CN105720251A - Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material - Google Patents
Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material Download PDFInfo
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- CN105720251A CN105720251A CN201610099175.1A CN201610099175A CN105720251A CN 105720251 A CN105720251 A CN 105720251A CN 201610099175 A CN201610099175 A CN 201610099175A CN 105720251 A CN105720251 A CN 105720251A
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- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 6
- 150000004763 sulfides Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019252 potassium sulphite Nutrition 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 29
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 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
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 2
- -1 Na 3 V 2 (PO 4 ) 3 Chemical class 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002133 porous carbon nanofiber Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052959 stibnite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了一种钠离子电池硫化锑基复合材料及其制备方法。该制备方法为：将硫化锑溶解于介质中，加入氧化石墨烯溶液，超声1~600min使其充分分散均匀，与亚硫酸盐和酸溶液混合，搅拌5~600min，通过固液分离、干燥得到无定形硫化锑与氧化石墨烯复合材料前驱体，前驱体在惰性或还原气氛下250~550℃煅烧1~24h，得钠离子电池硫化锑基复合材料。本发明制备的复合材料可用于钠离子电池负极材料，在电流密度为2Ag?1下比容量达680mAh g?1，100次循环后比容量保持率大于96%。与传统的水热法等相比，本发明具有流程短、过程简单、能耗较低、生产成本小，易于实现大规模生产等优点。
The invention discloses an antimony sulfide-based composite material for a sodium ion battery and a preparation method thereof. The preparation method is as follows: dissolving antimony sulfide in the medium, adding graphene oxide solution, ultrasonicating for 1-600 minutes to fully disperse it uniformly, mixing with sulfite and acid solution, stirring for 5-600 minutes, and obtaining by solid-liquid separation and drying Amorphous antimony sulfide and graphene oxide composite material precursor, the precursor is calcined at 250~550°C for 1~24h under an inert or reducing atmosphere to obtain an antimony sulfide based composite material for a sodium ion battery. The composite material prepared by the invention can be used as the negative electrode material of the sodium ion battery, and the specific capacity reaches 680mAh g ·1 at the current density of 2Ag ·1 , and the specific capacity retention rate is greater than 96% after 100 cycles. Compared with the traditional hydrothermal method, etc., the present invention has the advantages of short process, simple process, low energy consumption, low production cost, easy realization of large-scale production and the like.
Description
技术领域 technical field
本发明涉及钠离子电池材料领域，具体涉及一种钠离子电池硫化锑基复合材料及其制备方法。 The invention relates to the field of sodium ion battery materials, in particular to an antimony sulfide-based composite material for a sodium ion battery and a preparation method thereof.
背景技术 Background technique
锂离子电池作为高能量密度电池体系，在便携式电子产品、电动工具和电动汽车领域得到了飞速发展。但是锂资源在地壳中储量并不丰富且价格昂贵，可能会限制锂离子电池在大规模储能电源方面的发展。因此，发展资源丰富，成本低廉的先进电池体系，是解决未来大规模储电应用的必然出路。钠元素与锂处于同一主族，具有相似的电子结构和化学性能，并且钠元素在地壳中储量丰富，提炼成本低，使得钠离子电池成为一种非常有发展前景的能源转换和储存器件之一。因此，寻找与锂离子电池性能匹配，即高容量、高倍率及优异循环性能的钠电极材料已成为当前电池领域的研究热点。 As a high-energy-density battery system, lithium-ion batteries have developed rapidly in the fields of portable electronic products, power tools and electric vehicles. However, lithium resources are not abundant and expensive in the earth's crust, which may limit the development of lithium-ion batteries in large-scale energy storage. Therefore, the development of an advanced battery system with abundant resources and low cost is an inevitable way out for large-scale power storage applications in the future. Sodium is in the same main group as lithium, has similar electronic structure and chemical properties, and sodium is abundant in the earth's crust, and the cost of refining is low, making sodium-ion batteries one of the most promising energy conversion and storage devices. . Therefore, finding sodium electrode materials that match the performance of lithium-ion batteries, that is, high capacity, high rate and excellent cycle performance, has become a research hotspot in the current battery field.
由于钠元素和锂化学性质相近，锂离子电池的正极材料可以借鉴到钠离子负极材料，所以在钠离子电池正极极材料如含钠过渡金属氧化物（如Na x CoO2，Na x MnO2，NaNi0.5Mn0.5O2）和聚阴离子型化合物（如Na3V2(PO4)3、NaTi2(PO4)3、NaVPO4F，Na2FePO4F）的研发方面已经取得了非常大的进展。但是由于钠离子具有比锂离子大55%的离子半径，导致钠离子无法在具有良好嵌锂性能的石墨材料层间距有效嵌入和脱出。因此，高性能、低成本负极材料的开发与应用是钠离子电池走向商业化的重要一步。 Due to the similar chemical properties of sodium and lithium, the positive electrode material of lithium ion battery can be used for reference to the negative electrode material of sodium ion, so in the positive electrode material of sodium ion battery such as sodium-containing transition metal oxide (such as Na x CoO 2 , Na x MnO 2 , Great progress has been made in the research and development of NaNi 0.5 Mn 0.5 O 2 ) and polyanionic compounds (such as Na 3 V 2 (PO 4 ) 3 , NaTi 2 (PO 4 ) 3 , NaVPO 4 F, Na 2 FePO 4 F) Progress. However, since sodium ions have an ionic radius 55% larger than that of lithium ions, sodium ions cannot be effectively intercalated and extracted in the interlayer spacing of graphite materials with good lithium intercalation properties. Therefore, the development and application of high-performance and low-cost anode materials is an important step towards the commercialization of sodium-ion batteries.
表1 Table 1
碳类材料如硬碳、多孔炭、碳纳米纤维在钠离子电池负极材料上的应用得到深入的研究，但是该类材料的首次效率低、容量不高将难于满足实际应用。相比之下，单质锑及其化合物（如表1）因比容量高引起研究者的兴趣。在所有锑基化合物中，硫化锑比单质锑和锑氧化物具有更好的比能量密度、更小的体积变化和更优的循环性能。为了进一步提高硫化锑的电化学性能，纳米化以及复合石墨烯是有效缓解材料粉化、提高材料的循环寿命的有效手段。文献中报道的纳米锑及其化合物和石墨烯复合材料所需前驱体材料的价格高、并且很多报道的材料的制备过程复杂，这些缺点限制了硫化锑/石墨烯复合材料的大规模应用。本发明实施例以商业化的为主要原料，通过两步法即室温下的水系溶液中硫化锑与氧化石墨烯复合，低温烧结结晶制备了一种形貌可靠、制备方法简单、原材料易得、成本低廉、易于规模化生产的硫化锑/石墨烯复合材料。复合材料中的石墨烯提供多孔结构，有利于充放电过程中钠离子的传输，另外紧密包覆在硫化锑表面的石墨烯可以提高整个材料的电子导电性，而且包覆在硫化锑表面的石墨烯可以缓解硫化锑充放电过程中的体积变化，所得到的材料具有较高的容量、优越的倍率性能和循环性能，特别适合作为钠离子二次电池的负极材料。 The application of carbon materials such as hard carbon, porous carbon, and carbon nanofibers in anode materials for sodium-ion batteries has been in-depth researched, but the low efficiency and low capacity of such materials for the first time will be difficult to meet practical applications. In contrast, elemental antimony and its compounds (as shown in Table 1) have aroused the interest of researchers due to their high specific capacity. Among all antimony-based compounds, antimony sulfide has better specific energy density, smaller volume change and better cycle performance than simple antimony and antimony oxides. In order to further improve the electrochemical performance of antimony sulfide, nanonization and composite graphene are effective means to alleviate material pulverization and improve the cycle life of materials. The price of the precursor materials required for the nano-antimony and its compounds and graphene composites reported in the literature is high, and the preparation process of many reported materials is complicated. These shortcomings limit the large-scale application of antimony sulfide/graphene composites. In the embodiment of the present invention, the commercialized one is used as the main raw material, and a two-step method, that is, compounding antimony sulfide and graphene oxide in an aqueous solution at room temperature, and sintering and crystallizing at a low temperature, prepares a kind of graphene oxide with reliable appearance, simple preparation method, and easy-to-obtain raw materials. Antimony sulfide/graphene composites that are cheap and easy to scale up. The graphene in the composite material provides a porous structure, which is conducive to the transmission of sodium ions during the charge and discharge process. In addition, the graphene tightly coated on the surface of antimony sulfide can improve the electronic conductivity of the entire material, and the graphite coated on the surface of antimony sulfide Alkene can alleviate the volume change during the charge-discharge process of antimony sulfide, and the obtained material has high capacity, superior rate performance and cycle performance, and is especially suitable as an anode material for sodium-ion secondary batteries.
发明内容 Contents of the invention
本发明所要解决的技术问题是提供一种钠离子电池硫化锑基复合材料及其制备方法，所述复合材料的组成是Sb2S3/石墨烯。 The technical problem to be solved by the present invention is to provide an antimony sulfide-based composite material for a sodium ion battery and a preparation method thereof. The composition of the composite material is Sb 2 S 3 /graphene.
本发明的目的通过以下技术方案实现。 The purpose of the present invention is achieved through the following technical solutions.
一种钠离子电池硫化锑基复合材料的制备方法，包括以下步骤： A preparation method of an antimony sulfide-based composite material for a sodium ion battery, comprising the following steps:
(1)将硫化锑搅拌溶解在介质中形成溶液; (1) stirring and dissolving antimony sulfide in the medium to form a solution;
(2)往步骤(1)所得溶液中加入0.1~30mgml-1的氧化石墨烯溶液，超声1~600min，直到分散均匀； (2) Add 0.1 to 30 mgml -1 graphene oxide solution to the solution obtained in step (1), and ultrasonicate for 1 to 600 min until uniform dispersion;
(3)将步骤(2)所得溶液与亚硫酸盐和酸混合溶液充分混合，搅拌1~600min，通过固液分离、干燥固体得到无定形硫化锑与氧化石墨烯复合材料前驱体； (3) Fully mix the solution obtained in step (2) with the mixed solution of sulfite and acid, stir for 1-600 min, and obtain the precursor of amorphous antimony sulfide and graphene oxide composite material by solid-liquid separation and drying the solid;
(4)将复合材料前驱体在惰性或者还原气氛下250~550℃煅烧1~24h，即得到钠离子电池硫化锑基复合材料。 (4) Calcining the precursor of the composite material at 250-550° C. for 1-24 hours under an inert or reducing atmosphere to obtain an antimony sulfide-based composite material for a sodium-ion battery.
进一步地，步骤（1）所述介质为硫化钠、硫化钾和硫化铵水溶液中的一种或几种，浓度为0.1~5molL-1，硫化锑与介质发生化学反应形成[SbS3]3-而溶解。 Further, the medium in step (1) is one or more of sodium sulfide, potassium sulfide and ammonium sulfide aqueous solution, the concentration is 0.1~5molL -1 , antimony sulfide chemically reacts with the medium to form [SbS 3 ] 3- And dissolve.
进一步地，步骤（1）所述硫化锑加入量与介质中硫化盐的摩尔比为（0.001~3）：1。 Further, the molar ratio of the added amount of antimony sulfide in step (1) to the sulfide salt in the medium is (0.001-3):1.
进一步地，步骤（2）所述的氧化石墨烯溶液中的氧化石墨烯与硫化锑质量比为（0.001~0.5）：1。 Further, the mass ratio of graphene oxide to antimony sulfide in the graphene oxide solution described in step (2) is (0.001-0.5):1.
进一步地，步骤（3）所述亚硫酸盐为亚硫酸铵、亚硫酸钾、亚硫酸钠、亚硫酸氢铵、亚硫酸氢钾和亚硫酸氢钠中的一种或几种；亚硫酸盐的加入量与介质中硫化盐的摩尔比为（0.5~5）：1。 Further, the sulfite in step (3) is one or more of ammonium sulfite, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite and sodium bisulfite; the addition of sulfite The molar ratio of the amount to the sulfide in the medium is (0.5~5):1.
进一步地，步骤（3）所述的酸为盐酸、硫酸、硝酸、醋酸、草酸和柠檬酸中的一种或几种；酸的加入量与介质中硫化盐的摩尔比为（0.5~3）：1；酸的浓度小于5molL-1。 Further, the acid described in step (3) is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid; the molar ratio of the amount of acid added to the sulfide salt in the medium is (0.5~3) : 1; the acid concentration is less than 5molL -1 .
步骤（3）的亚硫酸盐与酸为沉淀剂，加入沉淀剂的目的是为了消耗溶液中的S2-离子，使硫化锑和硫沉淀在氧化石墨烯表面，发生的反应如下：4[SbS3]3-+3SO3 2-+18H+→6S+9H2O+2Sb2S3。 The sulfite and acid in step (3) are used as precipitant. The purpose of adding precipitant is to consume S 2- ions in the solution, so that antimony sulfide and sulfur can be precipitated on the surface of graphene oxide. The reaction is as follows: 4[SbS 3 ] 3- +3SO 3 2- +18H + → 6S+9H 2 O+2Sb 2 S 3 .
进一步地，步骤（3）所述搅拌时间为5~600min。 Further, the stirring time in step (3) is 5-600 min.
进一步地，步骤（3）所述干燥为冷冻干燥、真空干燥和鼓风干燥中的一种或几种。 Further, the drying in step (3) is one or more of freeze drying, vacuum drying and blast drying.
进一步地，步骤（4）所述惰性或者还原气氛为氮气、氩气、氢气或者它们的混合气。 Further, the inert or reducing atmosphere in step (4) is nitrogen, argon, hydrogen or a mixture thereof.
由上述制备方法制得的一种钠离子电池硫化锑基复合材料，该复合材料由硫化锑与硫掺杂的石墨烯复合而成。 An antimony sulfide-based composite material for a sodium ion battery prepared by the above preparation method, the composite material is composed of antimony sulfide and sulfur-doped graphene.
与现有技术相比，本发明具有如下优点与技术效果： Compared with the prior art, the present invention has the following advantages and technical effects:
1）本发明提供了两步法即室温下的水系溶液中硫化锑与氧化石墨烯复合，低温烧结结晶制备了一种形貌可控、制备方法简单、原材料易得、成本低廉、易于规模化生产的钠离子电池硫化锑基复合材料。 1) The present invention provides a two-step method, that is, compounding antimony sulfide and graphene oxide in an aqueous solution at room temperature, and then sintering and crystallizing at a low temperature to prepare a compound with controllable morphology, simple preparation method, readily available raw materials, low cost, and easy scale-up Production of antimony sulfide-based composites for sodium-ion batteries.
2）本发明的复合材料中的石墨烯提供多孔结构，有利于充放电过程中钠离子的传输，另外紧密包覆在硫化锑表面的石墨烯可以提高整个材料的电子导电性，而且包覆在硫化锑表面的石墨烯可以缓解硫化锑充放电过程中的体积变化，所得到的材料具有较高的容量、优越的倍率性能和循环性能。 2) The graphene in the composite material of the present invention provides a porous structure, which is beneficial to the transmission of sodium ions during charging and discharging. In addition, the graphene tightly coated on the surface of antimony sulfide can improve the electronic conductivity of the entire material, and it is coated on Graphene on the surface of antimony sulfide can alleviate the volume change during the charge-discharge process of antimony sulfide, and the obtained material has high capacity, superior rate performance and cycle performance.
附图说明 Description of drawings
图1是实施例1中商业Sb2S3和Sb2S3/graphene材料XRD图谱； Fig. 1 is commercial Sb in embodiment 1 2 S 3 and Sb 2 S 3 /graphene material XRD collection of patterns;
图2是实施例1中制备的Sb2S3/graphene材料SEM图； Fig. 2 is the SEM figure of Sb 2 S 3 /graphene material prepared in embodiment 1;
图3是实施例1中制备的Sb2S3/graphene材料电流密度为100mAhg-1时的首次充放电曲线图； Fig. 3 is the first charge and discharge curve when the current density of the Sb 2 S 3 /graphene material prepared in Example 1 is 100mAhg -1 ;
图4是实施例2中商业Sb2S3、石墨烯和制备的Sb2S3/graphene材料Raman图； Fig. 4 is commercial Sb 2 S 3 , graphene and the prepared Sb 2 S 3 /graphene material Raman figure in embodiment 2;
图5是实施例2中制备的Sb2S3/graphene材料TEM图； Fig. 5 is the Sb 2 S 3 /graphene material TEM figure prepared in embodiment 2;
图6是实施例2中商业Sb2S3与制备的Sb2S3/graphene材料在电流密度为2Ag-1时循环性能图； Fig. 6 is the cycle performance diagram when the current density of commercial Sb 2 S 3 and the prepared Sb 2 S 3 /graphene material in Example 2 is 2Ag -1 ;
图7是实施例3中制备的Sb2S3/graphene材料的倍率性能图； Figure 7 is a rate performance diagram of the Sb 2 S 3 /graphene material prepared in Example 3;
图8是实施例3中商业Sb2S3与制备的Sb2S3/graphene材料在100次循环后的SEM图。 Fig. 8 is an SEM image of the commercial Sb 2 S 3 and the prepared Sb 2 S 3 /graphene material in Example 3 after 100 cycles.
具体实施方式 detailed description
下面结合附图和具体实施方式对本发明作进一步说明。以下实施例旨在说明本发明而不是对本发明的进一步限定。 The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. The following examples are intended to illustrate the present invention without further limiting the invention.
实施例1： Example 1:
将0.1mmol商业化Sb2S3搅拌溶解在1000ml浓度为0.1molL-1的硫化钠溶液中（硫化锑与硫化钠的摩尔比为0.001：1），往上述溶液中加入0.1mgml-1的氧化石墨烯溶液，使氧化石墨烯溶液中的氧化石墨烯与硫化锑质量比为0.001：1，并超声处理1分钟。将超声处理后的溶液加入到50mmol的亚硫酸钠和浓度为5molL-1的硫酸的混合溶液中（使亚硫酸钠与硫化钠的摩尔比为0.5：1，硫酸与硫化钠的摩尔比为0.5：1），搅拌5分钟，离心、冷冻干燥沉淀物得到前驱体。将该前驱体在氮气气氛250oC烧结24小时，得到Sb2S3/graphene材料。Sb2S3/graphene材料的物化性能表征见图1和图2。XRD显示该方法合成的Sb2S3/graphene材料与原料是一样的物相，即纯相硫化锑材料。SEM表明复合材料疏松多孔，并且硫化锑颗粒非常细小，与石墨烯复合均匀。将所得产物组装成扣式电池测其充放电容量，在0.01-2.5V范围内进行充放电。如图3所示为电流密度为100mAhg-1时的首次充放电曲线，充放电曲线没有石墨烯的充放电平台，说明包覆层不参与脱嵌钠。同时，复合材料的容量达到792.8mAhg-1。 Stir and dissolve 0.1 mmol of commercial Sb 2 S 3 in 1000 ml of sodium sulfide solution with a concentration of 0.1 mol L -1 (the molar ratio of antimony sulfide to sodium sulfide is 0.001:1), and add 0.1 mg ml -1 of oxidized Graphene solution, the mass ratio of graphene oxide and antimony sulfide in the graphene oxide solution is 0.001:1, and ultrasonic treatment for 1 minute. Add the solution after ultrasonic treatment to the mixed solution of 50mmol sodium sulfite and sulfuric acid with a concentration of 5molL -1 (make the molar ratio of sodium sulfite and sodium sulfide be 0.5:1, and the molar ratio of sulfuric acid and sodium sulfide be 0.5:1), Stir for 5 minutes, centrifuge, and freeze-dry the precipitate to obtain the precursor. The precursor was sintered in a nitrogen atmosphere at 250 o C for 24 hours to obtain a Sb 2 S 3 /graphene material. The physical and chemical properties of the Sb 2 S 3 /graphene material are shown in Figure 1 and Figure 2 . XRD shows that the Sb 2 S 3 /graphene material synthesized by this method is the same phase as the raw material, that is, the pure phase antimony sulfide material. SEM shows that the composite material is loose and porous, and the antimony sulfide particles are very fine, and they are uniformly composited with graphene. The resulting product was assembled into a button battery to measure its charge and discharge capacity, and the charge and discharge were carried out in the range of 0.01-2.5V. As shown in Figure 3, the first charge-discharge curve when the current density is 100mAhg -1 , the charge-discharge curve does not have a charge-discharge platform of graphene, indicating that the coating layer does not participate in the deintercalation of sodium. Meanwhile, the capacity of the composite reaches 792.8mAhg -1 .
实施例2： Example 2:
将30mmol商业化Sb2S3搅拌溶解在2ml浓度为5molL-1的硫化钾溶液中（硫化锑与硫化钾的摩尔比为3：1），往上述溶液中加入30mgml-1的氧化石墨烯溶液，使氧化石墨烯溶液中的氧化石墨烯与硫化锑质量比为0.5：1，并超声处理600分钟。将超声处理后的溶液加入到50mmol的亚硫酸铵、亚硫酸钾混合物（亚硫酸铵与亚硫酸钾摩尔比1:1）与0.01molL-1硝酸与醋酸的混合溶液（硝酸与醋酸摩尔比1:3）中（使亚硫酸盐与硫化钾的摩尔比为5：1，酸与硫化钾的摩尔比为3：1），搅拌10小时，真空抽滤、鼓风干燥滤渣得到的前驱体。将该前驱体在氩气气氛550oC烧结1小时，得到Sb2S3/graphene材料。Sb2S3/graphene材料的物化性能表征见图4、图5和图6。图4中Raman显示石墨烯成功与硫化锑复合。图5中TEM结果也表明硫化锑与石墨烯复合均匀。由图6可知，复合材料的循环稳定性得到大幅提升，200次循环后容量保持率为96.3%。 Stir and dissolve 30mmol of commercial Sb2S3 in 2ml of potassium sulfide solution with a concentration of 5molL -1 ( the molar ratio of antimony sulfide to potassium sulfide is 3:1), and add 30mgml -1 of graphene oxide solution to the above solution , so that the mass ratio of graphene oxide and antimony sulfide in the graphene oxide solution is 0.5:1, and ultrasonic treatment for 600 minutes. Add the solution after ultrasonic treatment to 50mmol of ammonium sulfite, potassium sulfite mixture (molar ratio of ammonium sulfite to potassium sulfite is 1:1) and mixed solution of 0.01molL -1 nitric acid and acetic acid (molar ratio of nitric acid to acetic acid is 1 :3) (the molar ratio of sulfite to potassium sulfide is 5:1, and the molar ratio of acid to potassium sulfide is 3:1), stirred for 10 hours, vacuum filtered, and blown to dry the precursor obtained from the filter residue. The precursor was sintered in an argon atmosphere at 550 o C for 1 hour to obtain a Sb 2 S 3 /graphene material. The physical and chemical properties of the Sb 2 S 3 /graphene material are shown in Figure 4, Figure 5 and Figure 6. Raman in Figure 4 shows that graphene was successfully compounded with antimony sulfide. The TEM results in Figure 5 also show that antimony sulfide and graphene are evenly combined. It can be seen from Figure 6 that the cycle stability of the composite material has been greatly improved, and the capacity retention rate after 200 cycles is 96.3%.
实施例3： Example 3:
将30mmol商业化Sb2S3搅拌溶解在8ml浓度为2.5molL-1的硫化铵与硫化钠混合溶液（硫化铵与硫化钠摩尔比1:3）中（硫化锑与硫化盐的摩尔比为1.5：1），往上述溶液中加入15mgml-1的氧化石墨烯溶液，使氧化石墨烯溶液中的氧化石墨烯与硫化锑质量比为0.25：1，并超声处理300分钟。将55mmol亚硫酸氢铵和35mmol硝酸（使亚硫酸盐与硫化盐的摩尔比为2.75：1，酸与硫化盐的摩尔比为1.75：1）的混合液倒入到上述溶液中，搅拌8小时，离心、真空干燥沉淀物得到前驱体。将该前驱体在3%vol.H2/N2气氛300oC烧结5小时，得到Sb2S3/graphene材料。将所得产物组装成扣式电池测其充放电容量，在0.01-2.5V范围内进行倍率性能测试与循环寿命测试。如图7所示为Sb2S3/graphene材料在不同电流密度下的容量。从图中可以看出，复合材料具有优越的倍率性能，如5Ag-1电流密度时，Sb2S3/graphene材料容量为589.8mAhg-1。图8为商业Sb2S3和Sb2S3/graphene材料在电流密度为1Ag-1时循环200次后的电极上的活性物质SEM图。从图中看出，商业Sb2S3材料粉化严重（如图8中的a、b），复合材料的形貌得到很好的保护（如图8中的c、d）。 Dissolve 30 mmol of commercial Sb 2 S 3 in 8 ml of a mixed solution of ammonium sulfide and sodium sulfide at a concentration of 2.5 mol L -1 (the molar ratio of ammonium sulfide to sodium sulfide is 1:3) (the molar ratio of antimony sulfide to sulfide salt is 1.5 : 1), add 15mgml -1 graphene oxide solution to the above solution, make the mass ratio of graphene oxide and antimony sulfide in the graphene oxide solution to be 0.25:1, and ultrasonically treat for 300 minutes. Pour the mixture of 55mmol ammonium bisulfite and 35mmol nitric acid (the molar ratio of sulfite to sulfide is 2.75:1, and the molar ratio of acid to sulfide is 1.75:1) into the above solution, and stir for 8 hours , centrifuge and vacuum dry the precipitate to obtain the precursor. The precursor was sintered in a 3%vol.H 2 /N 2 atmosphere at 300 o C for 5 hours to obtain a Sb 2 S 3 /graphene material. The resulting product was assembled into a button battery to measure its charge and discharge capacity, and the rate performance test and cycle life test were performed in the range of 0.01-2.5V. Figure 7 shows the capacity of the Sb 2 S 3 /graphene material at different current densities. It can be seen from the figure that the composite material has excellent rate performance, for example, at the current density of 5Ag -1 , the capacity of Sb 2 S 3 /graphene material is 589.8mAhg -1 . Fig. 8 is a SEM image of the active material on the electrode after 200 cycles of commercial Sb 2 S 3 and Sb 2 S 3 /graphene materials at a current density of 1Ag -1 . It can be seen from the figure that the commercial Sb 2 S 3 material is severely pulverized (a, b in Figure 8), and the morphology of the composite material is well protected (c, d in Figure 8).
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