CN108615862B - Method for synthesizing composite material by using metal ion-containing liquid as medium and application - Google Patents

Method for synthesizing composite material by using metal ion-containing liquid as medium and application Download PDF

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CN108615862B
CN108615862B CN201810299818.6A CN201810299818A CN108615862B CN 108615862 B CN108615862 B CN 108615862B CN 201810299818 A CN201810299818 A CN 201810299818A CN 108615862 B CN108615862 B CN 108615862B
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丁雪妲
杜乘风
李建荣
黄小荥
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Fujian Institute of Research on the Structure of Matter of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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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Abstract

The application relates to a series of ionic liquids [ C ] containing metal halidenMMIm][FeCl4]Methods for synthesizing novel composite materials for metal sources, assembly media, and surface protectants and uses thereof. The application adopts crystalline state metal-containing long-chain ionic liquid [ C ] for the first time12MMIm][FeCl4]Compounding the multifunctional precursor with graphene oxide, performing simple solvothermal vulcanization to obtain a composite material containing ionic liquid, performing heat treatment under the protection of inert gas to remove the ionic liquid to obtain a composite material of iron disulfide and nitrogen-doped graphene, which is recorded as FeS2@ NG. After the obtained material is used as a lithium ion negative electrode material to be assembled into a battery, the reversible charge-discharge capacity can reach 950mAh/g after 140 charge-discharge cycles at the constant temperature of 25 ℃ and the current density of 150 mA/g; under the high current density of 5000mA/g, the charge-discharge capacity can reach 510mAh/g, which is more than that of many similar FeS reported before2The capacity of the base material is much higher. The composite material prepared by the method is expected to be applied to the next generation of lithium ion battery cathode materials.

Description

Method for synthesizing composite material by using metal ion-containing liquid as medium and application
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:
Figure BDA0001619399930000041

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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CN108987718B (en) * 2018-07-24 2021-06-29 西南科技大学 Lithium ion battery cathode material core-shell structure FeS2Preparation method of @ C nanoring
CN110085435B (en) * 2019-04-15 2021-01-01 东北大学 Nitrogen-sulfur-doped iron sulfide/graphene aerogel composite material and preparation method thereof
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CN113659135B (en) * 2021-08-11 2023-02-03 电子科技大学 Application of iron sulfide in lithium iron phosphate secondary battery

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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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* Cited by examiner, † Cited by third party
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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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