ZnSnO 3 Black powder @ C.
ZnSnO (zinc sulfide) 3 Placing @ C black powder into a porcelain boat, placing sublimed sulfur powder (the mass ratio of the two is 1:5) at the upstream, placing into a tube furnace protected by nitrogen atmosphere, heating to 400 ℃ at a heating rate of 5 ℃/min for reaction for 6h, and naturally cooling to obtain the composite material ZnS/SnS 2 @C-3。
Application example.
The 3 zinc-tin binary sulfide/carbon nanocube composite materials prepared in the embodiment are used as negative electrode materials of sodium ion batteries to prepare sodium ion batteries.
The sodium ion battery is composed of a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a current collector copper foil and a negative electrode material layer coated on the surface of the current collector copper foil, and the negative electrode material layer comprises a negative electrode active substance, a conductive agent and a binder. The ZnS/SnS prepared by the method 2 The @ C composite material was used as a negative electrode active material.
The specific preparation method of the sodium ion battery comprises the following steps: znS/SnS 2 Mixing the @ C composite material, conductive carbon and sodium carboxymethylcellulose according to the mass ratio of 7:2:1, adding deionized water to form slurry, uniformly coating the slurry on copper foil, and vacuum-drying at 60 ℃ for 12 hours to obtain the negative electrode. Glass fiber film heat with metallic sodium as counter electrodeAnd (3) man GF/C is a diaphragm, a mixed solution of sodium triflate dissolved with 1M sodium hexafluorophosphate is used as an electrolyte, and the CR2032 button half-cell is obtained by assembling in a glove box protected by argon, and after standing for 12h, an electrochemical test is carried out.
FIGS. 2 to 4 show ZnS/SnS respectively 2 @C-1、ZnS/SnS 2 @C-2 and ZnS/SnS 2 (r.) C-3 as a negative electrode material for sodium ion batteries at 2A ∙ g -1 Cycle performance at current density. In the figure, the charge and discharge curves overlap with each other, which shows that the charge and discharge specific capacities of 3 sodium ion batteries are very close, and the reversibility of the reaction is proved.
Wherein, 2A ∙ g in FIG. 2 -1 The first-circle charge-discharge efficiency of the battery under the current density reaches 80%, and the discharge specific capacity after 1000 circles of circulation is kept at 540mA ∙ h ∙ g -1 . In FIG. 3, 2A ∙ g -1 The specific discharge capacity of the battery after 1000 cycles under the current density can be kept at 210mA ∙ h ∙ g -1 The specific capacity stability is stronger in the circulating process; FIG. 4A ∙ g -1 The specific discharge capacity of the battery after 1000 circles under the current density is about 390mA ∙ h ∙ g -1 。
Furthermore, the performance of 3 sodium ion batteries prepared according to the present invention was compared with that reported in the following 3 documents, and is specifically shown in table 1.
As can be seen from Table 1, znS/SnS 2 @C-1、ZnS/SnS 2 @C-2 and ZnS/SnS 2 The @ C-3 material used as the negative electrode material of the sodium ion battery has optimal electrochemical performance, and has more excellent cycle performance and rate performance, particularly cycle stability under high current, compared with other sodium ion batteries, such as documents 1, 2 and 3, which shows the innovation of the invention.
Among them, the literature information cited in table 1 is as follows.
Document [1 ]]：X. Liu, Y. Hao, J. Shu, H.M.K. Sari, L. Lin, H. Kou, J. Li, W. Liu, B. Yan, D. Li, J. Zhang, X. Li, Nitrogen/sulfur dual-doping of reduced graphene oxide harvesting hollow ZnSnS 3 nano-microcubes with superior sodium storage[J]. Nano Energy, 57(2019): 414-423.。
Document [2 ]]：H. Jia, M. Dirican, N. Sun, C. Chen, C. Yan, P. Zhu, X. Dong, Z. Du, H. Cheng, J. Guo, X. Zhang, Advanced ZnSnS 3 @rGO Anode Material for Superior Sodium-Ion and Lithium-Ion Storage with Ultralong Cycle Life[J]. ChemElectroChem, 6(2018): 1183-1191.。
Document [3]：H. Jia, M. Dirican, C. Chen, P. Zhu, C. Yan, Y. Li, J. Zhu, Z. Li, J. Guo, X. Zhang, Rationally designed carbon coated ZnSnS 3 nano cubes as high-performance anode for advanced sodium-ion batteries[J]. Electrochimica Acta, 292(2018): 646-654.。
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (9)
1. A preparation method of zinc-tin binary sulfide/carbon nano-cube composite material comprises the following steps:
1) Adding ethanol solution of water-soluble tin salt into mixed water solution of water-soluble zinc salt and polyethylene glycol-4000, and dropwise adding alkali solution to react to prepare ZnSn (OH) 6 Precipitating the precursor;
2) ZnSn (OH) 6 Dispersing the precipitate in Tris buffer solution, adding dopamine hydrochloride to react to obtain ZnSn (OH) 6 An intermediate @ C;
3) ZnSn (OH) in an inert environment 6 Performing high-temperature carbonization reaction on @ C to prepare ZnSnO 3 @C；
4) By ZnSnO 3 Performing high-temperature vulcanization reaction on @ C and sublimed sulfur in an inert environment to prepare zinc-tin binary sulfur with a cubic microstructure particle size of 200-250 nm and a carbon material layer thickness of 5-10 nmZnS/SnS composite material of chemical compound/carbon nano cube 2 @C。
2. The method for preparing zinc tin binary sulfide/carbon nano cubic composite material according to claim 1, wherein ZnSn (OH) 6 Heating at 400-600 deg.c in inert environment for 2-8 hr.
3. The method for preparing zinc-tin binary sulfide/carbon nano cubic composite material according to claim 2, wherein ZnSn (OH) is added at a heating rate of 2-5 ℃/min 6 Heating to 400-600 ℃.
4. The preparation process of binary zinc tin sulfide/carbon nanometer cubic composite material as claimed in claim 1, characterized in that ZnSnO 3 Heating the @ C and sublimed sulfur to 400-600 ℃ in an inert environment to carry out high-temperature vulcanization reaction for 3-6 h.
5. The method for preparing zinc tin binary sulfide/carbon nano cubic composite material according to claim 4, wherein the zinc tin binary sulfide/carbon nano cubic composite material is heated to 400-600 ℃ at a heating rate of 2-5 ℃/min for high-temperature vulcanization reaction.
6. The method for preparing zinc tin binary sulfide/carbon nanocube composite material according to claim 1 or 4, characterized in that the ZnSnO 3 The mass ratio of the @ C to the sublimated sulfur is (1-3) to 5.
7. The zinc-tin binary sulfide/carbon nano-cube composite material prepared by the preparation method of claim 1, wherein the zinc-tin binary sulfide/carbon nano-cube composite material has a cube microstructure, the surface of the zinc-tin binary sulfide/carbon nano-cube composite material is coated with a carbon material, the grain size of the cube microstructure is 200-250 nm, and the thickness of the carbon material layer is 5-10 nm.
8. The use of the zinc tin binary sulfide/carbon nanocube composite material according to claim 7 as a negative electrode material of a sodium ion battery.
9. A sodium ion battery is composed of a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is formed by taking copper foil as a negative electrode current collector and coating a negative electrode material layer on the surface, and the negative electrode material layer is prepared by taking the zinc tin binary sulfide/carbon nano cubic composite material as a negative electrode active substance and mixing the zinc tin binary sulfide/carbon nano cubic composite material with a conductive agent and a binder.
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