CN108615862B - Method and application of composite material containing metal ionic liquid as medium - Google Patents
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000339 iron disulfide Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002114 nanocomposite Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003223 protective agent Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 229910052960 marcasite Inorganic materials 0.000 abstract description 13
- 229910052683 pyrite Inorganic materials 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 229910001507 metal halide Inorganic materials 0.000 abstract 1
- 150000005309 metal halides Chemical class 0.000 abstract 1
- 239000011814 protection agent Substances 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
本申请涉及一种以一系列含金属卤化物离子液体[CnMMIm][FeCl4]为金属源、组装媒介及表面保护剂合成新颖复合材料的方法及其用途。该申请首次采用晶态含金属长链离子液体[C12MMIm][FeCl4]作为多功能前驱体与氧化石墨烯复合，经过简单的溶剂热法硫化得到含离子液体的复合材料，然后在惰性气体的保护下热处理除去离子液体，得到二硫化铁与氮掺杂石墨烯的复合材料，记为FeS2@NG。所得材料作为锂离子负极材料组装电池后在恒温25℃、150mA/g的电流密度下，经过140个充放电循环后，可逆充放电容量可达950mAh/g；在5000mA/g的高电流密度下，充放电容量可达510mAh/g，这比之前报道的很多同类FeS2基材料的容量高很多。该方法制备的复合材料有望应用于下一代锂离子电池负极材料。
The present application relates to a method for synthesizing novel composite materials using a series of metal halide-containing ionic liquids [C n MMIm][FeCl 4 ] as metal sources, assembly media and surface protection agents and uses thereof. This application is the first to use crystalline metal-containing long-chain ionic liquid [C 12 MMIm][FeCl 4 ] as a multifunctional precursor to composite with graphene oxide. The ionic liquid was removed by heat treatment under the protection of gas, and the composite material of iron disulfide and nitrogen-doped graphene was obtained, which was denoted as FeS 2 @NG. The obtained material is used as a lithium ion anode material to assemble a battery at a constant temperature of 25 °C and a current density of 150 mA/g, and after 140 charge-discharge cycles, the reversible charge-discharge capacity can reach 950mAh/g; at a high current density of 5000mA/g. , the charge-discharge capacity can reach 510mAh/g, which is much higher than that of many similar FeS2 -based materials reported previously. The composite materials prepared by this method are expected to be used as anode materials for next-generation lithium-ion batteries.
Description
Technical Field
The invention is applied to the field of energy storage, and relates to a hierarchical nanocomposite synthesized by taking a metal ion-containing liquid as a medium.
Background
In recent years, lithium ion batteries have been developed rapidly and widely used in human life, but the demand for high-capacity and high-density energy storage devices has not been satisfied. FeS2As a natural mineral with abundant reserves, Fe and S in crystal lattices2The atomic layers are alternately arranged to form three-dimensional continuous crystals, and the crystal has the characteristics of stability, easy exploitation, low price and low toxicity. In recent years, with the research of electrode materials of lithium batteries, FeS2Such anode materials having typical conversion reaction characteristics are much higher than conventional intercalation-type reaction electrode materials (e.g., LiCoO)2,LiFePO4,LiMn2O4) The characteristics of capacity are of great interest to researchers. Unfortunately, FeS2Low conductivity, during charging and discharging reactionThe large structural change and the dissolution of polysulfide ions cause poor cycle stability, and the application of the material is seriously hindered. To solve this problem, researchers have designed and synthesized many FeS2The nanostructure (J.Power Sources,2016,328, 56-64; electrochim.acta,2018,260, 755-761; Mater.Lett.,2017,186,62-65) is further compounded with various high-conductivity carbon-based materials, so as to obtain the improvement of stability, but the improvement effect is not ideal. The main reason for this phenomenon is FeS2The faster nucleation and growth kinetics are more likely to lead to the formation of large grains, and the presence of large grains prolongs the lithium ion diffusion path, which also leads to difficulties in achieving FeS2Effective recombination with the conductive network. Therefore, how to regulate FeS2The growth kinetics of (A) is to increase the FeS grain size while allowing uniform recombination on the conductive substrate2The cycling stability of the/carbon composite material is one of the key problems to be solved.
In recent years, ionic liquids, in particular, imidazoles, have been increasingly used in the synthesis of composite materials (chem. eur.j.,2012,18, 8230-8239.; ACS appl.mater.interfaces,2017,9,8065-8074), which has a negligible vapor pressure, high stability, and high designability, making them a green solvent of great interest. The ionic liquid is used as a composite medium, plays a role in stabilizing, reducing the stacking of the layered objects and the like, thereby improving and enhancing the performance of the composite material and playing an important role in the synthesis of nano-micron materials. The metal-containing ionic liquid not only integrates the functions of a metal source, an assembly medium and a surface protective agent, but also has the special performance of better wettability with some carbon materials (Angew. chem., int. Ed.2015,54, 231-. Therefore, the ionic liquid is used as an assembly medium and applied to the synthesis of the carbon composite material, so that the bonding strength between the metal chalcogenide nanostructure and the carbon material can be improved, and the high-performance lithium ion battery electrode material is expected to be obtained. At present, the work of synthesizing the iron disulfide nano structure by using the metal-containing ionic liquid as a medium and compounding the iron disulfide nano structure with graphene to construct a novel composite material is not reported yet.
Disclosure of Invention
The invention aims to provide a liquid [ C ] containing metallic iron ionsnMMIm]FeCl4In which C isnMMIM is 1-n alkyl-2, 3-dimethyl imidazole; n is 3-12, and is used as a metal source, an assembly medium and a surface protective agent to synthesize the novel iron disulfide/nitrogen-doped graphene hierarchical nanocomposite FeS2The method of @ NG; by reacting [ CnMMIm]FeCl4Adding into graphene oxide ethanol dispersion solution, and stirring for a period of time to obtain [ C ]nMMIm]FeCl4Bonds well with oxygen-containing functional groups on graphene oxide. And further adding a sulfur source into the mixed solution, and stirring for a period of time to obtain a series of composite materials based on the graphene lamellar loaded crystalline iron disulfide nanodots. In the compound, the iron disulfide nanodots have a good crystalline structure, the size of the iron disulfide nanodots is controlled to be about tens of nanometers, and the iron disulfide nanodots are agglomerated to form microspheres, while the graphene conductive network is interpenetrated in the agglomerates to form a uniform nanocomposite structure and provide a good charge transport network. In other existing synthesis methods, no report on a crystalline iron disulfide nanodot and graphene oxide compound based on metal-containing ionic liquid as a precursor is found. It is worth mentioning that the ionic liquid not only has an important role in the synthesis and stability of the iron disulfide nanodots, but also has a strong electrostatic interaction with oxygen-containing groups on the surface of the graphene oxide, so that the iron disulfide nanodots can be induced to be better compounded with the carbon material.
The invention is realized by the following technical scheme: first through [ CnMMIm]FeCl4And mixing and stirring the mixture and graphene oxide ethanol dispersion liquid to obtain a mixture of ionic liquid and graphene oxide which are combined electrostatically, adding a sulfur source, stirring to obtain a composite structure of an iron disulfide nano-dot and a graphite oxide sheet layer, and finally removing the ionic liquid through heat treatment to obtain the final crystalline state iron disulfide/nitrogen-doped graphene hierarchical nanocomposite.
The invention comprises the following steps:
step a:mixing the ionic liquid and ferric chloride hexahydrate in a molar ratio of 1:1, stirring for a period of time, adding appropriate amount of water, heating in water bath to mix uniformly, and drying in a vacuum drying oven to obtain crystalline metal-containing ionic liquid [ CnMMIm]FeCl4。
The cation of the ionic liquid is imidazole, and the anion of the ionic liquid is halogen chloride ion;
step b: adding the product obtained in the step a into a graphene oxide ethanol dispersion solution synthesized in advance, and stirring for a period of time; then adding a sulfur source, stirring for a period of time, and then putting into a baking oven with a certain temperature for heating for a period of time.
Step c: c, centrifugally washing the product obtained in the step b by water and ethanol respectively, and drying the product in a vacuum drying oven at a certain temperature for a period of time;
step d: and c, carrying out heat treatment on the product obtained in the step c, pyrolyzing the ionic liquid serving as a metal source, an assembly medium and a multifunctional precursor of the surface protective agent, and reducing graphite oxide to form the final iron sulfide/nitrogen-doped graphene hierarchical nano composite material in one step.
Drawings
FIG. 1 different molar amounts of example 1 [ C12MMIm]FeCl4Synthesis schematic diagram (a) of composite material participating in synthesis and corresponding SEM FeS2@NG-0.5(b)，FeS2@NG-1(c)，FeS2@NG-2(d)；
FIG. 2 FeS of example 12A powder diffraction spectrum (a) and an XPS energy spectrum (b) of the @ NG-1 composite material;
FIG. 3 FeS of example 12XPS energy spectrum of @ NG-1;
FIG. 4 FeS of example 12A cyclic voltammogram of @ NG-1;
FIG. 5 example 1FeS2The results of cycles of lithium intercalation/deintercalation capacity (a) and rate (b) of @ NG-1.
Detailed Description
The invention selects [ C ]nMMIm]FeCl4As a medium, the ionic liquid cation helps to combine with the oxygen-containing functional pattern on the graphene oxide, and further introduces a sulfur sourceAnd obtaining the hierarchical nano composite structure compounded by the iron disulfide nano-dots and the graphene. In general, iron disulfide nanocrystals show cluster morphology in the process of compounding with graphene oxide due to the reason that the faster nucleation and growth kinetics are more likely to result in large grains, and graphene shows multilayer agglomeration morphology. In this series of compounds due to [ CnMMIm]FeCl4The existence of the graphene oxide nano-particles avoids the agglomeration among the nano-particles and stabilizes the surfaces of the nano-particles, thereby forming a uniform nano-dot structure, simultaneously slowing down the accumulation among layers of the graphene oxide, and finally forming a graphene conductive network which is inserted in the FeS2Nanocrystalline and further agglomerated to form a uniformly graded nanocomposite structure in the aggregate of microspheres.
Detailed Description
Example 1: by [ C ]12MMIm]FeCl4Synthesis of FeS as a Medium2@ NG nanocomposite.
Step a: will [ C ]12MMIm]Cl and FeCl3.6H2Mixing and stirring O according to the molar ratio of 1:1 for 1 hour, adding appropriate amount of water, heating in water bath to mix uniformly, and drying in a vacuum drying oven at 60 deg.C for 10 hours to obtain crystalline state [ C ]12MMIm]FeCl4(ChemtrySelect DOI:10.1002/slct.201800470)。
Step b: adding the product obtained in the step a into a 1mg/mL graphene oxide ethanol dispersion solution synthesized in advance, and stirring for 4 hours; then thiourea was added, stirred for 2 hours and put into an oven at 190 ℃ for 20 hours.
Step c: c, centrifugally washing the product obtained in the step b with water and ethanol for three times respectively, and then drying the product in a vacuum drying oven at 60 ℃ for 10 hours;
step d: and c, carrying out heat treatment on the product obtained in the step c at the heating rate of 1 ℃/min for 2 hours at 300 ℃ under the protection of high-purity argon, pyrolyzing the ionic liquid of the multifunctional precursor, and reducing graphite oxide to form the final iron disulfide/nitrogen-doped graphene hierarchical nanocomposite in one step.
Composites are also obtained by varying any of the variables according to claims 1 to 8 according to the above procedure, some examples are given in the following table:
Claims (7)
1. a method for synthesizing a composite material by using a liquid containing metal ions as a metal source, an assembly medium and a surface protective agent is characterized by comprising the following steps:
step a: mixing the ionic liquid and ferric chloride hexahydrate in the ratio of 1:1, stirring for a period of time, adding appropriate amount of water, heating in water bath to mix uniformly, and drying in vacuum drying oven to obtain ionic liquid [ C ] containing metallic FenMMIm][FeCl4]Wherein, CnMMIM is 1-n alkyl-2, 3-dimethyl imidazole, and n is 3-12; when n is 12, [ C ═ CnMMIm][FeCl4]Is in a crystalline state; when n is 3-11, [ C [ [ C ]nMMIm][FeCl4]The liquid-state material is in a liquid state,
the cation of the ionic liquid is imidazole, and the anion of the ionic liquid is halogen chloride ion;
step b: adding the product obtained in the step a into a graphene oxide ethanol dispersion solution with a certain concentration, which is synthesized in advance, and stirring for a period of time, wherein the concentration of the graphene oxide ethanol dispersion solution is 0.5-2 mg/mL;
step c: b, adding a sulfur source into the product obtained in the step b, and stirring for a period of time, wherein the sulfur source is thiourea; the molar ratio of the added sulfur source to the ionic liquid containing the metal Fe is 2: 1-6: 1,
step d: c, putting the product obtained in the step c into a drying oven at a certain temperature for a period of time;
step e: d, centrifugally washing the product obtained in the step d with water and ethanol for three times respectively, and then drying the product in a vacuum drying oven at a certain temperature for a period of time;
step f: and e, carrying out heat treatment on the product obtained in the step e, pyrolyzing the product to remove ionic liquid, and reducing and oxidizing graphene to form the final iron disulfide/nitrogen-doped graphene hierarchical nanocomposite, wherein the heat treatment temperature is 280-350 ℃, the heating rate is 1-5 ℃/min, and the heat treatment time is 2-5 hours.
2. The method according to claim 1, wherein the graphene oxide in step b is prepared by Hummers method or modified Hummers method.
3. The method of claim 1, wherein: and c, the concentration of the graphene oxide ethanol dispersion solution in the step b is 0.5-2 mg/mL.
4. The method of claim 1, wherein: and c, stirring for 1-4 hours in the step b.
5. The method of claim 1, wherein: and c, stirring for 0.5-2 hours.
6. The method of claim 1, wherein: the certain temperature in the step d is 190 ℃ and the period of time is 20 hours.
7. The method of claim 1, wherein: and f, the heat treatment protective atmosphere of the product is nitrogen or argon.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810299818.6A CN108615862B (en) | 2018-04-04 | 2018-04-04 | Method and application of composite material containing metal ionic liquid as medium |
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| CN201810299818.6A CN108615862B (en) | 2018-04-04 | 2018-04-04 | Method and application of composite material containing metal ionic liquid as medium |
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| Publication Number | Publication Date |
|---|---|
| CN108615862A CN108615862A (en) | 2018-10-02 |
| CN108615862B true CN108615862B (en) | 2021-08-06 |
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| CN106702423A (en) * | 2016-11-23 | 2017-05-24 | 广东轻工职业技术学院 | Iron disulfide/nitrogen-doped graphene nanocomposite, preparation and application |
| CN106981636A (en) * | 2017-04-11 | 2017-07-25 | 陕西科技大学 | A kind of preparation method of the nano combined anode material of lithium-ion batteries of FeS/RGO |
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| CN105304878A (en) * | 2015-11-13 | 2016-02-03 | 中国科学院福建物质结构研究所 | Nanometer tin diselenide/graphene composite material and its preparation method and use |
| CN106702423A (en) * | 2016-11-23 | 2017-05-24 | 广东轻工职业技术学院 | Iron disulfide/nitrogen-doped graphene nanocomposite, preparation and application |
| CN106981636A (en) * | 2017-04-11 | 2017-07-25 | 陕西科技大学 | A kind of preparation method of the nano combined anode material of lithium-ion batteries of FeS/RGO |
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