CN113097484B - Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof - Google Patents
Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN113097484B CN113097484B CN202110353501.8A CN202110353501A CN113097484B CN 113097484 B CN113097484 B CN 113097484B CN 202110353501 A CN202110353501 A CN 202110353501A CN 113097484 B CN113097484 B CN 113097484B
- Authority
- CN
- China
- Prior art keywords
- snse
- carbon
- solution
- compound
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 6
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 6
- 239000011669 selenium Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 74
- 239000011259 mixed solution Substances 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000967 suction filtration Methods 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005642 Oleic acid Substances 0.000 claims description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- -1 selenium ions Chemical class 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 238000012546 transfer Methods 0.000 description 18
- 239000012467 final product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 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 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910020813 Sn-C Inorganic materials 0.000 description 2
- 229910018732 Sn—C Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
技术领域technical field
本发明涉及钠离子电池负极材料技术领域，具体涉及一种碳包覆类三明治结构SnSe/r-GO@C复合物及其制备方法和应用。The invention relates to the technical field of anode materials for sodium ion batteries, in particular to a carbon-coated sandwich structure SnSe/r-GO@C composite and its preparation method and application.
背景技术Background technique
钠离子电池具有与锂离子电池相似的电化学储能原理，且钠资源储量丰富、价格低廉，被认为是实现规模化储能极具潜力的二次电池。然而Na+的直径远大于Li+，商业化锂离子电池石墨负极表现出差的Na+存储性能。因此，开发高性能储钠负极材料对钠离子电池至关重要。硒化锡作为合金类负极材料的一种，其嵌钠容量为780mAh g-1，具有极大的发展潜力。除此之外，SnSe是一种重要的IV-VI半导体材料，它的能隙大约为0.9eV，可广泛应用于红外光电装置、存储开关、薄膜电极、太阳能电池等。目前硒化锡基负极材料的钠离子电池性能极具潜力，但是其充放电结构稳定性仍需进一步改善。许多研究者选择将其与某种碳材料复合来改善上述问题，例如Xiaochuan Ren等人合成了Sn-C键连接的SnSe纳米盘垂直生长在掺氮的碳纳米带上，用于高性能钠离子电池的负极材料。通过计算表明，N原子在NC基体中的存在促进了Sn-C键的形成。SnSe具有较低的层间Na离子扩散势垒，从放电产物Sn到原始SnSe/NC具有较小的能量势垒，表明SnSe/NC具有快速的电化学动力学和良好的可逆性。Na-ion batteries have an electrochemical energy storage principle similar to lithium-ion batteries, and are rich in sodium resources and low in price. They are considered to be secondary batteries with great potential for large-scale energy storage. However, the diameter of Na + is much larger than that of Li + , and graphite anodes for commercial Li-ion batteries exhibit poor Na + storage performance. Therefore, the development of high-performance Na-storage anode materials is crucial for Na-ion batteries. As a kind of alloy negative electrode material, tin selenide has a sodium intercalation capacity of 780mAh g -1 , which has great potential for development. In addition, SnSe is an important IV-VI semiconductor material with an energy gap of about 0.9eV, which can be widely used in infrared optoelectronic devices, storage switches, thin film electrodes, solar cells, etc. At present, the performance of tin selenide-based anode materials for sodium-ion batteries is very promising, but the stability of its charge-discharge structure still needs to be further improved. Many researchers choose to compound it with some kind of carbon material to improve the above problems. For example, Xiaochuan Ren et al. synthesized Sn-C bonded SnSe nanodisks grown vertically on nitrogen-doped carbon nanobelts for high-performance sodium ions The negative electrode material of the battery. Calculations reveal that the presence of N atoms in the NC matrix promotes the formation of Sn-C bonds. SnSe has a low interlayer Na ion diffusion barrier and a small energy barrier from the discharge product Sn to pristine SnSe/NC, indicating the fast electrochemical kinetics and good reversibility of SnSe/NC.
发明内容Contents of the invention
为了解决现有技术中的问题，本发明提供了一种碳包覆类三明治结构SnSe/r-GO@C复合物及其制备方法和应用，将纳米颗粒状的SnSe均匀的生长在片状氧化石墨烯夹层之间，生长着硒化锡颗粒的三明治结构复合物外面包覆着一层碳材料，其结构稳定，作为钠离子电极材料具有较好的电化学性能。In order to solve the problems in the prior art, the present invention provides a carbon-coated sandwich structure SnSe/r-GO@C composite and its preparation method and application, in which the nano-particle SnSe is uniformly grown on the sheet-like oxide Between the graphene interlayers, the sandwich structure composite with tin selenide particles is covered with a layer of carbon material, which has a stable structure and has good electrochemical performance as a sodium ion electrode material.
为了实现以上目的，本发明提供了一种碳包覆类三明治结构SnSe/r-GO@C复合物的制备方法，包括以下步骤：In order to achieve the above objectives, the present invention provides a method for preparing a carbon-coated sandwich structure SnSe/r-GO@C composite, comprising the following steps:
1)将30～90mg的氧化石墨烯加入到30～70mL乙二醇或甘油中，分散后加入0.05696g～5.696g的无机锡盐，搅拌后再加入0.02g～0.2g的表面活性剂至完全溶解得到溶液A；1) Add 30-90mg of graphene oxide into 30-70mL of ethylene glycol or glycerin, add 0.05696g-5.696g of inorganic tin salt after dispersion, and then add 0.02g-0.2g of surfactant until complete Dissolving to obtain solution A;
2)将0.01975g～1.975g的硒粉加入到3～10ml的还原性溶剂中，搅拌至完全溶解得到溶液B；再将溶液B逐滴加入到溶液A中并搅拌，形成混合溶液C，混合溶液C中锡离子与硒离子按摩尔比为1：(1～4)；2) Add 0.01975g～1.975g of selenium powder into 3～10ml of reducing solvent, stir until completely dissolved to obtain solution B; then add solution B dropwise into solution A and stir to form mixed solution C, mix The molar ratio of tin ions and selenium ions in solution C is 1: (1-4);
3)将混合溶液C在120～200℃温度下水热反应，反应结束后冷却得到黑色的混合溶液D；3) hydrothermally reacting the mixed solution C at a temperature of 120-200° C., and cooling to obtain a black mixed solution D after the reaction;
4)将10～30g的氧化石墨烯加入到10～20ml的乙二醇或甘油中，分散后得到溶液E，将溶液E加入混合溶液D并搅拌，得到混合溶液F；4) Add 10-30 g of graphene oxide into 10-20 ml of ethylene glycol or glycerin, and disperse to obtain solution E, add solution E to mixed solution D and stir to obtain mixed solution F;
5)将混合溶液F在120～200℃温度下水热反应，反应结束后冷却得到黑色的混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体；5) The mixed solution F is hydrothermally reacted at a temperature of 120-200° C., cooled after the reaction to obtain a black mixed solution G, and the mixed solution G is collected by suction filtration to obtain a black powder;
6)将抽滤收集得到的黑色粉体冷冻干燥后得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨后得到混合物Y，将混合物Y在160～240℃温度下水热反应，反应结束后冷却得到黑色粉体，将黑色粉体经热处理后即得到碳包覆类三明治结构SnSe/r-GO@C复合物。6) Freeze-dry the black powder collected by suction filtration to obtain product X, mix and grind the product X and organic matter 2-methylimidazole in solid phase to obtain a mixture Y, and hydrothermally react the mixture Y at a temperature of 160-240°C, After the reaction is completed, the black powder is obtained by cooling, and the black powder is heat-treated to obtain a carbon-coated sandwich structure SnSe/r-GO@C composite.
进一步地，所述无机锡盐为SnCl2·2H2O。Further, the inorganic tin salt is SnCl 2 ·2H 2 O.
进一步地，所述表面活性剂为油酸。Further, the surfactant is oleic acid.
进一步地，所述还原性溶剂为乙二胺、三乙醇胺、水合肼或硼氢化钠水溶液。Further, the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution.
进一步地，所述搅拌采用磁力搅拌，搅拌速度为300～800r/min，搅拌时间30～120min。Further, the stirring adopts magnetic stirring, the stirring speed is 300-800 r/min, and the stirring time is 30-120 min.
进一步地，所述分散采用超声分散，超声时间为90～180min。Further, the dispersion adopts ultrasonic dispersion, and the ultrasonic time is 90-180 min.
进一步地，所述水热反应采用水热釜并将水热釜置于水热反应仪中进行，水热釜的填充度控制在50～80％。Further, the hydrothermal reaction is carried out by using a hydrothermal kettle and placing the hydrothermal kettle in a hydrothermal reactor, and the filling degree of the hydrothermal kettle is controlled at 50-80%.
本发明还提供了一种碳包覆类三明治结构SnSe/r-GO@C复合物，采用上述的一种碳包覆类三明治结构SnSe/r-GO@C复合物的制备方法制备得到。The present invention also provides a carbon-coated sandwich structure SnSe/r-GO@C composite, which is prepared by the above-mentioned preparation method of a carbon-coated sandwich structure SnSe/r-GO@C composite.
进一步地，所述复合物中氧化石墨烯片呈夹层结构，氧化石墨烯片上生长着SnSe纳米颗粒，夹层结构外包覆热解炭，SnSe纳米颗粒的尺寸为5～8nm。Further, the graphene oxide sheet in the composite has a sandwich structure, and SnSe nanoparticles grow on the graphene oxide sheet, and the sandwich structure is covered with pyrolytic carbon, and the size of the SnSe nanoparticles is 5-8 nm.
本发明还提供了一种上述的碳包覆类三明治结构SnSe/r-GO@C复合物的应用，所述复合物与粘结剂和导电剂混合后制备成钠离子电池负极材料。The present invention also provides an application of the above-mentioned carbon-coated sandwich structure SnSe/r-GO@C composite, which is prepared into a negative electrode material for a sodium-ion battery after being mixed with a binder and a conductive agent.
与现有技术相比，本发明以乙二醇或甘油作为溶剂，无机锡盐作为锡源，以乙二胺、三乙醇胺、水合肼或硼氢化钠水溶液作为还原剂，采用油酸作为表面活性剂，采用简单的溶剂热法结合热处理法制备出了纯相的碳包覆类三明治结构SnSe/r-GO@C复合物，且SnSe纳米颗粒的尺寸约为5～8nm，乙二胺、三乙醇胺、水合肼或硼氢化钠水溶液等作为还原剂不仅能够还原硒粉，提供Se2-，而且可以还原氧化石墨烯上的含氧官能团，进一步提高复合材料中石墨烯的导电性，另一方面，加入还原剂能够有效的与Sn2+络合，控制产物的尺寸，而纳米化材料对于提升电化学性能更有效。除此之外，本发明采用的制备方法简单，重复性高，加入氧化石墨烯经过水热反应后大大提高了SnSe基复合材料的导电性，与氧化石墨烯复合的基础上再包覆一层热解碳材料，可以有效提高复合物的结构稳定性，预计作为钠离子电极材料具有较好的电化学性能。Compared with the prior art, the present invention uses ethylene glycol or glycerin as solvent, inorganic tin salt as tin source, ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution as reducing agent, and oleic acid as surface active A pure-phase carbon-coated sandwich structure SnSe/r-GO@C composite was prepared by a simple solvothermal method combined with heat treatment, and the size of SnSe nanoparticles was about 5-8nm, ethylenediamine, three Ethanolamine, hydrazine hydrate or sodium borohydride aqueous solution as reducing agents can not only reduce selenium powder and provide Se 2- , but also reduce the oxygen-containing functional groups on graphene oxide, and further improve the conductivity of graphene in composite materials. On the other hand, , adding a reducing agent can effectively complex with Sn 2+ and control the size of the product, and nanomaterials are more effective for improving electrochemical performance. In addition, the preparation method adopted in the present invention is simple and highly repeatable. The conductivity of the SnSe-based composite material is greatly improved after adding graphene oxide through hydrothermal reaction, and then coated with graphene oxide on the basis of composite The pyrolytic carbon material can effectively improve the structural stability of the composite, and is expected to have good electrochemical performance as a sodium ion electrode material.
本发明制备了纯相的一种碳包覆类三明治结构SnSe/r-GO@C复合物，r-GO为均匀分布的片状结构，SnSe量子点均匀分布在r-GO片与片夹层之间，SnSe纳米颗粒为纯相的SnSe颗粒，颗粒的尺寸约为5～8nm，生长着硒化锡颗粒的三明治结构复合物外面包覆着一层碳材料，其结构稳定性，该复合电极有较好的钠离子存储性能，研究发现该复合电极储钠过程存在赝电容效应，具有较大的研究价值。本发明工艺简单，重复性高，制备周期短，反应温度低，降低了能耗和生产成本，适合大规模生产制备。The invention prepares a pure-phase carbon-coated sandwich structure SnSe/r-GO@C composite, r-GO is a uniformly distributed sheet structure, and SnSe quantum dots are evenly distributed between the r-GO sheet and the interlayer Among them, SnSe nanoparticles are pure-phase SnSe particles with a particle size of about 5-8nm. The sandwich structure composite with tin selenide particles is covered with a layer of carbon material, and its structure is stable. The composite electrode has Good sodium ion storage performance, the study found that the composite electrode has a pseudocapacitive effect in the sodium storage process, which has great research value. The invention has the advantages of simple process, high repeatability, short preparation cycle, low reaction temperature, reduced energy consumption and production cost, and is suitable for large-scale production and preparation.
附图说明Description of drawings
图1是本发明实施例1制备的复合物的X-射线衍射(XRD)图谱；Fig. 1 is the X-ray diffraction (XRD) collection of patterns of the complex prepared in the embodiment of the present invention 1;
图2是本发明实施例1制备的复合物的扫描电镜(SEM)照片；Fig. 2 is the scanning electron microscope (SEM) photo of the complex prepared in Example 1 of the present invention;
图3是本发明实施例1制备的复合物的透射电镜(TEM)照片。Fig. 3 is a transmission electron microscope (TEM) photo of the composite prepared in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合说明书附图和具体的实施例对本发明作进一步地解释说明，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The present invention will be further explained below in conjunction with the accompanying drawings and specific embodiments. Apparently, the described embodiments are part of the embodiments of the present application, not all of them. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the scope of protection of this application.
本发明提供了一种碳包覆类三明治结构SnSe/r-GO@C复合物的制备方法及应用，包括以下步骤：The invention provides a preparation method and application of a carbon-coated sandwich structure SnSe/r-GO@C composite, comprising the following steps:
步骤1)：将30～90mg的氧化石墨烯GO加入到30～70mL的乙二醇或甘油的溶剂中，超声分散后加入0.05696g～5.696g的SnCl2·2H2O，搅拌均匀后，再加入0.02g～0.2g的油酸至完全溶解形成溶液A；将0.01975g～1.975g的硒粉加入到3～10ml的乙二胺、三乙醇胺、水合肼或硼氢化钠水溶液中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；其中，锡离子与硒离子按摩尔比为1：(1～4)；氧化石墨烯在溶液A中的浓度为1～2mg·mL-1；Step 1): Add 30-90 mg of graphene oxide GO into 30-70 mL of ethylene glycol or glycerin solvent, ultrasonically disperse, add 0.05696 g-5.696 g of SnCl 2 ·2H 2 O, stir evenly, and then Add 0.02g～0.2g of oleic acid until completely dissolved to form solution A; add 0.01975g～1.975g of selenium powder into 3～10ml of ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution, and stir until completely Dissolve to obtain solution B; then add solution B dropwise to solution A to form mixed solution C, and stir evenly; wherein, the molar ratio of tin ions to selenium ions is 1: (1 ~ 4); graphene oxide in solution A The concentration in is 1~2mg·mL -1 ;
步骤2)：将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在120～200℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将10～30g的氧化石墨烯加入到10～20ml乙二醇或甘油中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在120～200℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体；将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在160～240℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z，即碳包覆类三明治结构SnSe/r-GO@C复合物。制备方法中搅拌采用磁力搅拌，搅拌速度为300～800r/min，搅拌时间30～120min，超声分散时间为90～180min，水热釜的填充度控制在50～80％。Step 2): Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 120-200°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution D; Add 10-30g of graphene oxide into 10-20ml of ethylene glycol or glycerin, and ultrasonically disperse evenly to obtain solution E, add solution E to solution D, stir evenly to obtain mixed solution F, and transfer mixed solution F to water Heat the kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 120-200°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution G, and collect the mixed solution G by suction filtration to obtain a black powder The powder obtained by suction filtration and separation is freeze-dried to obtain product X, and the product X is mixed and ground with organic matter 2-methylimidazole in a solid phase to obtain a mixture Y, and the mixture Y is transferred to a hydrothermal kettle, and then the hydrothermal kettle is placed In the hydrothermal reaction apparatus, fully react at 160-240°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black powder. Put the black powder in a tube furnace for heat treatment to obtain the final product Z, which is a carbon-coated sandwich Structural SnSe/r-GO@C composite. The stirring in the preparation method adopts magnetic stirring, the stirring speed is 300-800r/min, the stirring time is 30-120min, the ultrasonic dispersion time is 90-180min, and the filling degree of the hydrothermal kettle is controlled at 50-80%.
本发明还提供了一种采用上述方法制备的碳包覆类三明治结构SnSe/r-GO@C复合物，GO片上生长着细小的SnSe纳米颗粒，GO片与片之间呈夹层结构，表现为类三明治结构，三明治结构外包覆一层热解炭，其中SnSe纳米颗粒尺寸约为5～8nm。The present invention also provides a carbon-coated sandwich structure SnSe/r-GO@C composite prepared by the above method. Fine SnSe nanoparticles grow on the GO sheet, and the GO sheet has a sandwich structure, which is expressed as It has a sandwich structure, and the sandwich structure is covered with a layer of pyrolytic carbon, in which the size of SnSe nanoparticles is about 5-8nm.
本发明还提供了上述碳包覆类三明治结构SnSe/r-GO@C复合物的应用，作为钠离子电池负极材料使用时，碳包覆类三明治结构SnSe/r-GO@C复合物与粘结剂和导电剂按质量比8:1:1混合制备成负极片，粘结剂为羧甲基纤维素CMC，导电剂为super P。The present invention also provides the application of the carbon-coated sandwich structure SnSe/r-GO@C composite. When used as a negative electrode material for a sodium ion battery, the carbon-coated sandwich structure SnSe/r-GO@C composite and adhesive The binder and the conductive agent are mixed at a mass ratio of 8:1:1 to prepare a negative electrode sheet, the binder is carboxymethyl cellulose CMC, and the conductive agent is super P.
下面结合具体的实施例对本发明进行说明。The present invention will be described below in conjunction with specific embodiments.
实施例1：Example 1:
制备方法包括：Preparation methods include:
1)将30mg的氧化石墨烯GO加入到30mL乙二醇中，超声分散后加入0.07595g的SnCl2·2H2O，搅拌均匀后，再加入0.02g的油酸至完全溶解形成溶液A；将0.0263g硒粉加入到3ml的乙二胺水溶液中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 30 mg of graphene oxide GO to 30 mL of ethylene glycol, ultrasonically disperse and add 0.07595 g of SnCl 2 2H 2 O, stir evenly, then add 0.02 g of oleic acid until completely dissolved to form solution A; Add 0.0263g of selenium powder into 3ml of ethylenediamine aqueous solution, stir until completely dissolved to obtain solution B; then add solution B dropwise into solution A to form mixed solution C, and stir evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在120℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将10g氧化石墨烯加入到10ml乙二醇中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F；将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在120℃充分反应，反应结束后随炉冷却却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体，将抽滤分离得到的粉体冷冻干燥得到产物X；将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在160℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 120 ° C. After the reaction is completed, cool to room temperature with the furnace to obtain a black mixed solution D; 10 g of graphite oxide Add alkene into 10ml of ethylene glycol, ultrasonically disperse evenly to obtain solution E, add solution E to solution D, and stir to obtain mixed solution F; transfer mixed solution F to a hydrothermal kettle, and then place the hydrothermal kettle in In the hydrothermal reaction instrument, fully react at 120°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder, and the powder obtained by suction filtration is freeze-dried. Obtain product X; mix and grind product X and organic substance 2-methylimidazole in solid phase to obtain mixture Y, transfer mixture Y to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 160°C , After the reaction was completed, the black powder was obtained by cooling to room temperature with the furnace, and the black powder was placed in a tube furnace for heat treatment to obtain the final product Z.
采用日本理学D/max2000PCX-射线衍射仪分析样品SnSe/r-GO@C复合物，结果参见图1，发现样品与JCPDS编号为89-0232的SnSe结构一致，说明制备出SnSe纳米颗粒。将该样品用场发射扫描电子显微镜(FESEM)进行观察，结果参见图2，可以看出所制备的SnSe纳米颗粒均匀分散在片状氧化石墨烯表面。将该样品用透射电子显微镜(TEM)进行观察，结果参见图3，可以看出复合物中SnSe为大小约为5～8nm的纳米颗粒，均匀的生长在片状氧化石墨烯的表面。The sample SnSe/r-GO@C composite was analyzed by Rigaku D/max2000PC X-ray diffractometer. The results are shown in Figure 1. It was found that the sample was consistent with the SnSe structure of JCPDS No. 89-0232, indicating that SnSe nanoparticles were prepared. The sample was observed with a field emission scanning electron microscope (FESEM), and the results are shown in FIG. 2 . It can be seen that the prepared SnSe nanoparticles are uniformly dispersed on the surface of the flaky graphene oxide. The sample was observed with a transmission electron microscope (TEM), and the results are shown in Figure 3. It can be seen that the SnSe in the composite is a nano-particle with a size of about 5-8nm, which grows uniformly on the surface of the sheet-like graphene oxide.
实施例2：Example 2:
制备方法包括：Preparation methods include:
1)将45mg的氧化石墨烯GO加入到50mL的甘油中，超声分散后加入0.52785g的SnCl2·2H2O，搅拌均匀后，再加入0.08g的油酸至完全溶解形成溶液A；将0.0789g硒粉加入到5ml三乙醇胺水溶液中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 45mg of graphene oxide GO to 50mL of glycerin, after ultrasonic dispersion, add 0.52785g of SnCl 2 2H 2 O, stir evenly, then add 0.08g of oleic acid until completely dissolved to form solution A; Add g selenium powder into 5ml triethanolamine aqueous solution, stir until completely dissolved to obtain solution B; then add solution B dropwise to solution A to form mixed solution C, and stir evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在140℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将10g氧化石墨烯加入到10ml甘油中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在140℃充分反应，反应结束后随炉冷却却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体，将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在180℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 140 ° C. After the reaction is completed, cool to room temperature with the furnace to obtain a black mixed solution D; 10 g of graphite oxide Add alkene into 10ml of glycerin, ultrasonically disperse evenly to obtain solution E, add solution E to solution D, stir evenly to obtain mixed solution F, transfer mixed solution F to a hydrothermal kettle, and then place the hydrothermal kettle in a hydrothermal In the reactor, fully react at 140°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder, and the powder obtained by suction filtration is freeze-dried to obtain the product X, mix and grind the product X and the organic substance 2-methylimidazole in a solid state to obtain a mixture Y, transfer the mixture Y to a hydrothermal reactor, then place the hydrothermal reactor in a hydrothermal reactor, and fully react at 180°C. After the end, the furnace was cooled to room temperature to obtain a black powder, which was placed in a tube furnace for heat treatment to obtain the final product Z.
实施例3：Example 3:
制备方法包括：Preparation methods include:
1)将60mg氧化石墨烯GO加入到60mL甘油中，超声分散后加入1.0557g的SnCl2·2H2O，搅拌均匀后，再加入0.12g油酸至完全溶解形成溶液A；将0.2367g硒粉加入到6ml水合肼中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 60mg of graphene oxide GO to 60mL of glycerin, after ultrasonic dispersion, add 1.0557g of SnCl 2 2H 2 O, stir well, then add 0.12g of oleic acid until completely dissolved to form solution A; 0.2367g of selenium powder Add to 6ml of hydrazine hydrate, stir until completely dissolved to obtain solution B; then add solution B to solution A dropwise to form mixed solution C, and stir evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在160℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将20g氧化石墨烯加入到20ml甘油中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在160℃充分反应，反应结束后随炉冷却却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体，将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在200℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 160°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution D; put 20g of graphite oxide Add alkene into 20ml of glycerin, ultrasonically disperse evenly to obtain solution E, add solution E to solution D, stir evenly to obtain mixed solution F, transfer mixed solution F to a hydrothermal kettle, and then place the hydrothermal kettle in a hydrothermal In the reactor, fully react at 160°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder, and the powder obtained by suction filtration is freeze-dried to obtain the product X, the product X is mixed and ground with the organic substance 2-methylimidazole in solid phase to obtain the mixture Y, the mixture Y is transferred to a hydrothermal kettle, and then the hydrothermal kettle is placed in a hydrothermal reactor to fully react at 200°C. After the end, the furnace was cooled to room temperature to obtain a black powder, which was placed in a tube furnace for heat treatment to obtain the final product Z.
实施例4：Example 4:
制备方法包括：Preparation methods include:
1)将60mg氧化石墨烯GO加入到60mL乙二醇中，超声分散后加入3.1671g的SnCl2·2H2O，搅拌均匀后，再加入0.15g油酸至完全溶解形成溶液A；将0.7101g硒粉加入到5ml硼氢化钠水溶液中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 60mg of graphene oxide GO to 60mL of ethylene glycol, ultrasonically disperse, add 3.1671g of SnCl 2 ·2H 2 O, stir well, then add 0.15g of oleic acid until completely dissolved to form solution A; 0.7101g Add selenium powder into 5ml sodium borohydride aqueous solution, stir until completely dissolved to obtain solution B; then add solution B dropwise to solution A to form mixed solution C, and stir evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在180℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将20g氧化石墨烯加入到20ml乙二醇中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在180℃充分反应，反应结束后随炉冷却却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体，将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在220℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 180°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution D; put 20g of graphite oxide Add alkene into 20ml of ethylene glycol, ultrasonically disperse evenly to obtain solution E, add solution E to solution D, stir evenly to obtain mixed solution F, transfer mixed solution F to a hydrothermal kettle, and then place the hydrothermal kettle in In the hydrothermal reaction instrument, fully react at 180°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder, and the powder obtained by suction filtration is freeze-dried. The product X is obtained, and the product X is mixed and ground with the organic substance 2-methylimidazole in a solid phase to obtain a mixture Y, and the mixture Y is transferred to a hydrothermal kettle, and then the hydrothermal kettle is placed in a hydrothermal reactor, and fully reacted at 220°C , After the reaction was completed, the black powder was obtained by cooling to room temperature with the furnace, and the black powder was placed in a tube furnace for heat treatment to obtain the final product Z.
实施例5：Example 5:
制备方法包括：Preparation methods include:
1)将90mg氧化石墨烯GO加入到60mL乙二醇中，超声分散后加入5.696gSnCl2·2H2O，搅拌均匀后，再加入0.2g油酸至完全溶解形成溶液A；将1.975g硒粉加入到5ml水合肼中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 90mg graphene oxide GO to 60mL ethylene glycol, add 5.696g SnCl 2 ·2H 2 O after ultrasonic dispersion, stir well, then add 0.2g oleic acid until completely dissolved to form solution A; 1.975g selenium powder Add to 5ml of hydrazine hydrate, stir until completely dissolved to obtain solution B; then add solution B to solution A dropwise to form mixed solution C, and stir evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在160℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将20g氧化石墨烯加入到20ml乙二醇中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在180℃充分反应，反应结束后随炉冷却却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体，将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在240℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 160°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution D; put 20g of graphite oxide Add alkene into 20ml of ethylene glycol, ultrasonically disperse evenly to obtain solution E, add solution E to solution D, stir evenly to obtain mixed solution F, transfer mixed solution F to a hydrothermal kettle, and then place the hydrothermal kettle in In the hydrothermal reaction instrument, fully react at 180°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder, and the powder obtained by suction filtration is freeze-dried. The product X is obtained, the product X is mixed and ground with the organic substance 2-methylimidazole in solid phase to obtain the mixture Y, the mixture Y is transferred to a hydrothermal kettle, and then the hydrothermal kettle is placed in a hydrothermal reactor to fully react at 240°C , After the reaction was completed, the black powder was obtained by cooling to room temperature with the furnace, and the black powder was placed in a tube furnace for heat treatment to obtain the final product Z.
实施例6：Embodiment 6:
制备方法包括：Preparation methods include:
1)将30mg的氧化石墨烯GO加入到30mL的甘油中，超声分散后加入0.05696g的SnCl2·2H2O，搅拌均匀后，再加入0.02g的油酸至完全溶解形成溶液A；将0.01975g的硒粉加入到3ml的三乙醇胺水溶液中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 30mg of graphene oxide GO to 30mL of glycerin, after ultrasonic dispersion, add 0.05696g of SnCl 2 2H 2 O, stir evenly, then add 0.02g of oleic acid until completely dissolved to form solution A; g of selenium powder was added to 3ml of triethanolamine aqueous solution, stirred until completely dissolved to obtain solution B; then solution B was added dropwise to solution A to form mixed solution C, and stirred evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在120℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将10g的氧化石墨烯加入到10ml甘油中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在120℃充分反应，反应结束后随炉冷却却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体；将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在160℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 120°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution D; put 10 g of the oxidized Add graphene into 10ml glycerin, and obtain solution E after ultrasonic dispersion, add solution E to solution D, and stir to obtain mixed solution F, transfer mixed solution F to a hydrothermal kettle, and then place the hydrothermal kettle in water In the thermal reaction instrument, fully react at 120°C. After the reaction is completed, cool down to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder; the powder obtained by suction filtration is lyophilized to obtain Product X, the product X is mixed and ground with the organic substance 2-methylimidazole in solid phase to obtain a mixture Y, the mixture Y is transferred to a hydrothermal kettle, and then the hydrothermal kettle is placed in a hydrothermal reactor to fully react at 160°C, After the reaction is completed, cool down to room temperature with the furnace to obtain a black powder, which is placed in a tube furnace for heat treatment to obtain the final product Z.
实施例7：Embodiment 7:
制备方法包括：Preparation methods include:
1)将90mg的氧化石墨烯GO加入到70mL的乙二醇中，超声分散后加入5.696g的SnCl2·2H2O，搅拌均匀后，再加入0.2g的油酸至完全溶解形成溶液A；将1.975g的硒粉加入到10ml的乙二胺水溶液中，搅拌至完全溶解得到溶液B；然后将溶液B逐滴加入到溶液A中形成混合溶液C，并搅拌均匀；1) Add 90mg of graphene oxide GO to 70mL of ethylene glycol, ultrasonically disperse, add 5.696g of SnCl 2 ·2H 2 O, stir well, then add 0.2g of oleic acid until completely dissolved to form solution A; Add 1.975g of selenium powder into 10ml of ethylenediamine aqueous solution, stir until completely dissolved to obtain solution B; then add solution B dropwise to solution A to form mixed solution C, and stir evenly;
2)将混合液C转移至水热釜中，然后将水热釜置于水热反应仪中，在200℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液D；将30g的氧化石墨烯加入到20ml乙二醇中，超声分散均匀后得到溶液E，将溶液E加入溶液D，搅拌均匀后得到混合液F，将混合液F转移至水热釜中，然后将水热釜置于水热反应仪中，在200℃充分反应，反应结束后随炉冷却至室温得到黑色混合溶液G，将混合溶液G进行抽滤收集得到黑色粉体；将抽滤分离得到的粉体冷冻干燥得到产物X，将产物X与有机物2-甲基咪唑固相混合研磨得到混合物Y，将混合物Y转移至水热釜中，然后将水热釜置于水热反应仪中，在240℃充分反应，反应结束后随炉冷却至室温得到黑色粉体，将黑色粉体至于管式炉中经热处理得到最终产物Z。2) Transfer the mixed solution C to a hydrothermal kettle, then place the hydrothermal kettle in a hydrothermal reactor, and fully react at 200°C. After the reaction, cool to room temperature with the furnace to obtain a black mixed solution D; put 30g of oxidized Add graphene into 20ml of ethylene glycol, obtain solution E after ultrasonic dispersion, add solution E to solution D, and obtain mixed solution F after stirring evenly, transfer mixed solution F to a hydrothermal kettle, and then put the hydrothermal kettle Fully react in a hydrothermal reaction apparatus at 200°C. After the reaction is completed, cool to room temperature with the furnace to obtain a black mixed solution G. The mixed solution G is collected by suction filtration to obtain a black powder; the powder obtained by suction filtration is freeze-dried The product X is obtained, the product X is mixed and ground with the organic substance 2-methylimidazole in solid phase to obtain the mixture Y, the mixture Y is transferred to a hydrothermal kettle, and then the hydrothermal kettle is placed in a hydrothermal reactor to fully react at 240°C , After the reaction was completed, the black powder was obtained by cooling to room temperature with the furnace, and the black powder was placed in a tube furnace for heat treatment to obtain the final product Z.
本发明以乙二醇或甘油作为溶剂，采用简单的溶剂热法制备了碳包覆类三明治结构SnSe/r-GO@C复合物，其中SnSe纳米颗粒为尺寸大小约为5～8nm的纯相纳米颗粒，并均匀的分散在片状氧化石墨烯夹层间。本发明制备方法简单，周期短，并且以氧化石墨烯和热解碳作为碳基体，不仅提高了SnSe的导电性，而且提高了复合材料的结构稳定性，该复合物作为钠离子电池负极材料，有较好的电化学性能，研究发现SnSe/r-GO@C复合物电极储钠过程存在赝电容效应，具有较大的研究价值。该复合材料作为光催化材料和电极材料，具有较好的光催化和电化学性能。The present invention uses ethylene glycol or glycerin as a solvent to prepare a carbon-coated sandwich structure SnSe/r-GO@C composite by a simple solvothermal method, wherein the SnSe nanoparticles are pure phases with a size of about 5-8nm Nanoparticles, and uniformly dispersed in the sheet-like graphene oxide interlayer. The preparation method of the invention is simple, the cycle is short, and graphene oxide and pyrolytic carbon are used as the carbon matrix, which not only improves the conductivity of SnSe, but also improves the structural stability of the composite material. The composite is used as a negative electrode material for a sodium ion battery. It has good electrochemical performance, and the study found that there is a pseudocapacitive effect in the sodium storage process of the SnSe/r-GO@C composite electrode, which has great research value. As a photocatalytic material and an electrode material, the composite material has good photocatalytic and electrochemical properties.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it still The technical solutions described in the foregoing embodiments can be modified, or some or all of the technical features can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110353501.8A CN113097484B (en) | 2021-04-01 | 2021-04-01 | Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110353501.8A CN113097484B (en) | 2021-04-01 | 2021-04-01 | Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113097484A CN113097484A (en) | 2021-07-09 |
| CN113097484B true CN113097484B (en) | 2023-04-28 |
Family
ID=76673060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110353501.8A Active CN113097484B (en) | 2021-04-01 | 2021-04-01 | Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113097484B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114843464A (en) * | 2022-04-21 | 2022-08-02 | 陕西科技大学 | A three-dimensional cross-linked SnSe/3D r-GO composite material and its preparation method and application |
| CN114988419B (en) * | 2022-05-25 | 2023-12-08 | 陕西科技大学 | SiO (silicon dioxide) 2 SnSe/C nanospheres and preparation method thereof |
| CN114890392B (en) * | 2022-06-08 | 2024-01-30 | 陕西科技大学 | Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof |
| CN115893331B (en) * | 2022-11-30 | 2024-11-22 | 陕西科技大学 | A SnSe/SnO2@C composite and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212176A (en) * | 2019-05-16 | 2019-09-06 | 南京工业大学 | Preparation method of graphene/molybdenum disulfide nanosphere/carbon black composite material |
| CN110492068A (en) * | 2019-08-05 | 2019-11-22 | 中南大学 | Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof |
| CN111180707A (en) * | 2020-01-14 | 2020-05-19 | 中南大学 | Tin diselenide/tin oxide-rGO nanocomposite anode material and preparation method |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103887488B (en) * | 2014-04-04 | 2015-12-02 | 哈尔滨工业大学 | Lithium ion battery peach kernel shape SnO 2the preparation method of-Graphene-carbon composite |
| CN106328952A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Lithium electrode material, and preparation method and application thereof |
| CN105964238A (en) * | 2016-07-26 | 2016-09-28 | 宁波大学 | Porous carbon coated ZnO nanometer composite material and preparing method thereof |
| CN107123794B (en) * | 2017-05-08 | 2019-11-15 | 陕西科技大学 | A preparation method of carbon-coated manganese monoxide/nitrogen-doped reduced graphene oxide lithium-ion battery negative electrode material |
| CN107017395B (en) * | 2017-05-22 | 2020-04-21 | 中南大学 | A carbon-coated sodium manganese pyrophosphate@reduced graphene oxide composite material with sandwich structure and its preparation method and application |
| CN107893218B (en) * | 2017-10-27 | 2020-01-10 | 苏州大学 | Titanium dioxide/sulfonated graphene oxide/silver nanoparticle composite membrane and preparation method and application thereof |
| CN107887592B (en) * | 2017-11-17 | 2020-09-01 | 武汉理工大学 | Carbon-coated ZnO nanowires, preparation method and application thereof |
| CN109052367B (en) * | 2018-09-30 | 2020-02-14 | 华中科技大学 | Preparation method of pyridine nitrogen-enriched ultrathin carbon nanosheet material and metal composite material thereof |
| CN109585831B (en) * | 2018-12-04 | 2022-04-01 | 浙江理工大学 | Composite material with sandwich structure and preparation method and application thereof |
| CN109742353B (en) * | 2018-12-29 | 2021-05-25 | 陕西科技大学 | SnSe quantum dot/r-GO compound and preparation method and application thereof |
| CN111825119A (en) * | 2019-04-23 | 2020-10-27 | 赵彦霖 | Preparation method of zinc ion battery positive electrode material |
| CN112490430A (en) * | 2020-12-07 | 2021-03-12 | 江苏师范大学 | Preparation method of high-performance negative electrode material for lithium/sodium ion battery |
-
2021
- 2021-04-01 CN CN202110353501.8A patent/CN113097484B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212176A (en) * | 2019-05-16 | 2019-09-06 | 南京工业大学 | Preparation method of graphene/molybdenum disulfide nanosphere/carbon black composite material |
| CN110492068A (en) * | 2019-08-05 | 2019-11-22 | 中南大学 | Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof |
| CN111180707A (en) * | 2020-01-14 | 2020-05-19 | 中南大学 | Tin diselenide/tin oxide-rGO nanocomposite anode material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 李婷 ; 龙志辉 ; 张道洪 ; .Fe_2O_3/rGO纳米复合物的制备及其储锂和储钠性能.物理化学学报.2016,(第02期),全文. * |
| 钱翔英 ; .三明治结构G@SnO_2 @C复合材料的合成、表征及其钠离子电池负极性能研究.电子显微学报.2019,(第02期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113097484A (en) | 2021-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113097484B (en) | Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof | |
| CN105870447B (en) | Sodium-ion battery N doping rutile TiO2The preparation method of/C negative materials | |
| CN113346054B (en) | Preparation method and application of MXene-carbon nanocage-sulfur composite material | |
| WO2022032747A1 (en) | Method for preparing sulfur-doped rese2/mxene composite material | |
| CN108899504A (en) | A kind of antimony-carbon nanotube-carbon composite, preparation method and application | |
| CN105883940B (en) | Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery | |
| CN103227317A (en) | V2O5 quantum dot/graphene composite material and its preparation method and application | |
| CN106058181A (en) | Preparation method of graphene-supported carbon-coated silicone nanoparticle composite electrode material | |
| CN109742353A (en) | A kind of SnSe quantum dot/r-GO composite and its preparation method and application | |
| CN108695495A (en) | Redox graphene modifies antimonous sulfide cell negative electrode material | |
| CN110165171B (en) | In situ self-assembled nano-flower-like cobalt disulfide/rGO composite material and its preparation method and application | |
| CN106711432A (en) | A kind of three-dimensional network structure MoO2 nanometer material and its preparation and application | |
| CN110071272A (en) | A kind of boron doping silicon substrate composite negative pole material and its preparation method and application | |
| Zhu et al. | Free-standing hybrid films comprising of ultra-dispersed titania nanocrystals and hierarchical conductive network for excellent high rate performance of lithium storage | |
| CN106848246A (en) | A kind of three-dimensional structure TiO2/ graphene aerogel compound and its preparation method and application | |
| Hu et al. | A new method of synthesis of Sb 2 Se 3/rGO as a high-rate and low-temperature anode for sodium–ion batteries | |
| Liang et al. | Ultrafine SnO2 coated by wheat straw-derived carbon used as anode for high-performance lithium ion batteries | |
| CN114243007A (en) | A kind of nickel disulfide/carbon nanotube composite electrode material and preparation method and application | |
| CN113097485B (en) | Sandwich-like structure SnSe/r-GO compound and preparation method and application thereof | |
| CN108598377A (en) | The preparation method of sulphur-silicon carbide doped carbon nano-tube material | |
| CN113054170A (en) | Preparation method of nickel-nickel molybdenum oxide-graphene composite material and application of nickel-nickel molybdenum oxide-graphene composite material in lithium ion battery | |
| CN112938952A (en) | Preparation and application of cathode material with two-dimensional structure tungsten trioxide coated with graphene | |
| CN116161709B (en) | Graphene oxide coated nano lithium cobalt oxide positive electrode material and preparation method thereof | |
| CN108417824B (en) | A kind of preparation method of high performance lithium battery negative electrode material carbon-coated lithium titanate | |
| CN114314528B (en) | Two-dimensional layered nano-sheet and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |