CN114920283A - Zinc-tin binary sulfide/carbon nano cubic composite material and preparation method thereof - Google Patents
Zinc-tin binary sulfide/carbon nano cubic composite material and preparation method thereof Download PDFInfo
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- CN114920283A CN114920283A CN202210318857.2A CN202210318857A CN114920283A CN 114920283 A CN114920283 A CN 114920283A CN 202210318857 A CN202210318857 A CN 202210318857A CN 114920283 A CN114920283 A CN 114920283A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 38
- 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 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 238000004073 vulcanization Methods 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
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 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
- 239000002245 particle Substances 0.000 claims abstract description 3
- 150000003751 zinc Chemical class 0.000 claims abstract description 3
- 239000007773 negative electrode material Substances 0.000 claims description 21
- 229910007717 ZnSnO Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 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
- 239000002243 precursor Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims 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 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 8
- 239000010406 cathode material Substances 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 33
- 229910052573 porcelain Inorganic materials 0.000 description 20
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- 230000001351 cycling effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000000967 suction 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
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 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
- 239000010405 anode material Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 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
- 239000013543 active substance Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004146 energy storage Methods 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
- 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
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 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
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000015556 catabolic process 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
- 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
- 230000009969 flowable effect Effects 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
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 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
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
Images
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a zinc-tin binary sulfide/carbon nano cubic composite material and a preparation method thereof, wherein the zinc-tin binary sulfide/carbon nano cubic composite material has a cubic microstructure, the particle size is about 200-250 nm, the surface is coated with a carbon material with the thickness of about 5-10 nm, and water-soluble zinc salt, water-soluble tin salt and polyethylene glycol are used in alkaliPreparation of ZnSn (OH) under neutral conditions 6 Precipitating, dispersing in Tris buffer solution, reacting with dopamine hydrochloride to obtain ZnSn (OH) 6 @ C, after high-temperature carbonization reaction in an inert environment, carrying out high-temperature vulcanization reaction with sublimed sulfur in the inert environment to obtain the product. The zinc-tin binary sulfide/carbon nano cubic composite material has excellent sodium storage performance, can be used as a sodium ion battery cathode material, and is applied to the preparation of sodium ion batteries.
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 as well as preparation and application thereof.
Background
Under the global requirement for realizing the carbon neutralization goal, the demand of people for clean energy such as wind energy, solar energy and the like rises year by year, and the development of large-scale energy storage technology becomes the research focus of the current world.
Lithium ion batteries have been widely used in life because of their stable cyclicity, high capacity, and no memory effect. However, the storage amount of lithium in the earth crust is low and the lithium is distributed unevenly, so that people are prompted to research novel energy storage equipment except for the lithium ion battery.
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 is similar to that of the lithium ion battery, and the development difficulty is relatively low. However, the electrochemical performance of current sodium ion batteries is not ideal due to the larger radius of sodium ions.
Qualified cathode materials are one of the main factors restricting the development of sodium ion batteries. The necessary conditions for becoming a qualified cathode material of the sodium-ion battery need to have considerable sodium storage capacity, good circulation and rate characteristics. For example, SnS x And the single metal sulfides such as ZnS and the like have higher theoretical specific capacity and are the key points of research and development of the negative electrode material of the sodium-ion battery.
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 ions still causes great development work on the cathode material of the sodium ion batteryThere is a great concern. The different ionic radii cause changes in the kinetics of the electrode reaction and differences in the internal reaction potential, such as Zhang et al (Hierarchical assembly and super/sodium storage properties of a flowable 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]In a study of Chemical Engineering Journal, 332: 370-376, 2018), it was found that the lithium and sodium storage properties of the same metal sulfide anode material are very different. Therefore, the development of the negative electrode material for the sodium ion battery cannot fully follow the development experience of the negative electrode material for the lithium ion battery.
As a negative electrode material of a sodium ion battery, the ion diffusivity of metal sulfide is low, so that the rate performance of the battery is poor; the dissolution of the intermediate product in the electrolyte during the charging and discharging process causes the degradation of the cycle performance. Therefore, it is necessary to develop a metal sulfide having both cyclability and rate capability.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc-tin binary sulfide/carbon nano cubic composite material, which is characterized in that gaps with different sizes are formed in the material by combining in-situ assembly with a high-temperature vulcanization process so as to be beneficial to infiltration of electrolyte, shorten ion diffusion distance and improve the overall conductivity of the material by coating a carbon material.
The invention provides a zinc-tin binary sulfide/carbon nano cubic composite material with excellent cycle performance and rate capability based on the preparation method, which is used as a negative electrode material of a sodium ion battery and is another object of the invention.
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 alkaline solution to react to prepare ZnSn (OH) 6 Precipitating a precursor;
mixing ZnSn (OH) 6 Dispersing the precipitate in Tris buffer solution, adding dopamine hydrochloride to react to obtain ZnSn (OH) 6 The @ C intermediate;
para ZnSn (OH) under inert atmosphere 6 The reaction of @ C and high-temperature carbonization to prepare ZnSnO 3 @C；
By ZnSnO 3 Carrying out high-temperature sulfuration reaction on the @ C and sublimed sulfur in an inert environment to prepare the zinc-tin binary sulfide/carbon nano cubic composite material ZnS/SnS 2 @C。
Wherein, the polyethylene glycol is preferably polyethylene glycol-4000, and the alkali solution is preferably sodium hydroxide solution.
Further, in the preparation method, after the dropwise addition of the alkali solution is completed, the stirring reaction is continuously carried out for 12-24 hours so as to fully prepare ZnSn (OH) 6 And precipitating the precursor.
Specifically, the Tris buffer is preferably 0.01M Tris buffer, and the preparation of ZnSn (OH) 6 The reaction time of the @ C intermediate is 12-24 h.
Further, the invention relates to ZnSn (OH) 6 Heating the @ C to 400-600 ℃ in an inert environment for carrying out high-temperature carbonization reaction for 2-8 h to obtain ZnSnO 3 @C。
Further, it is preferable that ZnSn (OH) is added at a temperature rise rate of 2 to 5 ℃/min 6 @ C is heated to 400-600 ℃.
Specifically, the invention uses ZnSnO 3 The @ C and the sublimed sulfur are heated 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): 5, and the heating is performed at a temperature rise rate of 2-5 ℃/min.
The zinc-tin binary sulfide/carbon nano cubic composite material prepared by the method has a cubic microstructure, and the surface of the composite material is coated with a carbon material. The cubic microstructure has a particle size of about 200 to 250nm, and the thickness of the carbon material layer is about 5 to 10 nm.
The zinc-tin binary sulfide/carbon nano cubic composite material can be used as a negative electrode material of a sodium ion battery and is applied to the 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 coating a negative electrode material layer on the surface of a copper foil serving as a negative electrode current collector, and the negative electrode material layer is prepared by mixing the zinc-tin binary sulfide/carbon nano cubic composite material serving as a negative electrode active substance, a conductive agent and a binder.
The invention prepares the zinc-tin binary sulfide/carbon nano cubic composite material with a three-dimensional cubic structure simply, effectively and in high volume by combining PEG in-situ assembly with a high-temperature vulcanization process. Wherein, the polyethylene glycol used in the in-situ assembly process is a polymer which is commonly used in production and life, is non-toxic and harmless, and promotes ZnSn (OH) as a high polymer in the reaction process of the polyethylene glycol 6 Formation of nanocubes, in turn, in the reaction to ZnSn (OH) 6 The obtained zinc-tin binary sulfide/nano cubic composite material with a three-dimensional cubic structure has excellent sodium storage performance after high-temperature carbonization and high-temperature vulcanization treatment of @ C.
The invention effectively improves the binding force of zinc-tin binary sulfide nanoparticles and a carbon nano cubic framework in the zinc-tin binary sulfide/carbon nano cubic composite material by using an in-situ growth method, so that the zinc-tin binary sulfide nanoparticles are firmly anchored on the carbon framework, and the structural collapse and the polymerization of nanoparticles in the charge and discharge processes are prevented.
The zinc-tin binary sulfide/carbon nano cubic composite material prepared by the invention is used as a sodium ion battery cathode material, the first-turn charge-discharge efficiency under high current density reaches 80%, in the process of circulating 1000 turns, the charge-discharge efficiency is kept above 90%, 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 each product prepared in example 1.
FIG. 2 is ZnS/SnS 2 @ C-1 as a negative electrode material for sodium ion batteries at 2A ∙ g -1 Cycling performance at current density.
FIG. 3 is ZnS/SnS 2 @ C-2 as negative electrode material of sodium ion battery at 2A ∙ g -1 Cycling performance at current density.
FIG. 4 is a ZnS/SnS 2 @ C-3 as a negative electrode material for sodium ion batteries at 2A ∙ g -1 Cycling performance at current density.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are provided only for more clearly illustrating the technical solution of the present invention so that those skilled in the art can well understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention are those commonly known in the art and are clearly and clearly understood 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 conditions suggested by the manufacturers.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in their sources, and are all conventional products commercially available. They may also be prepared according to conventional methods well known to those skilled in the art.
The zinc-tin binary sulfide/carbon nano cubic composite material can be prepared by three processes of precursor preparation, precursor carbon coating and high-temperature reaction.
Specifically, 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 a solution A; adding 2-6 mmol of anhydrous stannic chloride into 10-20 ml of anhydrous ethanol, and fully stirring and dissolving to obtain a solution B; then, the solution B is dripped into the solution A, and the mixed solution is obtained after the solution B is fully stirred for 1 hour.
And dissolving sodium hydroxide in deionized water to obtain a 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 h, carrying out suction filtration, and collectingCollecting reaction precipitates, washing the reaction precipitates by deionized water and absolute ethyl alcohol in sequence, and drying the reaction precipitates for 12 to 24 hours at the temperature of between 60 and 100 ℃ to obtain ZnSn (OH) 6 White powder.
Weighing 0.2-0.4 g ZnSn (OH) 6 Ultrasonically dispersing the powder in 100-200 ml of 0.01M Tris buffer solution, stirring for 0.5h, adding 100-150 mg of dopamine hydrochloride, continuously stirring for reaction for 12-24 h, performing suction filtration, collecting precipitate, sequentially washing with deionized water and absolute ethyl alcohol, and drying at 60-80 ℃ for 12-24 h to obtain ZnSn (OH) 6 @ C black powder.
Mixing ZnSn (OH) 6 Putting the @ C black powder into a porcelain boat, then putting the porcelain boat into a tube furnace under the protection of nitrogen atmosphere, heating the porcelain boat to 400-600 ℃ at a heating rate of 2-5 ℃/min, reacting for 2-8 h, and naturally cooling to obtain ZnSnO 3 @ C black powder.
ZnSnO 3 Respectively placing the black powder of @ C and the yellow powder of sublimed sulfur in a mass ratio of (1-3): 5 into a porcelain boat, wherein the sublimed sulfur is positioned at the upstream of the porcelain boat, then placing the porcelain boat into a tubular furnace protected by nitrogen atmosphere, heating the porcelain boat to 400-600 ℃ at a heating rate of 2-5 ℃/min for reacting for 3-6 h, and naturally cooling to prepare the zinc-tin binary sulfide/carbon nano cubic composite material ZnS/SnS 2 @C。
Example 1.
0.2726g (2mmol) of zinc chloride and 0.4g of polyethylene glycol-4000 are weighed and added into 30ml of deionized water together, and the solution A is obtained after full stirring and dissolution.
0.521g (2mmol) of anhydrous tin tetrachloride was dissolved in 10ml of anhydrous ethanol, and the resultant solution was sufficiently stirred and dissolved to obtain a solution B.
0.82g (20.5mmol) of sodium hydroxide was added to 50ml of deionized water and dissolved uniformly to give a 0.41M aqueous solution of sodium hydroxide, labeled as solution C.
And 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 for 24 hours at room temperature, carrying out suction filtration, collecting reaction precipitates, washing with deionized water and absolute ethyl alcohol in sequence, and drying for 12-24 hours at the temperature of 60-100 ℃ to obtain ZnSn (OH) 6 White powder.
FIG. 1(a) toOut of ZnSn (OH) 6 The SEM image of the white powder shows that the white powder has a clear cubic structure, and the side length of the cube is about 200-300 nm. Thus, polyethylene glycol-4000 acts as a high polymer, promoting the formation of cubic structures.
Weighing 0.2g ZnSn (OH) 6 Adding 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, carrying out suction filtration to collect a reaction product, washing and drying to obtain ZnSn (OH) 6 @ C black powder.
ZnSn (OH) 6 Putting the @ C black powder in a porcelain boat, putting the porcelain boat in a tubular furnace protected by nitrogen atmosphere, heating to 400 ℃ at the heating rate of 2 ℃/min, reacting for 2h, and naturally cooling to obtain ZnSnO 3 @ C black powder.
ZnSnO 3 The SEM image of the @ C black powder is still a cubic structure as shown in FIG. 1(b), the side length is maintained at about 200 to 300nm, and the surface structure is rough as compared with FIG. 1(a), which is a cause of coating with the carbon material.
ZnSnO 3 The @ C black powder is placed in a porcelain boat, sublimed sulfur yellow powder (the mass ratio of the sublimed sulfur yellow powder to the sublimed sulfur yellow powder is 1: 5) is placed on the upstream of the porcelain boat, the porcelain boat is placed in a tubular furnace protected by nitrogen atmosphere, the temperature is raised to 600 ℃ at the rate of 2 ℃/min for reaction for 3 hours, and the composite material ZnS/SnS is obtained by natural cooling 2 @C-1。
FIG. 1(c) is an SEM image showing ZnS/SnS after high temperature vulcanization 2 @ C-1 morphology with ZnSnO 3 @ C remains substantially the same. Further, 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 10 nm.
Example 2.
0.4g of ZnSn (OH) prepared in example 1 6 Adding white powder into 200ml of 0.01M Tris buffer solution, stirring for 0.5h to disperse uniformly, adding 150mg of dopamine hydrochloride, stirring for 24h, performing suction filtration to collect a reaction product, washing and drying to obtain ZnSn (OH) 6 @ C black powder.
Mixing ZnSn (OH) 6 The @ C black powder is put into a porcelain boat and is put into a tube furnace protected by nitrogen atmosphere, and the temperature is increased to the temperature of 5 ℃/minReacting for 4 hours at 400 ℃, and naturally cooling to obtain ZnSnO 3 @ C black powder.
ZnSnO 3 The @ C black powder is placed in a porcelain boat, sublimed sulfur yellow powder (the mass ratio of the sublimed sulfur yellow powder to the sublimed sulfur yellow powder is 1: 5) is placed on the upstream of the porcelain boat, the porcelain boat is placed in a tubular furnace protected by nitrogen atmosphere, the temperature is raised to 500 ℃ at the rate of 2 ℃/min for reaction for 3 hours, and the composite material ZnS/SnS is obtained by natural cooling 2 @C-2。
Example 3.
0.2g of ZnSn (OH) prepared in example 1 6 Adding white powder into 100ml of 0.01M Tris buffer solution, stirring for 0.5h to disperse uniformly, adding 100mg of dopamine hydrochloride, stirring for 24h, performing suction filtration to collect a reaction product, washing and drying to obtain ZnSn (OH) 6 @ C black powder.
Mixing ZnSn (OH) 6 The @ C black powder is put into a porcelain boat and is put into a tube furnace protected by nitrogen atmosphere, the temperature is raised to 400 ℃ at the rate of 5 ℃/min for reaction for 6h, and the ZnSnO is obtained by natural cooling 3 @ C black powder.
ZnSnO 3 Putting the @ C black powder into a porcelain boat, putting sublimed sulfur yellow powder (the mass ratio of the two is 1: 5) on the upstream of the porcelain boat, putting the porcelain boat into a tubular furnace protected by nitrogen atmosphere, heating to 400 ℃ at the heating rate of 5 ℃/min, reacting for 6h, and naturally cooling to obtain the composite material ZnS/SnS 2 @C-3。
Application example.
The 3 zinc-tin binary sulfide/carbon nano cubic composite materials prepared in the embodiment are used as negative electrode materials of the sodium ion battery to prepare the sodium ion battery.
The sodium ion battery consists 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 also comprises a negative electrode active substance, a conductive agent and a binder. ZnS/SnS prepared by the application example 2 @ C composite material as the 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 waterForming slurry by using the sub-water, uniformly coating the slurry on a copper foil, and drying the slurry in vacuum at 60 ℃ for 12 hours to obtain the cathode. And (2) assembling the CR2032 type button half-cell in a glove box with argon protection by using metal sodium as a counter electrode, a glass fiber membrane Whatman GF/C as a diaphragm and sodium trifluoromethanesulfonate mixed solution dissolved with 1M sodium hexafluorophosphate as electrolyte, standing for 12h, and then carrying out electrochemical test.
FIGS. 2 to 4 show ZnS/SnS 2 @C-1、ZnS/SnS 2 @ C-2 and ZnS/SnS 2 @ C-3 as a negative electrode material for sodium ion batteries at 2A ∙ g -1 Cycling performance at current density. The charging and discharging curves in the figure are mutually overlapped, which shows that the charging and discharging specific capacities of 3 sodium ion batteries are very close to each other, and the reversibility of the reaction is proved.
Wherein 2A ∙ g in FIG. 2 -1 The charge-discharge efficiency of the battery in the first circle under the current density reaches 80 percent, 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 capacity after 1000 cycles under the current density can be kept at 210mA ∙ h ∙ g -1 The stability of the specific capacity is stronger in the circulating process; 2A ∙ g in FIG. 4 -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 by the invention is compared with the performance of the sodium ion batteries reported in the following 3 documents, which are specifically listed 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 serving as a negative electrode material of the sodium-ion battery has the optimal electrochemical performance, and compared with other sodium-ion batteries such as documents 1, 2 and 3, the @ C-3 negative electrode material has more excellent cycling performance and rate capability, particularly cycling stability under high current, and 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 present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (10)
1. A preparation method of a zinc-tin binary sulfide/carbon nano cubic composite material comprises the following steps:
1) 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 a precursor;
2) ZnSn (OH) 6 Dispersing the precipitate in Tris buffer solution, adding dopamine hydrochloride to react to obtain ZnSn (OH) 6 The @ C intermediate;
3) para ZnSn (OH) under inert atmosphere 6 The @ C is subjected to high-temperature carbonization reaction to prepare ZnSnO 3 @C；
4) ZnSnO 3 @ C with sublimed sulphur in an inert atmosphereHigh-temperature sulfurizing reaction to prepare zinc-tin binary sulfide/carbon nano cubic composite material ZnS/SnS 2 @C。
2. The method for preparing zinc-tin binary sulfide/carbon nano-cubic composite material according to claim 1, wherein the polyethylene glycol is polyethylene glycol-4000.
3. The preparation method of zinc-tin binary sulfide/carbon nano-cubic composite material as claimed in claim 1, wherein ZnSn (OH) 6 Heating the @ C to 400-600 ℃ in an inert environment for carrying out high-temperature carbonization reaction for 2-8 h.
4. The preparation method of the zinc-tin binary sulfide/carbon nano-cubic composite material as claimed in claim 3, wherein ZnSn (OH) is added at a heating rate of 2-5 ℃/min 6 @ C is heated to 400-600 ℃.
5. The preparation method of zinc-tin binary sulfide/carbon nano-cubic composite material as claimed in claim 1, characterized in that ZnSnO is used 3 The @ C and the sublimed sulfur are heated to 400-600 ℃ in an inert environment to carry out high-temperature vulcanization reaction for 3-6 h.
6. The method for preparing a zinc-tin binary sulfide/carbon nano-cubic composite material as claimed in claim 5, wherein the high temperature vulcanization reaction is carried out by heating to 400-600 ℃ at a heating rate of 2-5 ℃/min.
7. The process for preparing a zinc-tin binary sulfide/carbon nanocube composite material as set forth in claim 1 or 5, wherein said ZnSnO is 3 The mass ratio of @ C to sublimed sulfur is (1-3) to 5.
8. The zinc-tin binary sulfide/carbon nano-cubic composite material prepared by the preparation method of claim 1, which has a cubic microstructure, the surface of the zinc-tin binary sulfide/carbon nano-cubic composite material is coated with a carbon material, the cubic microstructure has a particle size of 200-250 nm, and the thickness of the carbon material layer is 5-10 nm.
9. The use of the zinc-tin binary sulfide/carbon nanocube composite material of claim 8 as a negative electrode material for sodium-ion batteries.
10. A sodium ion battery, which consists of a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is formed by coating a negative electrode material layer on the surface of a copper foil which is used as a negative electrode current collector, and the negative electrode material layer is prepared by mixing the zinc-tin binary sulfide/carbon nano cubic composite material as claimed in claim 8, a conductive agent and a binder.
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