CN114890458A - Metal oxide-carbon-based composite material with bowl-shaped structure and preparation method and application thereof - Google Patents
Metal oxide-carbon-based composite material with bowl-shaped structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal oxide-carbon-based composite material with a bowl-shaped structure, and a preparation method and application thereof, and belongs to the technical field of lithium ion battery electrode materials. The method comprises the following steps: (1) dissolving dopamine hydrochloride, triblock copolymer and metal source in ethanol water solution, adding 1,3, 5-trimethylbenzene, carrying out ultrasonic treatment, adding ammonia water under the condition of stirring, and reacting to obtain precipitate; (2) and dispersing the precipitate in an ethanol water solution, carrying out hydrothermal curing reaction, washing, drying, and carrying out high-temperature calcination treatment to obtain the metal oxide-carbon-based composite material with the bowl-shaped structure. Unnecessary idle space in traditional hollow particle has been got rid of to this bowl form hollow structure, compares with the clean shot that the diameter is the same, has higher bulk density, has improved the volume energy and the power density of electrode, has overcome the shortcoming that traditional hollow particle volume energy density is low.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a metal oxide-carbon-based composite material with a bowl-shaped structure, and a preparation method and application thereof.
Background
The lithium ion battery is used as a renewable clean energy source, has the advantages of high energy density, wide working temperature range, long cycle life, no memory effect, small environmental pollution and the like, is widely applied to battery markets of various mobile electronic devices, such as mobile phones, notebook computers and the like, and the research and development of the power lithium ion battery are further promoted due to the appearance and rapid development of new energy automobiles.
Graphite has been used for a long time as a negative electrode material for lithium ion batteries. But the demand of rapid development of lithium ion batteries cannot be met due to low lithium intercalation capacity. SnO 2 The lithium ion battery has the characteristics of high specific capacity, relatively safe working voltage, environmental friendliness and the like, so that the lithium ion battery is widely concerned, and is considered to be a new generation of lithium ion battery cathode material capable of replacing commercial graphite cathode materials. However, SnO 2 During the charge-discharge cycle, a large volume change (more than 300%) and the active material are pulverized and peeled off from the current collector, so that the capacity of the battery is rapidly attenuated. Further, SnO 2 Is a semiconductor material, and has poor conductivity, resulting in poor rate capability. These disadvantages severely restrict SnO 2 The cathode material is practically applied to the lithium ion battery.
To overcome the defect of pure SnO 2 These disadvantages of the negative electrode material, nano-structured SnO 2 And carbon material are compounded in a suitable manner, so that SnO can be greatly improved 2 Cycle performance and rate capability of the negative electrode material. In particular hollow core-shell structure SnO 2 -a C-based composite anode material, which has some specific advantages: (1) the cavity part of the hollow structure can be buffer SnO 2 The huge volume change and stress generated in the charge-discharge cycle process provide a larger free space; (2) large ratio tableThe area and the thin shell structure can respectively increase the contact area between the active material and the electrolyte and shorten the transmission distance of electrons and ions; (3) carbon coating can also inhibit nanoscale SnO 2 The agglomeration and pulverization between the two components can ensure that the structural integrity of the electrode material can be still maintained after the electrode material is subjected to long-term charge-discharge cycles. However, most of the hollow structural materials (hollow spheres, hollow cubes, hollow tubes and the like) prepared at present have large cavities, except for being used for buffering the volume change generated by cyclic stress, a large part of space is idle and not effectively utilized, and the part of space does not contribute to the electrochemical performance of the material, so that the volume energy density of the lithium ion battery is reduced. Thus, SnO 2 The cathode material still has the defects of low volume energy density, low cycle performance and rate performance, and in addition, SnO 2 Limited resources, research on SnO only 2 The negative electrode materials also limit further development of lithium ion batteries. Thus, novel SnO was developed 2 The negative electrode material or other lithium ion battery negative electrode materials are necessary for further development of the lithium ion battery to improve the cycle performance and rate capability of the lithium ion battery.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a metal oxide-carbon-based composite material with a bowl-shaped structure, and a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is a preparation method of a metal oxide-carbon-based composite material with a bowl-shaped structure, which comprises the following steps:
(1) dissolving dopamine hydrochloride, triblock copolymer and metal source in ethanol water solution, adding 1,3, 5-trimethylbenzene, carrying out ultrasonic treatment, adding ammonia water under the condition of stirring, and reacting to obtain precipitate;
(2) and dispersing the precipitate in an ethanol water solution, carrying out hydrothermal curing reaction, washing, drying, and carrying out high-temperature calcination treatment in an inert atmosphere to obtain the metal oxide-carbon-based composite material with the bowl-shaped structure.
Further, the precipitate is polydopamine nanoparticles that chelate metal ions.
Further, the ammonia water is added dropwise under the stirring condition, the ammonia water is used as a catalyst of a reaction system, dopamine is subjected to polymerization reaction under the alkaline condition formed by the ammonia water, and the ammonia water is uniformly dispersed by dropwise addition, so that local pH is not too high.
Further, in the step (1), the triblock copolymer is one or a mixture of two of polyether F127 and polyether P123, and the metal source is a metal salt.
Further, the dopamine hydrochloride is used as a carbon source and a nitrogen source in a reaction system, the triblock copolymer is used as a pore-forming agent in the reaction system, and the 1,3, 5-trimethylbenzene is used as a pore-expanding agent and an emulsion drop template in the reaction system.
Further, the metal salt is a metal ion salt which can be complexed with aqueous ammonia, or a hydroxide compound of the metal ion in the metal salt is soluble in an alkali solution.
Further, the metal salt is Sn 2+ Salt, Sn 4+ Salt, Zn 2+ Salt, Ce 4+ Salt, Co 2+ Salt, Ni 2+ Salt, Mn 2+ Salt, Fe 2+ One of a salt; the triblock copolymer is one or two of polyether F127 and polyether P123.
Further, the Sn 2+ The salt is stannous chloride, Sn 4+ The salt is ammonium hexachlorostannate (IV) and the Zn 2+ The salt is zinc chloride or zinc sulfate ammonium hydrate, the Ce 4+ The salt is cerium sulfate, the Co 2+ The salt is cobalt nitrate or cobalt (II) sulfate ammonium hydrate, the Ni 2+ The salt is nickel acetate, the Mn 2+ The salt is manganese acetate or manganese (II) sulfate ammonium hydrate, the Fe 2+ The salt is ferrous chloride or ferrous ammonium sulfate hydrate.
Further, the metal salt is Sn 2+ Salt or Sn 4+ When the metal oxide-carbon-based composite material is salted, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is tin oxide-carbon (SnO) 2 A radical of-C)Combining materials; the metal salt is Zn 2+ When in salt treatment, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is a zinc oxide-carbon-based composite material; the metal salt is Ce 4+ When in salt treatment, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is a cerium oxide-carbon-based composite material; the metal salt is Co 2+ When in salt treatment, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is cobaltosic oxide-carbon-based composite material; the metal salt is Ni 2+ When in salt treatment, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is a nickel oxide-carbon-based composite material; the metal salt is Mn 2+ When in salt treatment, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is a manganese dioxide-carbon-based composite material; the metal salt is Fe 2+ And in the salt process, the obtained metal oxide-carbon-based composite material with the bowl-shaped structure is a ferroferric oxide-carbon-based composite material or a ferric oxide-carbon-based composite material.
Further, in step (1), in terms of molar ratio, the ratio of dopamine hydrochloride: triblock copolymer: 1,3, 5-trimethylbenzene: metal source: NH (NH) 3 ·H 2 O＝1：0.008～0.016：1.6～2.4：0.05～0.5：4～30。
Further, the concentration of the triblock copolymer in the reaction system of the step (1) is 1.0-1.5 wt%.
The calculation method of the concentration of the triblock copolymer referred to herein is: the triblock copolymer concentration is the triblock copolymer mass/(triblock copolymer mass + ethanol aqueous solution mass).
In the whole experiment process, the concentration of the pore-forming agent triblock copolymer is required to be ensured to be within a certain range for preparing the specific pore structure, namely the dosage of the pore-forming agent triblock copolymer and the solvent ethanol water solution is required to be determined firstly, and under the condition of quantitative quantity of the pore-forming agent triblock copolymer, the pore-forming agent triblock copolymer is mixed with dopamine hydrochloride, 1,3, 5-trimethylbenzene, a metal source and NH in ammonia water 3 ·H 2 The molar ratio of O determines the amounts of the other substances.
Further, dissolving dopamine hydrochloride, triblock copolymer and metal source in ethanol water solution in two ways, namely dissolving dopamine hydrochloride and triblock copolymer in ethanol water solution, adding metal source, mixing and stirring uniformly; the second mode is that dopamine hydrochloride, triblock copolymer and metal source are mixed and added into ethanol water solution for dissolution.
Further, the ethanol aqueous solution in the step (1) is formed by mixing absolute ethanol and water according to the volume ratio of 1:1, and the ethanol aqueous solution in the step (2) is formed by mixing absolute ethanol and water according to the volume ratio of 1: 1.
Further, the reaction time in the step (1) is 2-6 h.
Further, the power of ultrasonic treatment is 100W, and the time of ultrasonic treatment is 2-5 min.
Further, the mass-to-volume ratio of the dopamine hydrochloride in the step (1) to the ethanol water solution in the step (2) is 0.05-0.5 g: 10 mL.
Further, the temperature of the hydrothermal curing reaction in the step (2) is 80-150 ℃, and the time is 12-30 h; the drying temperature is 50-80 ℃, and the drying time is 6-24 hours; firstly heating to 300-500 ℃, carrying out heat preservation treatment for 1-2 h, and then heating to 600-900 ℃ for high-temperature calcination for 2-4 h.
Further, the temperature rise rate of the first temperature rise process in the high-temperature calcination treatment is 1-5 ℃/min, and the temperature rise rate of the second temperature rise process is 1-5 ℃/min.
Further, the inert atmosphere is argon or nitrogen.
The second technical scheme of the invention is that the metal oxide-carbon-based composite material with the bowl-shaped structure is prepared according to the preparation method.
Further, nitrogen and the metal element are uniformly dispersed in the metal oxide-carbon based composite particles.
In the third technical scheme of the invention, the application of the metal oxide-carbon-based composite material with the bowl-shaped structure in the lithium ion battery is provided.
Further, the metal oxide-carbon-based composite material with the bowl-shaped structure is used as a negative electrode material of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the metal oxide-carbon-based composite material with the bowl-shaped structure prepared by the invention has the following advantages: 1) abundant mesoporous structure and higher specific surface area can provide more reactive sites, thereby improving the reaction efficiency; 2) the uniformly dispersed nitrogen element improves the conductivity of the carbon skeleton, thereby enhancing the lithium storage performance of the carbon skeleton; 3) the uniform dispersion of metal elements, namely metal oxide nanoparticles, in the nitrogen-doped carbon skeleton can more easily provide reaction active sites for the material, so that the electrochemical performance of the electrode material is improved; 4) the bowl-shaped hollow structure has the advantages of the traditional hollow structure, including the adoption of a volume expansion cavity and a short charge transmission distance when lithium ions are inserted; 5) unnecessary void space in the traditional hollow particles is eliminated by the bowl-shaped hollow structure, and compared with hollow spheres with the same diameter, the bowl-shaped hollow structure has higher bulk density, so that the volume energy density of the battery is greatly improved; 6) bowl-shaped particles may have a larger contact area with neighboring particles than spherical particles, thereby enhancing charge transport and stability of the electrode structure. The special bowl-shaped structure enables the electrode material to have higher volume energy density, excellent rate capability and cycle performance.
(2) The method comprises the steps of utilizing dopamine hydrochloride as a carbon source and a nitrogen source, utilizing metal salt as a metal source, utilizing a triblock copolymer as a pore-forming agent, utilizing 1,3, 5-Trimethylbenzene (TMB) as an emulsion droplet template and a pore-expanding agent, carrying out emulsion-induced heterogeneous interface co-assembly to synthesize polydopamine/triblock copolymer/metal oxide polymer particles, and carrying out high-temperature calcination treatment to obtain the nitrogen-doped metal oxide-carbon-based composite material with a bowl-shaped structure. The bowl-shaped hollow structure composite carbon-based lithium ion battery cathode material synthesized by the method has rich mesopores, and N element and metal element are uniformly dispersed in the bowl-shaped structure. The co-assembly method is an adjustable and universal preparation method, and the composition and structure of the material are controlled by adjusting and controlling reaction conditions, so that the performance of the lithium ion battery cathode material is improved, the types and properties of the metal oxide-carbon-based composite material are greatly enriched, the application range of the composite material is expanded, and a foundation is laid for synthesis and wide application of the lithium ion battery cathode material with a novel bowl-shaped nano structure and excellent performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an SEM image of a tin oxide-carbon based composite material with a bowl-shaped structure prepared in the first mode of example 1;
FIG. 2 is a TEM-mapping image of a tin oxide-carbon-based composite material having a bowl-like structure prepared in example 1 by the first method;
FIG. 3 is an SEM image of a tin oxide-carbon based composite material with a bowl-shaped structure prepared by the second method in example 2;
FIG. 4 is an SEM image of a tin oxide-carbon based composite material with a bowl-shaped structure prepared by the first method in example 3;
FIG. 5 is a TEM-mapping image of a tin oxide-carbon-based composite material having a bowl-like structure prepared by the first method in example 3;
FIG. 6 is an SEM image of a zinc oxide-carbon based composite material with a bowl-shaped structure prepared by the first method in example 4;
fig. 7 is an SEM image of a tin oxide-carbon based composite material having a spherical structure prepared in comparative example 1;
fig. 8 is a schematic view showing a stacking effect of a tin oxide-carbon-based composite material having a spherical structure and a tin oxide-carbon-based composite material having a bowl-shaped structure, in which (a) at the left side is the tin oxide-carbon-based composite material having a spherical structure and (b) at the right side is the tin oxide-carbon-based composite material having a bowl-shaped structure;
FIG. 9 is SnO of example 3 2 -cyclic voltammogram of the C-based bowl-shaped composite material as the negative electrode of the lithium ion battery in the range of 0-3V and under the scanning condition of 0.1 mV/s;
FIG. 10 shows SnO in example 3 2 -a rate performance curve diagram of the C-based bowl-shaped composite material as the negative electrode of the lithium ion battery under the current densities of 0.2, 0.5, 1.0 and 2.0A/g;
FIG. 11 is SnO of example 3 2 -C-based bowl-shaped composite material as negative electrode of lithium ion battery and SnO of comparative example 1 2 A cycle performance curve diagram of the-C-based spherical composite material as a lithium ion battery cathode at a current density of 0.4A/g.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The first step is as follows: at room temperature, 0.10g of triblock copolymer polyether F127 and 0.15g of dopamine hydrochloride are firstly dissolved in 8mL of ethanol aqueous solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), then 0.01g of stannous chloride is added, and the mixture is uniformly stirred (mode one).
The second step is that: 0.22mL of 1,3, 5-Trimethylbenzene (TMB) is dropwise added into the solution, ultrasonic treatment is carried out for 2min (the ultrasonic power is 100W), then 0.40mL of ammonia water (the concentration of the ammonia water is 28%) is dropwise added under the condition of stirring, after 3.5h of reaction, the reaction solution is firstly centrifugally cleaned for 2 times by absolute ethyl alcohol and then centrifugally cleaned for 2 times by deionized water, and a black precipitate is obtained.
The third step: dispersing the obtained black precipitate into 25mL of ethanol water solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), placing the mixture into a hydrothermal reaction kettle with a 50mL volume and stainless steel polytetrafluoroethylene lining, carrying out hydrothermal curing reaction at 100 ℃ for 24h, carrying out centrifugal cleaning on the hydrothermal curing reaction product for 2 times by using absolute ethanol, carrying out centrifugal cleaning for 2 times by using deionized water, and drying in an oven at 50 ℃ for 12h to obtain the polymer composite particles.
The fourth step: and (2) carrying out high-temperature calcination treatment on the obtained polymer composite particles under the protection of nitrogen, wherein the high-temperature calcination process comprises the following steps: heating to 350 ℃ for heat preservation treatment for 1h, then heating to 800 ℃ for high-temperature calcination for 3h, wherein the heating rates of the two heating processes are both 2.5 ℃/min, so as to remove polyether F127 in the polymer composite particles, and obtain the final tin oxide-carbon-based composite material (SnO with a bowl-shaped structure) with a bowl-shaped structure 2 -a C-based composite).
This example adopts the SnO synthesized by the method one 2 SEM and TEM images of the morphology structure of the-C nanoparticles are shown in FIGS. 1 and 2, and it can be seen from FIGS. 1 and 2 that SnO 2 -C nanoparticles are bowl-shaped structures and N, O, Sn element is uniformly dispersed in SnO 2 -C nanoparticles.
Example 2
The first step is as follows: at room temperature, 0.10g of triblock copolymer polyether F127, 0.15g of dopamine hydrochloride and 0.01g of stannous chloride are mixed together and added into 8mL of ethanol aqueous solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), and the mixture is stirred and dissolved uniformly (mode II).
The second step is that: 0.22mL of 1,3, 5-Trimethylbenzene (TMB) is dropwise added into the solution, ultrasonic treatment is carried out for 2min (the ultrasonic power is 100W), 0.40mL of ammonia water (the concentration of the ammonia water is 28%) is dropwise added under the condition of stirring, after 3.5h of reaction, the reaction solution is firstly centrifugally cleaned for 2 times by absolute ethyl alcohol and then centrifugally cleaned for 2 times by deionized water, and a black precipitate is obtained.
The third step: dispersing the obtained black precipitate into 25mL of ethanol water solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), placing the mixture into a hydrothermal reaction kettle with a 50mL volume and stainless steel polytetrafluoroethylene lining, carrying out hydrothermal curing reaction at 100 ℃ for 24h, carrying out centrifugal cleaning on the hydrothermal curing reaction product for 2 times by using absolute ethanol, carrying out centrifugal cleaning for 2 times by using deionized water, and drying in an oven at 50 ℃ for 12h to obtain the polymer composite particles.
The fourth step: and (2) carrying out high-temperature calcination treatment on the obtained polymer composite particles under the protection of nitrogen, wherein the high-temperature calcination process comprises the following steps: heating to 350 ℃ for heat preservation treatment for 1h, then heating to 800 ℃ for high-temperature calcination for 3h, wherein the heating rates of the two heating processes are both 2.5 ℃/min, so as to remove polyether F127 in the polymer composite particles, and obtain the final tin oxide-carbon-based composite material (SnO with a bowl-shaped structure) with a bowl-shaped structure 2 -a C-based composite).
SnO synthesized by the second embodiment 2 The SEM image of the morphology structure of the-C nanoparticles is shown in FIG. 3, and it can be seen from FIG. 3 that SnO 2 The C nanoparticles are substantially bowl-shaped and have a slightly larger particle size compared to the nanoparticles synthesized in the first embodiment of fig. 1; different synthesis modes can be seen, and the morphology and structure of the particles are influenced.
Example 3
The first step is as follows: at room temperature, 0.10g of triblock copolymer polyether F127 and 0.15g of dopamine hydrochloride are firstly dissolved in 10mL of ethanol solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), then 0.04g of stannous chloride is added, and the mixture is stirred uniformly (mode one).
The second step is that: 0.25mL of 1,3, 5-Trimethylbenzene (TMB) is dropwise added into the solution, ultrasonic treatment is carried out for 2.5min (the ultrasonic power is 100W), 0.50mL of ammonia water (the concentration of the ammonia water is 28%) is dropwise added under the condition of stirring, after 5.0h of reaction, the reaction solution is firstly centrifugally cleaned for 2 times by absolute ethyl alcohol and then centrifugally cleaned for 2 times by deionized water, and black precipitates are obtained.
The third step: dispersing the obtained black precipitate into 25mL of ethanol water solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), placing the mixture into a hydrothermal reaction kettle with a 50mL volume and stainless steel polytetrafluoroethylene lining, carrying out hydrothermal curing reaction at 100 ℃ for 24h, carrying out centrifugal cleaning on the hydrothermal curing reaction product for 2 times by using absolute ethanol, carrying out centrifugal cleaning for 2 times by using deionized water, and drying in an oven at 50 ℃ for 12h to obtain the polymer composite particles.
The fourth step: and (2) carrying out high-temperature calcination treatment on the obtained polymer composite particles under the protection of nitrogen, wherein the high-temperature calcination process comprises the following steps: heating to 350 ℃ for heat preservation treatment for 2h, heating to 800 ℃ for high-temperature calcination for 3h, wherein the heating rates of the two heating processes are both 1.0 ℃/min, so as to remove polyether F127 in the polymer composite particles, and obtain the final tin oxide-carbon-based composite material (SnO with a bowl-shaped structure) with a bowl-shaped structure 2 -a C-based composite).
This example adopts the SnO synthesized by the method one 2 SEM and TEM images of the morphology structure of the-C nanoparticles are shown in FIGS. 4 and 5, and it can be seen from FIGS. 4 and 5 that SnO 2 the-C nano-particles are basically in a bowl-shaped structure, and the N, O, Sn elements are uniformly dispersed in the nano-particles.
Example 4
The first step is as follows: 0.10g of triblock copolymer polyether F127 and 0.15g of dopamine hydrochloride are firstly dissolved in 8mL of ethanol aqueous solution (the ethanol and the water are mixed according to the volume ratio of 1: 1) at room temperature, then 0.01g of zinc chloride is added, and the mixture is stirred uniformly (mode one).
The second step is that: 0.22mL of 1,3, 5-Trimethylbenzene (TMB) is dropwise added into the solution, ultrasonic treatment is carried out for 2min (the ultrasonic power is 100W), 0.44mL of ammonia water (the concentration of the ammonia water is 28%) is dropwise added under the condition of stirring, after 3.5h of reaction, the reaction solution is firstly centrifugally cleaned for 2 times by absolute ethyl alcohol and then centrifugally cleaned for 2 times by deionized water, and a black precipitate is obtained.
The third step: dispersing the obtained black precipitate into 25mL of ethanol water solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), placing the mixture into a hydrothermal reaction kettle with a 50mL volume and stainless steel polytetrafluoroethylene lining, carrying out hydrothermal curing reaction at 100 ℃ for 24h, carrying out centrifugal cleaning on the hydrothermal curing reaction product for 2 times by using absolute ethanol, carrying out centrifugal cleaning for 2 times by using deionized water, and drying in an oven at 50 ℃ for 12h to obtain the polymer composite particles.
The fourth step: and (2) carrying out high-temperature calcination treatment on the obtained polymer composite particles under the protection of nitrogen, wherein the high-temperature calcination process comprises the following steps: heating to 350 ℃ for heat preservation treatment for 1h, then heating to 700 ℃ for high-temperature calcination for 3h, wherein the heating rates of the two heating processes are both 2.5 ℃/min, so as to remove polyether F127 in the polymer composite particles, and obtain the final zinc oxide-carbon-based composite material (ZnO-C-based composite material with a bowl-shaped structure) with the bowl-shaped structure.
In this embodiment, an SEM image of the morphology structure of the ZnO-C nanoparticles synthesized by the first method is shown in fig. 6, and it can be seen from fig. 6 that the ZnO-C nanoparticles are substantially bowl-shaped.
Example 5
The first step is as follows: mixing 0.30g of triblock copolymer polyether F127, 0.36g of dopamine hydrochloride and 0.19g of tetrahydrate cerium sulfate together at room temperature, adding the mixture into 25mL of ethanol aqueous solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), and stirring and dissolving uniformly (mode II); the molar ratio of dopamine hydrochloride/metal ion salt/triblock copolymer was 1:0.25: 0.012.
The second step is that: 0.70mL of 1,3, 5-Trimethylbenzene (TMB) is dropwise added into the solution, ultrasonic treatment is carried out for 3min (the ultrasonic power is 100W), 1.8mL of ammonia water (the concentration of the ammonia water is 28%) is dropwise added under the condition of stirring, after 6h of reaction, the reaction solution is firstly centrifugally washed for 2 times by absolute ethyl alcohol and then centrifugally washed for 2 times by deionized water, and black precipitates are obtained.
The third step: dispersing the obtained black precipitate into 25mL of ethanol water solution (the ethanol and the water are mixed according to the volume ratio of 1: 1), placing the mixture into a hydrothermal reaction kettle with a 50mL volume and stainless steel polytetrafluoroethylene lining, carrying out hydrothermal curing reaction at 120 ℃ for 24h, carrying out centrifugal cleaning on the hydrothermal curing reaction product for 2 times by using absolute ethanol, carrying out centrifugal cleaning for 2 times by using deionized water, and drying in an oven at 70 ℃ for 12h to obtain the polymer composite particles.
The fourth step: and (2) carrying out high-temperature calcination treatment on the obtained polymer composite particles under the protection of nitrogen, wherein the high-temperature calcination process comprises the following steps: heating to 350 ℃ for heat preservation treatment for 2h, then heating to 800 ℃ for high-temperature calcination for 4h, wherein the heating rates of the two heating processes are both 1.0 ℃/min, so as to remove polyether F127 in the polymer composite particles, and obtain the final cerium oxide-carbon-based composite material with a bowl-shaped structure.
Comparative example 1
Adding 0.04g of stannous chloride and 0.15g of dopamine hydrochloride into 200mL of deionized water at room temperature, and stirring for 1h until the stannous chloride and the dopamine hydrochloride are completely dissolved to prepare a DA/Sn solution; dissolving 1.6g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water to prepare a Tris buffer solution; and quickly injecting the prepared Tris buffer solution into the prepared DA/Sn solution, stirring for reaction for 3h, centrifugally cleaning for 2 times by using deionized water and ethanol respectively, and drying in an oven at 70 ℃ for 12h to obtain the polymer composite particles. Heating the polymer composite particles to 800 ℃ at a heating rate of 1.0 ℃/min under the protection of nitrogen, and calcining for 4 hours to obtain SnO with a spherical structure 2 -C particles.
SnO synthesized by the comparative example 2 The SEM image of the morphology structure of the-C nanoparticles is shown in FIG. 7, and it can be seen from FIG. 7 that SnO prepared by the comparative example is 2 -the C nanoparticles are spherical in structure.
Effect verification
(1) Stack effect
Metal oxide-carbon-based composite material (SnO) with bowl-shaped structure prepared by various embodiments of the invention 2 C bowl-shaped particles, etc.) and the stacking effect of comparative example 1 and the metal oxide-carbon-based composite material having a spherical structure prepared using other prior art are shown in fig. 8, in which (a) at the left side is one having a spherical structureFig. 8 shows that the bowl structure can increase the packing density and contact area compared to the spherical structure.
(2) Electrochemical performance test
SnO prepared from example 3 and having a bowl-shaped structure 2 -C-based composite material and SnO having spherical structure obtained in comparative example 1 2 The C-based composite material is used as a lithium ion battery cathode material to be assembled into a half battery, and the electrochemical performance of the half battery is tested; SnO 2 The cyclic voltammetry curve of the-C-based bowl-shaped composite material negative electrode under the scanning conditions of 0-3V and 0.1mV/s is shown in FIG. 9, and SnO 2 The multiplying power performance curve of the negative electrode of the C-based bowl-shaped composite material under the current densities of 0.2, 0.5, 1.0 and 2.0A/g is shown in FIG. 10; SnO 2 -C-based bowl-shaped composite negative electrode and SnO of comparative example 1 2 The cycle performance curve of the-C-based spherical composite negative electrode at a current density of 0.4A/g is shown in FIG. 11. As can be seen from FIG. 9, there is a significant SnO in the negative sweep 2 Reduction peak (0.8-1.6V), i.e. SnO 2 Is reduced into Sn by Li, and the reduction peak between 0.3 and 0.7V corresponds to the alloying reaction of Sn and Li; the oxidation peak between 0.4 and 0.8V in the positive sweep corresponds to the dealloying process of Sn-Li alloy, and appears at the oxidation peak of 1.15V, corresponding to Li 2 O to SnO 2 The conversion process is beneficial to improving the reversible specific capacity of the material, and part of the process is considered to be reversible and SnO 2 Is associated with a uniform distribution. As can be seen from FIGS. 10 and 11, SnO 2 The negative electrode of the-C-based bowl-shaped composite material has excellent rate performance and cycling stability; as can be seen from FIG. 11, compared with ordinary SnO having a spherical structure 2 -C nanoparticle negative electrode, SnO 2 The negative electrode of the-C-based bowl-shaped composite material has higher specific capacity and cycle performance.
Using other Sn 2+ Salt, Sn 4+ Salt, Zn 2+ Salt, Ce 4+ Salt, Co 2+ Salt, Ni 2+ Salt, Mn 3+ Salt, Fe 2+ Salt as a metal salt, produced by the production method of the present inventionThe obtained metal oxide-carbon-based composite material having a bowl-shaped structure, the tin oxide-carbon-based composite material having a bowl-shaped structure, the zinc oxide-carbon-based composite material having a bowl-shaped structure, and the cerium oxide-carbon-based composite material having a bowl-shaped structure, which were prepared in the above examples, had similar effects.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a metal oxide-carbon-based composite material with a bowl-shaped structure is characterized by comprising the following steps:
(1) dissolving dopamine hydrochloride, triblock copolymer and metal source in ethanol water solution, adding 1,3, 5-trimethylbenzene, carrying out ultrasonic treatment, adding ammonia water under the condition of stirring, and reacting to obtain precipitate;
(2) and dispersing the precipitate in an ethanol water solution, carrying out hydrothermal curing reaction, washing, drying, and carrying out high-temperature calcination treatment in an inert atmosphere to obtain the metal oxide-carbon-based composite material with the bowl-shaped structure.
2. The method for preparing a metal oxide-carbon-based composite material with a bowl-shaped structure as claimed in claim 1, wherein the triblock copolymer in the step (1) is one or a mixture of polyether F127 and polyether P123, and the metal source is a metal salt.
3. The method of claim 2, wherein the metal salt is Sn, and wherein the metal salt is a metal oxide-carbon-based composite material having a bowl structure 2+ Salt, Sn 4+ Salt, Zn 2+ Salt, Ce 4+ Salt, Co 2+ Salt, Ni 2+ Salt, Mn 2+ Salt, Fe 2+ One kind of salt.
4. Having a bowl according to claim 1The preparation method of the metal oxide-carbon-based composite material with the structure is characterized in that in the step (1), the molar ratio of dopamine hydrochloride: triblock copolymer: 1,3, 5-trimethylbenzene: metal source: NH (NH) 3 ·H 2 O＝1：0.008～0.016：1.6～2.4：0.05～0.5：4～30。
5. The method for preparing a metal oxide-carbon-based composite material having a bowl-shaped structure according to claim 1, wherein the concentration of the triblock copolymer in the reaction system of the step (1) is 1.0 to 1.5 wt%.
6. The method for preparing a metal oxide-carbon-based composite material having a bowl-shaped structure according to claim 1, wherein the ethanol aqueous solution in the step (1) is formed by mixing absolute ethanol and water in a volume ratio of 1:1, and the ethanol aqueous solution in the step (2) is formed by mixing absolute ethanol and water in a volume ratio of 1: 1.
7. The method for preparing a metal oxide-carbon-based composite material with a bowl-shaped structure according to claim 1, wherein the reaction time in the step (1) is 2-6 h.
8. The method for preparing a metal oxide-carbon-based composite material with a bowl-shaped structure according to claim 1, wherein the temperature of the hydrothermal curing reaction in the step (2) is 80-150 ℃ and the time is 12-30 hours; the drying temperature is 50-80 ℃, and the drying time is 6-24 hours; the high-temperature calcination treatment comprises the following specific operations: firstly heating to 300-500 ℃, carrying out heat preservation treatment for 1-2 h, and then heating to 600-900 ℃ for high-temperature calcination for 2-4 h.
9. A metal oxide-carbon-based composite material having a bowl-like structure prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a metal oxide-carbon based composite material having a bowl-like structure according to claim 9 in a lithium ion battery.
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