CN109728264A - The laminated film and its preparation method and application of the hollow open microballoon of carbon-based frame load nanometer sheet assembling - Google Patents
The laminated film and its preparation method and application of the hollow open microballoon of carbon-based frame load nanometer sheet assembling Download PDFInfo
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Abstract
The invention belongs to lithium ion battery material technical field, specially a kind of laminated film and its preparation method and application of the hollow open microballoon of carbon-based frame load nanometer sheet assembling.Laminated film is by the three-dimensional multistage structure that the nickel, cobalt and manganese oxide microballoon of hollow open is that nanometer sheet assembles.The present invention obtains the nickel, cobalt and manganese oxide microballoon of the hollow open of nanometer sheet assembling, the mixed solution of graphene by two step hydro-thermal reactions；Carbon nanotube is added, then by vacuum filtration, obtains the fexible film that hollow open microballoon is embedded in three-dimensional porous carbon nano tube/graphene conductive network.The micro-sphere structure combines the advantages of nanometer sheet, hollow spherical structure, in turn avoids the easy sedimentation of nanometer sheet, improves accessible active surface area.Microballoon has height hole and open characteristic, and the both ends of nanometer sheet can be exposed in the hole of storage electrolyte, it is possible to provide more active surfaces and ion transmission path are inside and outside ball.
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to the hollow opening of carbon-based frame load nanometer sheet assembling
The application of laminated film of mouth microballoon and preparation method thereof and film in lithium ion battery.
Background technique
Instantly, ever-increasing energy demand causes non-renewable Fossil fuel consumption amount to increase severely, a series of in addition
The appearance of environmental problem causes people to produce keen interest to the energy of clean and effective[1, 2].In main electrochemical energy
In the storage of source, lithium ion battery successfully realizes commercialization, is answered extensively in portable electronic product, electric car etc.
With[3, 4].Therefore, for high-energy density and the research of small and portable safety lithium ion cell very extensively[5, 6].And it researches and develops
The electrode material of design high capacity is the key that the small and portable big electric energy storage device of development[7].In view of this demand, mistake
The advantages of metal oxide is due to its theoretical capacity height, safety and rich reserves are crossed, it is very promising to be counted as lithium ion battery
Negative electrode material and be widely studied[8, 9].Wherein, ternary transition metal oxide (such as Ni-Co-Mn oxide, ZnCoMnO4) ratio
Play single transition metal oxide, tool there are three types of a kind of characteristic of the different metal atom in crystal structure, therefore its possess it is rich
Rich defect and synergistic effect, shows potential excellent electrochemical performance[10, 11].However, the low electric conductivity of this type oxide,
Serious volume change hinders their application in low ionic conductivity, charge and discharge process[12]。
To alleviate these problems, the active material particle of sophisticated design suitable construction and size necessitates, and designing needs
It will be in view of the big active surface area of structure, short ion transmission path and preferable stability[13, 14].Currently, having registered
Transition metal oxide or transition metal oxide, the carbon composite of different morphologies structure, such as hollow ball[15], nanometer
Piece[16], nanotube[17], nano wire[18]Etc. structures.Wherein, hollow ball can preferably receiving volume expansion, preferably control fills
The strain generated in discharge process, it is significant for the holding of structure[19, 20].However, closed Hollow sphere particles is interior
Portion's active material can not be fully used to provide capacity.Another structure, two-dimensional nanostructure nanometer sheet possess big surface
Active area, excellent structural stability, opening, short ion transmission path.However, the characteristic that smooth nanometer sheet is easily accumulated
The advantages of leading to structure, closely loses[21].Form Design by the inspiration of both structures, material can combine the excellent of two kinds of structures
Point, while avoiding weakness.In addition to structure design, it is also contemplated that the nothing by Lacking oxygen introducing ternary transition metal oxide lattice
It destroys, this mode can provide more active sites, improve intrinsic conductivity, accelerate the mistake of ion insertion and abjection
Journey[22, 23]。
In the present invention, by simple synthetic technology, the hollow open nickel, cobalt and manganese oxide microballoon of nanometer sheet assembling is obtained,
It, which has, enriches stable interlayer hole.The both ends of each nanometer sheet are both exposed in enough spaces in the structure, are conducive to
Lithium ion transport path is shortened in infiltration of the electrolyte inside and outside ball, expands active area, improves ion transmission efficiency.The structure
Original appearance structure can be preferably kept in cyclic process, improve the process of ion insertion and abjection.Meanwhile by a large amount of oxygen
Vacancy is introduced into active material, improves the chemical property of material.Secondly, by the carbon nanometer of hollow open microballoon insertion lightweight
In pipe/graphene conductive network, the flexible composite film constructed is not only avoided using the macromolecule bonding for hindering electron-transport
Agent possesses high conductivity, reduces electrode weight also relative to conventional batteries, this be conducive to obtain the lithium of high-energy density from
Sub- battery.To sum up, which shows excellent electrical property as negative electrode of lithium ion battery.In addition, the method for this simplicity
It can be used for synthesizing the transition metal oxide particle of various hollow opens for other potential applications.
Summary of the invention
The purpose of the present invention is to provide a kind of height ratio capacity, long-life, the good carbon-based framves of high rate performance to load nanometer
The laminated film and its preparation method and application of the hollow open microballoon of piece assembling.
The laminated film of the hollow open microballoon of carbon-based frame load nanometer sheet assembling provided by the invention, is three-dimensional porous carbon
The laminated film for the hollow open nickel, cobalt and manganese oxide microballoon that nanotube/graphene-supported nanometer sheet assembles, wherein nanometer sheet
In the hollow open micro-sphere structure of self assembly, the both ends of nanometer sheet are both exposed in stable hole, it means that can be exposed to
In electrolyte, lithium ion transport efficiency is improved, increases surface-active area；And enough spatial stabilities are present in hollow ball
Between internal and nanoscale twins, the volume change in cyclic process can be accommodated, the cyclical stability of material is improved；In addition, a large amount of
Lacking oxygen be present in hollow open microballoon crystal structure, can be improved conductivity, increase active site, accelerate ion insertion and
The process of abjection；Moreover, compound as carbon substrate using one-dimensional carbon nanotube, two-dimensional graphene, reduce carbon nanotube winding and
The stacking of graphene improves the conductivity of electrode.
The hollow open nickel, cobalt, manganese and oxygen of the nanometer sheet assembling of three-dimensional porous carbon nano tube/graphene load provided by the invention
The laminated film of compound microballoon can be used as flexible lithium ion battery negative electrode material, show excellent electrical property.
The present invention provides the hollow open nickel, cobalt, manganese and oxygen of above-mentioned three-dimensional porous carbon nano tube/graphene load nanometer sheet assembling
The preparation method of the laminated film of compound microballoon, specific steps are as follows:
(1) hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material preparation of nanometer sheet assembling:
Firstly, by 262.9 ± 0.5 mg nickel sulfate hexahydrates, 281.2 ± 0.5 mg cobalt sulfates, 158 ± 0.5 mg permanganic acid
Potassium and 1420 ± 0.5 mg sodium sulphate are dissolved in 50 ± 0.5 mL deionized waters, and ultrasonic disperse 10 ± 5 minutes；
Then, above-mentioned solution is transferred in water heating kettle, is kept for 10 ± 2 hours at 160 ± 20 DEG C；
Then, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, it is dry, obtain presoma；
Then, 10 ± 2 mg presomas and 5 ± 2 mg graphene oxides (can be prepared with Hummer method) are dissolved in 100 ±
In the deionized water of 0.5 mL, ultrasonic disperse 30 ± 5 minutes；
Then, above-mentioned solution is transferred in water heating kettle, is kept for 10 ± 6 hours at 160 ± 20 DEG C；
Again, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, it is dry, obtain the hollow open nickel cobalt of nanometer sheet assembling
Mn oxide microballoon/graphene composite material；
(2) hollow open nickel, cobalt and manganese oxide microballoon/graphene/carbon nanotube composite film preparation of nanometer sheet assembling:
Firstly, 10 ± 2 mg hollow open microballoons/graphene composite material is dissolved in 50 ± 0.5 mL deionized waters, ultrasound
Dispersion 10 ± 2 minutes；
Then, carbon nano tube dispersion liquid (5 ± 1 mg of carbon nanotubes) is instilled in above-mentioned solution, is dispersed with stirring 15 ± 2 minutes；
Then, above-mentioned solution is filtered by vacuum to obtain laminated film, it is dry；
It is wherein annealed 4 ± 0.1 hours, is obtained porous with 350 ± 1 DEG C finally, obtained laminated film is mixed in nitrogen, hydrogen
Flexible composite film.
The hollow open nickel, cobalt, manganese and oxygen of the nanometer sheet assembling of three-dimensional porous carbon nano tube/graphene load prepared by the present invention
The laminated film of compound microballoon, may be used as lithium ion battery negative material, has height ratio capacity, excellent high rate performance and follows
Ring performance.After 300 circle of circulation, in 2 Ag-1Under can reach 1595mAhg-1Specific capacity.
Above-mentioned Three-dimensional porous compound film can be used to prepare lithium ion battery, specifically directly as negative electrode of lithium ion battery
Step are as follows:
In the glove box full of argon gas, using the appropriately sized film of above-mentioned preparation as working electrode, lithium piece is used as to electricity
Pole, 2400 porous polypropylene of Celgard are dissolved in the lithium hexafluoro phosphate conduct of ethylene carbonate, diethyl carbonate as diaphragm
Electrolyte is fitted into CR2016 button cell.
Battery specific capacity is calculated with the total quality of film.
Detailed description of the invention
Fig. 1 is hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material X-ray diffraction of nanometer sheet assembling
Spectrum.
Fig. 2 is the stereoscan photograph of the hollow open nickel, cobalt and manganese oxide microballoon of nanometer sheet assembling.
Fig. 3 is the transmission electron microscope photo of the hollow open nickel, cobalt and manganese oxide microballoon of nanometer sheet assembling.
Fig. 4 is that porous carbon nanotube/graphene-supported nanometer sheet assembling hollow open nickel, cobalt and manganese oxide of preparation is micro-
The photo and stereoscan photograph of the laminated film of ball.Wherein, a is the photo of film, and b is that the scanning electron microscope of film surface is shone
Piece, c are the stereoscan photographs of thin-membrane section.
Fig. 5 is answering for porous carbon nanotube/graphene-supported nanometer sheet assembling hollow open nickel, cobalt and manganese oxide microballoon
Close the x-ray photoelectron spectroscopy of film.Wherein, a is the fine spectrum of Ni 2p；B is the fine spectrum of Co 2p；C is the essence of Mn 2p
Thin spectrum；D is the fine spectrum of O 1s；E is the fine spectrum of C 1s.
Fig. 6 is answering for porous carbon nanotube/graphene-supported nanometer sheet assembling hollow open nickel, cobalt and manganese oxide microballoon
Film is closed in 0.1 mVs-1Cyclic voltammetric (CV) curve under sweep speed.
Fig. 7 is answering for porous carbon nanotube/graphene-supported nanometer sheet assembling hollow open nickel, cobalt and manganese oxide microballoon
Film is closed in 2Ag-1Constant current charge-discharge curve under current density.
Fig. 8 is answering for porous carbon nanotube/graphene-supported nanometer sheet assembling hollow open nickel, cobalt and manganese oxide microballoon
Film is closed in 2 Ag-1Cyclic curve under current density.
Specific embodiment
Embodiment 1:
(1) hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material preparation of nanometer sheet self assembly:
Firstly, by 262.9 mg nickel sulfate hexahydrates, 281.2 mg cobalt sulfates, 158 mg potassium permanganate and 1420mg sulfuric acid
Sodium is dissolved in 50 mL deionized waters, and ultrasonic disperse 5 minutes.Then, above-mentioned solution is transferred in water heating kettle, at 160 DEG C
It is lower to be kept for 12 hours.Then, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, it is dry, obtain presoma.Then, will
10 mg presomas and with Hummer method prepare 5 mg graphene oxides be dissolved in the deionized water of 100 mL, ultrasound point
It dissipates 30 minutes.Then, above-mentioned solution is transferred in water heating kettle, is kept for 5 hours at 180 DEG C.Finally, using deionized water and
Ethyl alcohol distinguishes multiple centrifuge washing, dry, obtains nickel, cobalt and manganese oxide microballoon/graphene composite material.Finally obtained nickel cobalt
Mn oxide micro-sphere structure is hollow structure, and most particles are simultaneously not opening.
(2) hollow open nickel, cobalt and manganese oxide microballoon/graphene/carbon nanotube composite film system of nanometer sheet assembling
It is standby:
Firstly, microballoon/graphene composite material of 10 mg is dissolved in 50 mL deionized waters, ultrasonic disperse 10 minutes.So
Afterwards, carbon nano tube dispersion liquid (5 mg of carbon nanotubes) is instilled in above-mentioned solution, is dispersed with stirring 15 minutes.It then, will be above-mentioned
Solution is filtered by vacuum to obtain laminated film, dry.Finally, by obtained laminated film with 350 in nitrogen, hydrogen mixed gas
DEG C annealing 4 hours, obtain porous flexible laminated film.
Embodiment 2:
(1) hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material preparation of nanometer sheet self assembly:
Firstly, by 262.9 mg nickel sulfate hexahydrates, 281.2 mg cobalt sulfates, 158 mg potassium permanganate and 1420mg sulfuric acid
Sodium is dissolved in 50 mL deionized waters, and ultrasonic disperse 5 minutes.Then, above-mentioned solution is transferred in water heating kettle, at 160 DEG C
It is kept for 12 hours.Then, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, it is dry, obtain presoma.Then, by 10
Mg presoma and with Hummer method prepare 5 mg graphene oxides be dissolved in the deionized water of 100 mL, ultrasonic disperse 30
Minute.Then, above-mentioned solution is transferred in water heating kettle, is kept for 16 hours at 180 DEG C.Finally, using deionized water and second
Alcohol distinguishes multiple centrifuge washing, dry, obtains hollow open nickel, cobalt and manganese oxide microballoon/graphene composite wood of nanometer sheet assembling
Material.Finally obtained nickel, cobalt and manganese oxide micro-sphere structure is hollow open configuration, but it is very serious to reunite.
(2) hollow open nickel, cobalt and manganese oxide microballoon/graphene/carbon nanotube composite film system of nanometer sheet assembling
It is standby:
Firstly, hollow open microballoon/graphene composite material of 10 mg is dissolved in 50 mL deionized waters, ultrasonic disperse 10
Minute.Then, carbon nano tube dispersion liquid (carbon nanotubes 4mg) is instilled in above-mentioned solution, is dispersed with stirring 15 minutes.Then,
Above-mentioned solution is filtered by vacuum to obtain laminated film, it is dry.Finally, by obtained laminated film in nitrogen, hydrogen mixed gas
It is annealed 4 hours with 350 DEG C, obtains porous flexible laminated film.
Embodiment 3:
(1) hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material preparation of nanometer sheet self assembly:
Firstly, by 262.9 mg nickel sulfate hexahydrates, 281.2 mg cobalt sulfates, 158 mg potassium permanganate and 1420mg sulfuric acid
Sodium is dissolved in 50 mL deionized waters, and ultrasonic disperse 5 minutes.Then, above-mentioned solution is transferred in water heating kettle, at 160 DEG C
It is kept for 10 hours.Then, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, it is dry, obtain presoma.Then, by 10
Mg presoma and with Hummer method prepare 5 mg graphene oxides be dissolved in the deionized water of 100 mL, ultrasonic disperse 30
Minute.Then, above-mentioned solution is transferred in water heating kettle, is kept for 10 hours at 160 DEG C.Finally, using deionized water and second
Alcohol distinguishes multiple centrifuge washing, dry, obtains hollow open nickel, cobalt and manganese oxide microballoon/graphene composite wood of nanometer sheet assembling
Material.Finally obtained nickel, cobalt and manganese oxide micro-sphere structure be hollow open configuration, about 2 μm of size.
(2) hollow open nickel, cobalt and manganese oxide microballoon/graphene/carbon nanotube composite film system of nanometer sheet assembling
It is standby:
Firstly, hollow open microballoon/graphene composite material of 10 mg is dissolved in 50 mL deionized waters, ultrasonic disperse 10
Minute.Then, carbon nano tube dispersion liquid (carbon nanotubes 4mg) is instilled in above-mentioned solution, is dispersed with stirring 15 minutes.Then,
Above-mentioned solution is filtered by vacuum to obtain laminated film, it is dry.Finally, by obtained laminated film in nitrogen, hydrogen mixed gas
It is annealed 4 hours with 350 DEG C, obtains porous flexible laminated film.
The morphology and size of the hollow open nickel, cobalt and manganese oxide microballoon of nanometer sheet self assembly passes through scanning electron microscope
(1 Kv of SEM, Hitachi FE-SEM S-4800 operated at) characterization, i.e., disperse powder sample in ethyl alcohol, then
It is added dropwise to silicon chip drying.The Microstructure Information of the hollow open nickel, cobalt and manganese oxide microballoon of nanometer sheet self assembly passes through transmitted electron
Electronic Speculum (200 kV of TEM, JEOL JEM-2100F operated at) characterization, i.e., disperse powder sample in ethyl alcohol, then
It is added dropwise to copper mesh drying.X- difraction spectrum is in Bruker D8 X-ray diffractometer (Germany) with
Gained is tested on 40 kV and of Ni-filtere Cu KR radiation operated at, 40 mA.X-ray photoelectron
Power spectrum is as obtained by KratosAxis Ultra DLD test.By gained film directly as negative electrode of lithium ion battery, electricity
Chemical property is tested by electrochemical workstation (CHI 660D, Shanghai Chen Hua Instrument Ltd.).
Fig. 1 is that hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material X-ray of nanometer sheet self assembly is spread out
Penetrate (XRD) analysis.It reflects the information such as the crystal phase, purity, crystallinity of product.Diffraction maximum and Co3O4Cubic spinel phase
(JCPDS 74-1657) coincide well.In addition, about 25 ° diffraction maximum correspond to graphitized carbon (002) face.Sample is pure
Degree is high, and the degree of graphitization of carbon matrix is high.
Fig. 2 is by the hollow open nickel, cobalt and manganese oxide microballoon pattern of the nanometer sheet self assembly of scanning electron microscope (SEM) characterization.
Nanometer sheet is self-assembled into the microballoon of hollow open, and piece interlayer is stablized hole there is a large amount of, do not stacked, in the microballoon of opening
Portion surface not only increases active area, is also conducive to the infiltration of electrolyte.
The transmission electron microscope photo of Fig. 3 also demonstrates the hollow open configuration of microballoon, and a large amount of holes are present between nanoscale twins.
As shown in fig. 4 a, thin film, flexible has flexible the photo of the porous compound film of preparation.The scanning electron microscope of Fig. 4 b is shone
Piece shows the surface topography of film, and there is a large amount of hole, holes to rise and fall with ripple on surface, shows soft graphene
Lamella and carbon nanotube are tightly wrapped in hollow open microballoon.It is worth noting that, coarse and porous surface can provide fastly
The path of fast ion diffusion.The stereoscan photograph of Fig. 4 c illustrates the section structure of film, and about 33 μm of thickness.
The x-ray photoelectron spectroscopy (XPS) of Fig. 5 further analyzes the composition information of composite material.Nickel cobalt is shown in figure
There is the chemical valence of divalent and trivalent in three kinds of elements of manganese.The peak O 1s of Fig. 5 d is right respectively in 529.8,531.5,532.6 eV
It should be in the related oxygen species of Lattice Oxygen, Lacking oxygen and chemisorption[24, 25].Wherein, strong Lacking oxygen relevant peaks show in microballoon
The presence of Lacking oxygen.The C 1s spectrum of Fig. 5 e is decomposed into 2 peaks in 284.6eV, 285.5eV, corresponds respectively to graphitic carbon
And carbon defects[26]。
Nickel, cobalt and manganese oxide, graphene, carbon nanotube can be used as electrode material, and the CV curve of laminated film has bright
Aobvious redox peaks.As shown in fig. 6, main peak corresponds to the redox reaction of three kinds of metallic elements of nickel cobalt manganese.
Hollow open microballoon/graphene/carbon nanotube composite film of nanometer sheet assembling shows excellent electrochemistry
Energy.As shown in fig. 7, in 2 Ag-1Current density under, for the first time electric discharge reach 2410 mAhg-1Superelevation specific capacity.With
In circulation afterwards, specific capacity is gradually stable in about 1500 mAhg-1, this shows have electrode at higher current densities
There are excellent invertibity and high reversible capacity.Fig. 8 shows excellent cycle performance, in 2 Ag-1Current density under, circulation
300 circle specific capacities remain to reach 1595 mAhg-1。
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Claims (3)
1. a kind of preparation method of the laminated film of the hollow open microballoon of carbon-based frame load nanometer sheet assembling, which is characterized in that
Specific steps are as follows:
(1) hollow open nickel, cobalt and manganese oxide microballoon/graphene composite material preparation of nanometer sheet assembling:
Firstly, by 262.9 ± 0.5 mg nickel sulfate hexahydrates, 281.2 ± 0.5 mg cobalt sulfates, 158 ± 0.5 mg permanganic acid
Potassium and 1420 ± 0.5 mg sodium sulphate are dissolved in 50 ± 0.5 mL deionized waters, and ultrasonic disperse 10 ± 5 minutes；
Then, above-mentioned solution is transferred in water heating kettle, is kept for 10 ± 2 hours at 160 ± 20 DEG C；
Then, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, it is dry, obtain presoma；
Then, 100 ± 0.5 are dissolved in by 10 ± 2 mg presomas and with 5 ± 2 mg graphene oxides prepared by Hummer method
In the deionized water of mL, ultrasonic disperse 30 ± 5 minutes；
Then, above-mentioned solution is transferred in water heating kettle, is kept for 10 ± 6 hours at 160 ± 20 DEG C；
Finally, multiple centrifuge washing is distinguished using deionized water and ethyl alcohol, and it is dry, obtain the hollow open nickel cobalt of nanometer sheet assembling
Mn oxide microballoon/graphene composite material；
(2) hollow open nickel, cobalt and manganese oxide microballoon/graphene/carbon nanotube composite film preparation of nanometer sheet assembling:
Firstly, 10 ± 2 mg hollow open microballoons/graphene composite material is dissolved in 50 ± 0.5 mL deionized waters, ultrasound
Dispersion 10 ± 2 minutes；
Then, the carbon nano tube dispersion liquid of 5 ± 1 mg of carbon nanotubes is instilled in above-mentioned solution, is dispersed with stirring 15 ± 2 minutes；
Then, above-mentioned solution is filtered by vacuum to obtain laminated film, it is dry；
Finally, obtained laminated film is annealed 4 ± 0.1 hours in nitrogen, hydrogen mixed gas with 350 ± 1 DEG C, obtain porous
Flexible composite film.
2. the THIN COMPOSITE of the hollow open microballoon for the carbon-based frame load nanometer sheet assembling that the preparation method as described in claim 1 obtains
Film is the compound of the hollow open nickel, cobalt and manganese oxide microballoon of the nanometer sheet assembling of three-dimensional porous carbon nano tube/graphene load
Film.
3. the laminated film of the hollow open microballoon of carbon-based frame load nanometer sheet assembling as claimed in claim 2, as lithium from
The application of sub- cell negative electrode material.
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| CN116130257A (en) * | 2023-04-13 | 2023-05-16 | 河南科技学院 | Preparation method and application of NiCoMn ternary metal oxide hollow microsphere electrode material |
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