CN109728264B - Composite film of carbon-based frame loaded nanosheet assembled hollow open microspheres and preparation method and application thereof - Google Patents
Composite film of carbon-based frame loaded nanosheet assembled hollow open microspheres and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a composite film of a carbon-based frame loaded nanosheet assembled hollow open microsphere, and a preparation method and application thereof. The composite film is a three-dimensional multilevel structure assembled by nano-sheets of nickel-cobalt-manganese oxide microspheres with hollow openings. According to the invention, a mixed solution of nano-sheet assembled nickel-cobalt-manganese oxide microspheres with hollow openings and graphene is obtained through two-step hydrothermal reaction; and adding the carbon nano tube, and performing vacuum filtration to obtain the flexible film with the hollow open microspheres embedded in the three-dimensional porous carbon nano tube/graphene conductive network. The microsphere structure combines the advantages of the nano-sheet and the hollow sphere structure, avoids the easy accumulation of the nano-sheet, and improves the contactable active surface area. The microspheres have high porosity and open characteristics, and both ends of the nanosheets can be exposed to pores for storing electrolyte, so that more active surfaces and ion transmission paths can be provided inside and outside the sphere.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a composite film of a carbon-based frame loaded nanosheet assembled hollow open microsphere, a preparation method of the composite film, and application of the composite film in a lithium ion battery.
Background
At present, the increasing energy demand leads to the dramatic increase of the consumption of non-renewable fossil fuels, and a series of environmental problems, which leads to the strong interest of people in clean and efficient energy[1, 2]. Among the main electrochemical energy storage, lithium ion batteries have been successfully commercialized, and have been widely used in portable electronic products, electric vehicles, and the like[3, 4]. Therefore, research into a high energy density and small and portable safety lithium ion battery has been widely conducted[5, 6]. The development and design of high-capacity electrode materials are key to the development of small and portable large electric energy storage devices[7]. In view of this demand, transition metal oxides have been widely studied as potential negative electrode materials for lithium ion batteries due to their advantages of high theoretical capacity, safety and abundance[8, 9]. Among them, ternary transition metal oxides (e.g., Ni-Co-Mn oxides, ZnCoMnO)4) Compared with single transition metal oxide, the oxide has the characteristics of three different metal atoms in one crystal structure, so that the oxide has rich defects and synergistic effects and shows potential excellent electrochemical performance[10, 11]. However, their use is hampered by the low conductivity, low ionic conductivity, and severe volume changes during charging and discharging of such oxides[12]。
To alleviate these problems, it is necessary to precisely design particles of active material of suitable structure and size, which design takes into account the large active surface area of the structure, the short ion transport path and the good stability[13, 14]. At present, transition metal oxides or transition metal oxides, carbon composites of various morphologies, such as hollow spheres, have been reported[15]And a nanosheet[16]Nanotube, and method for producing the same[17]Nanowires, and a method for producing the same[18]And the like. The hollow ball can better accommodate the expansion of the volume, better control the strain generated in the charging and discharging process, and has important significance for maintaining the structure[19, 20]. However, a closed hollow ballThe internal active of the particle cannot be fully utilized to provide capacity. In another structure, the two-dimensional nano-structured nanosheet has a large surface active area, excellent structural stability, and an open, short ion transport path. However, the property of smooth nanoplates to be prone to stacking results in a loss of advantage in the structure[21]. Inspired by the two structures, the shape design of the material can combine the advantages of the two structures and avoid the weak points. Besides structural design, oxygen vacancy can be introduced into the ternary transition metal oxide crystal lattice without damage, so that more active sites can be provided, the inherent conductivity can be improved, and the ion embedding and extracting processes can be accelerated[22, 23]。
According to the invention, the nanosheet-assembled hollow open nickel-cobalt-manganese oxide microspheres are obtained through a simple synthesis technology, and have rich and stable interlayer pores. In the structure, two ends of each nanosheet are exposed in enough space, so that the infiltration of electrolyte inside and outside the sphere is facilitated, the lithium ion transmission path is shortened, the active area is enlarged, and the ion transmission efficiency is improved. The structure can better keep the original shape and structure in the circulating process, and the process of ion embedding and ion releasing is improved. Meanwhile, a large number of oxygen vacancies are introduced into the active material, so that the electrochemical performance of the material is improved. Secondly, the hollow open microspheres are embedded into the light carbon nano tube/graphene conductive network, so that the constructed flexible composite film not only avoids the use of a high-molecular binder which hinders electron transmission, has high conductivity, but also reduces the weight of an electrode compared with the traditional battery, and is beneficial to obtaining the lithium ion battery with high energy density. In conclusion, the film is used as a lithium ion battery cathode and shows excellent electrical performance. In addition, this facile method can also be used to synthesize various hollow open transition metal oxide particles for other potential applications.
Disclosure of Invention
The invention aims to provide a composite film of hollow open microspheres assembled by carbon base frame loaded nanosheets, which has high specific capacity, long service life and good rate capability, and a preparation method and application thereof.
The composite film of the carbon-based frame loaded nanosheet assembled hollow open microsphere is a composite film of a three-dimensional porous carbon nanotube/graphene loaded nanosheet assembled hollow open nickel-cobalt-manganese oxide microsphere, wherein in the nanosheet self-assembled hollow open microsphere structure, two ends of the nanosheet are exposed in stable pores, which means that the nanosheet can be exposed in electrolyte, the lithium ion transmission efficiency is improved, and the surface active area is increased; enough space exists in the hollow sphere and among the nano-sheet layers stably, so that the volume change in the circulating process can be accommodated, and the circulating stability of the material is improved; in addition, a large number of oxygen vacancies exist in the hollow open microsphere crystal structure, so that the conductivity can be improved, the active sites can be increased, and the ion embedding and removing processes can be accelerated; in addition, the one-dimensional carbon nanotubes and the two-dimensional graphene are compounded to serve as the carbon substrate, so that the winding of the carbon nanotubes and the stacking of the graphene are reduced, and the conductivity of the electrode is improved.
The composite film of the hollow open nickel-cobalt-manganese oxide microspheres assembled by the three-dimensional porous carbon nanotube/graphene loaded nanosheets can be used as a negative electrode material of a flexible lithium ion battery and shows excellent electrical performance.
The invention provides a preparation method of a composite film of hollow open nickel-cobalt-manganese oxide microspheres assembled by three-dimensional porous carbon nanotubes/graphene loaded nanosheets, which comprises the following specific steps:
(1) preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material:
firstly, dissolving 262.9 +/-0.5 mg of nickel sulfate hexahydrate, 281.2 +/-0.5 mg of cobalt sulfate heptahydrate, 158 +/-0.5 mg of potassium permanganate and 1420 +/-0.5 mg of sodium sulfate in 50 +/-0.5 mL of deionized water, and performing ultrasonic dispersion for 10 +/-5 minutes;
then, transferring the solution into a hydrothermal kettle, and keeping the solution at the temperature of 160 +/-20 ℃ for 10 +/-2 hours;
then, centrifugally washing and drying the precursor for multiple times by using deionized water and ethanol respectively to obtain a precursor;
then, dissolving 10 +/-2 mg of precursor and 5 +/-2 mg of graphene oxide (which can be prepared by a Hummer method) in 100 +/-0.5 mL of deionized water, and carrying out ultrasonic dispersion for 30 +/-5 minutes;
then, transferring the solution into a hydrothermal kettle, and keeping the solution at the temperature of 160 +/-20 ℃ for 10 +/-6 hours;
thirdly, respectively carrying out centrifugal washing and drying on deionized water and ethanol for multiple times to obtain a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material;
(2) preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene/carbon nanotube composite film:
firstly, dissolving 10 +/-2 mg of hollow open microsphere/graphene composite material in 50 +/-0.5 mL of deionized water, and carrying out ultrasonic dispersion for 10 +/-2 minutes;
then, dripping carbon nanotube dispersion liquid (containing 5 +/-1 mg of carbon nanotubes) into the solution, and stirring and dispersing for 15 +/-2 minutes;
then, carrying out vacuum filtration on the solution to obtain a composite film, and drying the composite film;
and finally, annealing the obtained composite film in a nitrogen and hydrogen mixture at 350 +/-1 ℃ for 4 +/-0.1 hours to obtain the porous flexible composite film.
The composite film of the hollow open nickel-cobalt-manganese oxide microspheres assembled by the three-dimensional porous carbon nanotube/graphene loaded nanosheets, which is prepared by the invention, can be used as a lithium ion battery cathode material and has high specific capacity, excellent rate capability and cycle performance. After 300 cycles, at 2A g-1Can reach 1595 mAh.g-1The specific capacity of (A).
The three-dimensional porous composite film can be directly used as a lithium ion battery cathode for preparing a lithium ion battery, and comprises the following specific steps:
the appropriate size film prepared above was used as a working electrode, a lithium sheet as a counter electrode, Celgard 2400 porous polypropylene as a separator, and lithium hexafluorophosphate dissolved in ethylene carbonate or diethyl carbonate as an electrolyte in a glove box filled with argon, and charged into a CR2016 coin cell.
The specific capacity of the battery is calculated based on the overall mass of the film.
Drawings
Fig. 1 is an X-ray diffraction spectrum of a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material.
FIG. 2 is a scanning electron microscope photograph of the nanosheet-assembled hollow open nickel-cobalt-manganese oxide microspheres.
FIG. 3 is a transmission electron microscope photograph of the nanosheet assembled hollow open nickel-cobalt-manganese oxide microspheres.
Fig. 4 is a photograph and a scanning electron microscope photograph of a composite film of hollow open nickel-cobalt-manganese oxide microspheres assembled by the prepared porous carbon nanotube/graphene loaded nanosheet. Wherein a is a photograph of the film, b is a scanning electron micrograph of the surface of the film, and c is a scanning electron micrograph of a cross section of the film.
FIG. 5 is an X-ray photoelectron spectrum of a composite film of hollow open nickel-cobalt-manganese oxide microspheres assembled by porous carbon nanotube/graphene loaded nanosheets. Wherein a is the fine spectrum of Ni 2 p; b is the fine spectrum of Co 2 p; c is a fine spectrum of Mn 2 p; d is the fine spectrum of O1 s; e is the fine spectrum of C1 s.
FIG. 6 shows that the composite film of hollow open nickel-cobalt-manganese-oxide microspheres assembled by porous carbon nanotubes/graphene loaded nanosheets has a thickness of 0.1 mV.s-1Cyclic Voltammetry (CV) curves at scan rate.
FIG. 7 shows that the composite film of hollow open nickel-cobalt-manganese oxide microspheres assembled by porous carbon nanotube/graphene loaded nanosheet is at 2 A.g-1Constant current charge and discharge curve under current density.
FIG. 8 shows that the composite film of hollow open nickel-cobalt-manganese oxide microspheres assembled by porous carbon nanotube/graphene loaded nanosheet is at 2 A.g-1Cycling profile at current density.
Detailed Description
Example 1:
(1) preparing a nanosheet self-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material:
first, 262.9 mg of nickel sulfate hexahydrate, 281.2 mg of cobalt sulfate heptahydrate, 158 mg of potassium permanganate, and 1420mg of sodium sulfate were dissolved in 50 mL of deionized water, and ultrasonically dispersed for 5 minutes. Subsequently, the solution was transferred to a hydrothermal reactor and kept at 160 ℃ for 12 hours. And then, centrifugally washing and drying the precursor for multiple times by using deionized water and ethanol respectively to obtain the precursor. Next, 10 mg of the precursor and 5 mg of graphene oxide prepared by the Hummer method were dissolved in 100 mL of deionized water, and ultrasonically dispersed for 30 minutes. Then, the above solution was transferred to a hydrothermal kettle and kept at 180 ℃ for 5 hours. And finally, respectively carrying out centrifugal washing and drying on deionized water and ethanol for multiple times to obtain the nickel-cobalt-manganese oxide microsphere/graphene composite material. The structure of the nickel-cobalt-manganese oxide microsphere finally obtained is a hollow structure, and most particles are not provided with openings.
(2) Preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene/carbon nanotube composite film:
first, 10 mg of the microsphere/graphene composite material was dissolved in 50 mL of deionized water and ultrasonically dispersed for 10 minutes. Then, a carbon nanotube dispersion (containing 5 mg of carbon nanotubes) was dropped into the above solution, and stirred and dispersed for 15 minutes. And then, carrying out vacuum filtration on the solution to obtain a composite film, and drying the composite film. And finally, annealing the obtained composite film in a mixed gas of nitrogen and hydrogen at 350 ℃ for 4 hours to obtain the porous flexible composite film.
Example 2:
(1) preparing a nanosheet self-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material:
first, 262.9 mg of nickel sulfate hexahydrate, 281.2 mg of cobalt sulfate heptahydrate, 158 mg of potassium permanganate, and 1420mg of sodium sulfate were dissolved in 50 mL of deionized water, and ultrasonically dispersed for 5 minutes. Subsequently, the solution was transferred to a hydrothermal reactor and kept at 160 ℃ for 12 hours. And then, centrifugally washing and drying the precursor for multiple times by using deionized water and ethanol respectively to obtain the precursor. Next, 10 mg of the precursor and 5 mg of graphene oxide prepared by the Hummer method were dissolved in 100 mL of deionized water, and ultrasonically dispersed for 30 minutes. Then, the above solution was transferred to a hydrothermal kettle and kept at 180 ℃ for 16 hours. And finally, respectively carrying out centrifugal washing and drying on deionized water and ethanol for multiple times to obtain the nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material. The nickel-cobalt-manganese oxide microsphere structure obtained finally is a hollow open structure, but the agglomeration is very serious.
(2) Preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene/carbon nanotube composite film:
first, 10 mg of the hollow open microsphere/graphene composite material was dissolved in 50 mL of deionized water and ultrasonically dispersed for 10 minutes. Then, the carbon nanotube dispersion (containing 4mg of carbon nanotubes) was dropped into the above solution, and stirred and dispersed for 15 minutes. And then, carrying out vacuum filtration on the solution to obtain a composite film, and drying the composite film. And finally, annealing the obtained composite film in a mixed gas of nitrogen and hydrogen at 350 ℃ for 4 hours to obtain the porous flexible composite film.
Example 3:
(1) preparing a nanosheet self-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material:
first, 262.9 mg of nickel sulfate hexahydrate, 281.2 mg of cobalt sulfate heptahydrate, 158 mg of potassium permanganate, and 1420mg of sodium sulfate were dissolved in 50 mL of deionized water, and ultrasonically dispersed for 5 minutes. Subsequently, the solution was transferred to a hydrothermal reactor and kept at 160 ℃ for 10 hours. And then, centrifugally washing and drying the precursor for multiple times by using deionized water and ethanol respectively to obtain the precursor. Next, 10 mg of the precursor and 5 mg of graphene oxide prepared by the Hummer method were dissolved in 100 mL of deionized water, and ultrasonically dispersed for 30 minutes. Then, the above solution was transferred to a hydrothermal kettle and kept at 160 ℃ for 10 hours. And finally, respectively carrying out centrifugal washing and drying on deionized water and ethanol for multiple times to obtain the nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material. The structure of the nickel-cobalt-manganese oxide microsphere finally obtained is a hollow open structure, and the size is about 2 mu m.
(2) Preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene/carbon nanotube composite film:
first, 10 mg of the hollow open microsphere/graphene composite material was dissolved in 50 mL of deionized water and ultrasonically dispersed for 10 minutes. Then, the carbon nanotube dispersion (containing 4mg of carbon nanotubes) was dropped into the above solution, and stirred and dispersed for 15 minutes. And then, carrying out vacuum filtration on the solution to obtain a composite film, and drying the composite film. And finally, annealing the obtained composite film in a mixed gas of nitrogen and hydrogen at 350 ℃ for 4 hours to obtain the porous flexible composite film.
The shape and size of the nanosheet self-assembled hollow open nickel-cobalt-manganese oxide microsphere are characterized by a scanning electron microscope (SEM, Hitachi FE-SEM S-4800 operated at 1 Kv), namely, a powder sample is dispersed in ethanol and then is dripped into a silicon wafer for drying. The microstructure information of the nanosheet self-assembled hollow open nickel-cobalt-manganese oxide microspheres is characterized by a transmission electron microscope (TEM, JEOL JEM-2100F operated at 200 kV), namely, a powder sample is dispersed in ethanol and then is dripped into a copper mesh for drying. The X-ray diffraction spectra were measured on a Bruker D8X-ray diffractometer (Germany) with Ni-filter Cu KR radiation operated at 40 kV and 40 mA. X-ray photoelectron spectroscopy was performed by KratosAxis Ultra DLD test. The obtained film is directly used as a lithium ion battery cathode, and the electrochemical performance of the lithium ion battery cathode is tested by an electrochemical workstation (CHI 660D, Shanghai Chenghua apparatus Co., Ltd.).
Fig. 1 is an X-ray diffraction (XRD) analysis of a nanosheet self-assembled hollow open nickel cobalt manganese oxide microsphere/graphene composite. It reflects the information of the crystal phase, purity, crystallinity and the like of the product. Diffraction peak and Co3O4The cubic spinel phase (JCPDS 74-1657) coincided well. Further, the diffraction peak at about 25 ° corresponds to the (002) plane of the graphitized carbon. The sample has high purity and the graphitization degree of the carbon matrix is high.
FIG. 2 is a nano-sheet self-assembled hollow open-ended nickel cobalt manganese oxide microsphere morphology characterized by a Scanning Electron Microscope (SEM). The nanosheets are self-assembled into the microspheres with the hollow openings, a large number of stable pores exist among the nanosheets, stacking is avoided, the internal surfaces of the microspheres with the openings are large in active area, and the microspheres are beneficial to infiltration of electrolyte.
The transmission electron micrograph of fig. 3 also demonstrates the hollow open structure of the microspheres, with a large number of pores present between the nanosheet layers.
The photograph of the prepared porous composite film is shown as a in fig. 4, and the film is flexible. The scanning electron micrograph b in fig. 4 shows the surface morphology of the thin film, and a large number of pores exist on the surface, and the pores fluctuate with ripples, which indicates that the flexible graphene sheet layers and the carbon nanotubes tightly wrap the hollow open microspheres. Notably, rough and porous surfaces can provide a path for rapid ion diffusion. The scanning electron micrograph of c in FIG. 4 shows the cross-sectional structure of the film, with a thickness of about 33 μm.
The compositional information of the composite was further analyzed by X-ray photoelectron spectroscopy (XPS) of fig. 5. The figure shows that divalent and trivalent valences of three elements of nickel, cobalt and manganese exist. The O1 s peaks for d in fig. 5 are 529.8, 531.5, 532.6 eV, respectively, corresponding to lattice oxygen, oxygen vacancies and chemisorbed oxygen species of interest[24, 25]. Wherein a strong oxygen vacancy related peak indicates the presence of oxygen vacancies in the microspheres. The C1 s spectrum of e in FIG. 5 can be decomposed into 2 peaks at 284.6eV and 285.5eV, corresponding to graphitic carbon and carbon defects, respectively[26]。
The nickel-cobalt-manganese oxide, the graphene and the carbon nano tube can be used as electrode materials, and the CV curve of the composite film has an obvious oxidation-reduction peak. As shown in fig. 6, the main peaks correspond to the redox reactions of the three metallic elements of nickel, cobalt and manganese.
The nanosheet-assembled hollow open microsphere/graphene/carbon nanotube composite film shows excellent electrochemical performance. As shown in FIG. 7, at 2A · g-1Under the current density of (2), the first discharge reaches 2410 mAh.g-1The ultra-high specific capacity. In subsequent cycles, the specific capacity gradually stabilized at about 1500 mAh g-1This indicates that the electrode has excellent reversibility and high reversible capacity even at high current density. FIG. 8 shows excellent cycle performance at 2A g-1The specific capacity of 300 cycles of the circuit can still reach 1595 mAh.g-1。
Reference to the literature
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Claims (3)
1. A preparation method of a composite film of a carbon-based frame loaded nanosheet assembled hollow open microsphere is characterized by comprising the following specific steps:
(1) preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material:
firstly, dissolving 262.9 +/-0.5 mg of nickel sulfate hexahydrate, 281.2 +/-0.5 mg of cobalt sulfate heptahydrate, 158 +/-0.5 mg of potassium permanganate and 1420 +/-0.5 mg of sodium sulfate in 50 +/-0.5 mL of deionized water, and performing ultrasonic dispersion for 10 +/-5 minutes;
then, transferring the obtained solution into a hydrothermal kettle, and keeping the solution at the temperature of 160 +/-20 ℃ for 10 +/-2 hours;
then, centrifugally washing and drying the precursor for multiple times by using deionized water and ethanol respectively to obtain a precursor;
then, dissolving 10 +/-2 mg of precursor and 5 +/-2 mg of graphene oxide prepared by a Hummer method in 100 +/-0.5 mL of deionized water, and ultrasonically dispersing for 30 +/-5 minutes;
then, transferring the obtained solution into a hydrothermal kettle, and keeping the solution at the temperature of 160 +/-20 ℃ for 10 +/-6 hours;
finally, respectively carrying out centrifugal washing and drying on deionized water and ethanol for multiple times to obtain a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material;
(2) preparing a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene/carbon nanotube composite film:
firstly, dissolving 10 +/-2 mg of hollow open nickel-cobalt-manganese oxide microsphere/graphene composite material in 50 +/-0.5 mL of deionized water, and performing ultrasonic dispersion for 10 +/-2 minutes;
then, 5 plus or minus 1 mg of carbon nanotube dispersion liquid containing carbon nanotubes is dripped into the obtained solution, and stirred and dispersed for 15 plus or minus 2 minutes;
then, carrying out vacuum filtration on the obtained solution to obtain a composite film, and drying the composite film;
and finally, annealing the obtained composite film in a mixed gas of nitrogen and hydrogen at the temperature of 350 +/-1 ℃ for 4 +/-0.1 hours to obtain the porous flexible composite film.
2. The composite film of the carbon-based frame supported nanosheet-assembled hollow open microsphere obtained by the preparation method of claim 1 is a nanosheet-assembled hollow open nickel-cobalt-manganese oxide microsphere/graphene/carbon nanotube composite film.
3. The composite film of the carbon-based frame supported nanosheet assembled hollow open microsphere as defined in claim 2, for use as a negative electrode material of a lithium ion battery.
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