CN104241602A - Preparation method of hollow bowl-shaped carbon-based metal oxide composite material - Google Patents
Preparation method of hollow bowl-shaped carbon-based metal oxide composite material Download PDFInfo
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- CN104241602A CN104241602A CN201410406726.5A CN201410406726A CN104241602A CN 104241602 A CN104241602 A CN 104241602A CN 201410406726 A CN201410406726 A CN 201410406726A CN 104241602 A CN104241602 A CN 104241602A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a hollow bowl-shaped carbon-based metal oxide composite material. The preparation method comprises the following steps: preparing a precursor of the hollow bowl-shaped carbon-based metal oxide composite material through a precipitation method; carrying out calcination carbonation to obtain a hollow bowl-shaped carbon-based metal oxide composite lithium storage active material; preparing component and structure controllable composite by adjusting the ratio among a template, metal salt, hexamethylenetetramine and citrate, so as to realize the purpose of controllable electrochemical performance. The preparation method has the characteristic that a hollow bowl-shaped polystyrene micro ball template is adopted and hollow bowl-shaped carbon-based metal oxide composite materials of various components are prepared through a common method; not only does the material of the shape reserve all the advantages of a hollow structure material, more importantly, the problem that the space utilization rate of the hollow material is low, is solved; the filling density of the active material is improved; the volume energy density is extremely improved; thus the energy density, capacity, cycle performance and magnification performance of a single cell are improved.
Description
Technical field
The present invention relates to the preparation of energy storage material, in particular to the preparation method of a kind of hollow bowl-shape carbon based metal oxide composite for lithium ion battery negative, be specifically related to tin ash, zinc oxide, nickel oxide, cobaltosic oxide, di-iron trioxide, tri-iron tetroxide, manganese dioxide, zinc manganate, mangaic acid iron, mangaic acid cobalt, mangaic acid nickel, cobalt acid nickel, sub-cobalt acid nickel, cobalt acid iron, cobalt acid nickel, the preparation of cobalt ferrite and hollow bowl-shape carbon tiny balloon composite material.
Technical background
Lithium ion battery, as a kind of novel, clean, chargeable power supply, has the advantages such as operating voltage is high, energy density is high, quality is light, self-discharge rate is low, the portable electric appts such as mobile phone, notebook computer is widely applied.Widely used electrode material in lithium ion, through optimization for many years, performance has reached its limit.The main target of lithium ion battery exploitation of future generation extends cycle life, improves energy density and charging and discharging capacity.At present, the pulsating stress that change in volume produces in charge and discharge process accelerates the mechanical failure of electrode material, battery capacity after repeatedly circulating is declined fast, and a lot of research concentrates on and utilizes adjustment structure strategy namely to prepare hollow structure material to alleviate above problem.Cavity in hollow structure material is that in charge and discharge cycles process, change in volume provides cushion space, adds the memory space of lithium ion simultaneously.But, hollow-core construction (hollow ball prepared at present, hollow cubic body, hollow pipe etc.) all there is larger cavity, except the change in volume produced for buffer cycles stress, greatly space is all idle, and this part idle space is do not have contributive to material electrochemical performance, thus reduces the volume energy density of battery.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of hollow bowl-shape carbon based metal oxide composite, utilize the shell of linear polystyrene tiny balloon softness and large cavity, become hollow bowl-shape hollow ball by the method for drying; The advantage of the method is that hollow bowl structure not only remains the advantage of hollow-core construction buffer electrode material volume change but also can get rid of " leaving unused " space, increases packing density; In addition the pattern of the metal oxide of hollow bowl-shape polystyrene microsphere load be can regulate and control from nano particle, nano wire is to nanometer sheet; This method is a kind of controllable, universality and high-volume preparation method, the performance of lithium ion battery negative material is improved by controlling the Nomenclature Composition and Structure of Complexes, by the kind of extreme enrichment carbon based metal oxide electrode material and character, greatly expand their range of application, for the industrial production and extensive use with the nanostructure composite material of inorganic matter of new structure and excellent properties lays the foundation.
In order to achieve the above object, technical scheme of the present invention is achieved in that
A preparation method for hollow bowl-shape carbon based metal oxide composite, comprises the following steps:
The first step: take hollow bowl-shape polystyrene microsphere and put into round-bottomed flask, adding its mass ratio is 1:(10 ~ 100) mass concentration be the concentrated sulfuric acid of 98%, ultrasonic disperse 1 ~ 60 minute, then stirring reaction 0 ~ 24 hour at 20 ~ 80 DEG C, the hollow bowl-shape sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby; Described ultrasonic power is 250W; Mixing speed is 400r/min;
Second step: the hollow bowl-shape sulfonated polystyrene ball taking the preparation of 10 ~ 500mg step one, join in the mercaptoacetic acid solution of the 10 ~ 100mM of 10 ~ 100mL, ultrasonic disperse 1 ~ 60 minute, described ultrasonic power is 250W; Then 10 ~ 1000mg SnCl is added successively
22H
2the hydrochloric acid of O, 100 ~ 1000mg urea and 0.1 ~ 2mL mass concentration 37%, then stirring reaction 2 ~ 24 hours at 40 ~ 80 DEG C, mixing speed is 400r/m; By the product centrifugation obtained, then use ethanol eccentric cleaning 1 ~ 10 time, obtain hollow bowl-shape tin dioxide composite material presoma, drying for standby;
Or second step: the hollow bowl-shape sulfonated polystyrene microballoon taking the preparation of 10 ~ 500mg step one, join in 40 ~ 4000mL deionized water, ultrasonic disperse 10 minutes, add 7.2 ~ 725mg citrate successively again, 35.5 ~ 3550mg hexamethylenetetramine, the salt of 75 ~ 7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape metal oxide composite; Metal ion contained by the salt of described metal ion comprises zinc, nickel, cobalt, iron and manganese; Described hexamethylenetetramine can substitute with hexamethylene diamine or six methine triamines.
3rd step: by the product in second step in inert atmosphere stove 350 ~ 800 DEG C calcining 1 ~ 12 hour, heating rate is 0.5 ~ 5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon based metal oxide composite.
The hollow bowl-shape carbon based metal oxide compound storage lithium active material utilizing the present invention to prepare has the following advantages: 1) higher specific area, thus can provide more active reaction sites, thus improves reaction efficiency; 2) from the angle that material is filled, the hollow bowl-shape ball of circular hollow ball comparing same particle diameter has larger packing density in identical volume, greatly improves the volume energy density of battery; 3) have the material of hollow bowl structure, its capacity, cycle performance and high rate performance are obviously better than other hollow-core construction metal oxide materials.Hollow bowl-shape hollow-core construction not only can retain all advantages of hollow material, and fully can compress those spaces of " leaving unused ".The easily stacking characteristic of hollow bowl structure can make the packing density of material greatly improve, thus makes electrode material have higher volume energy density, capacity, cycle performance and high rate performance.Undertaken processing by p-poly-phenyl ethene tiny balloon and obtain hollow hollow bowl-shape polystyrene hollow microballoon, with this hollow bowl-shape polystyrene microsphere for template, be there is by the precipitation method and calcination processing synthesis the hollow bowl-shape carbon based metal oxide combination electrode material of good electrical chemical property.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the hollow bowl-shape carbon back tin ash of embodiment one product.
Fig. 2 is the transmission electron microscope photo of the hollow bowl-shape carbon back tin ash of embodiment one product.
Fig. 3 is embodiment one product X x ray diffraction collection of illustrative plates.
Fig. 4 is that embodiment one product contrasts figure with the cycle performance of hollow circular carbon back tin ash, and wherein in figure, A represents embodiment one product, and in figure, B represents hollow circular carbon back tin ash.
Embodiment
Embodiment one
The present embodiment comprises the following steps:
The first step: take the hollow bowl-shape polystyrene microsphere of 0.1g and put into flask, the mass concentration adding 40mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 4 hours at 40 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby; Described ultrasonic power is 250W; Mixing speed is 400r/m.
Second step: get the hollow bowl-shape sulfonated polystyrene microballoon of 10mg, join in the mercaptoacetic acid solution of the 35mM of 30mL, ultrasonic disperse 10 minutes, described ultrasonic power is 250W; Then 30mg SnCl is added successively
2, 30mg urea and 0.3mL strong acid, then stirring reaction 4 hours at 40 DEG C, mixing speed is 400r/m; By the product centrifugation obtained, then use ethanol eccentric cleaning 6 times, obtain hollow bowl-shape tin dioxide composite material presoma, drying for standby.
3rd step: by the product in second step in inert atmosphere stove 350 DEG C calcining 3 hours, heating rate is 0.5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon back tin dioxide composite material.
With reference to the stereoscan photograph that Fig. 1 is the hollow bowl-shape carbon back tin ash of the present embodiment product, illustrate that products therefrom is bowl structure.
With reference to the transmission electron microscope photo that Fig. 2 is the hollow bowl-shape carbon back tin ash of the present embodiment product, illustrate that products therefrom possesses hollow-core construction.
Reference Fig. 3 is the present embodiment product X x ray diffraction collection of illustrative plates, illustrates that this product is tin ash.
Reference Fig. 4 is that the present embodiment product contrasts figure with the cycle performance of hollow circular carbon back tin ash, illustrates that the tin ash cycle performance of hollow bowl structure is better than hollow circular carbon back tin ash.
Embodiment two
The present embodiment comprises the following steps:
The first step: take the hollow bowl-shape polystyrene microsphere of 0.5g and put into flask, the mass concentration adding 40mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 80 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m.
Second step: the hollow bowl-shape sulfonated polyphenyl second microballoon taking the above-mentioned preparation of 10mg joins in 120mL deionized water, ultrasonic disperse 10 minutes, add 36.2mg natrium citricum successively again, 177.5mg hexamethylenetetramine, 177.5mg zinc nitrate, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape sulfoxidation zinc composite material.
3rd step: by the product in second step in inert atmosphere stove 400 DEG C calcining 6 hours, heating rate is 0.5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon back zinc oxide composite.
Embodiment three
The present embodiment comprises the following steps:
The first step: take the hollow bowl-shape polystyrene spheres of 1g and put into flask, the mass concentration adding 50mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 80 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m.
Second step: take the hollow bowl-shape sulfonated polystyrene microballoon of 50mg, join in 400mL deionized water, ultrasonic disperse 10 minutes, add 72.5mg natrium citricum successively again, 355mg six methine triamine, 750mg nickelous sulfate, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape nickel oxide composite material.
3rd step: by product in second step in inert atmosphere stove 500 DEG C calcining 6 hours, heating rate is 1 DEG C of min
-1, the product obtained is hollow bowl-shape carbon back nickel oxide composite material.
The present embodiment through this product of X-ray diffractogram analysis of spectrum be nickel oxide, under the current density of 200mA g-1, through 150 circulations, its capacity still remains on 955mA h g-1, illustrates that its capacity and cycle performance are better than the nickel oxide composite material of other structures.
Embodiment four
The present embodiment comprises the following steps:
The first step: take the hollow bowl-shape polystyrene microsphere of 2g and put into flask, the mass concentration adding 50mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 80 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m.
Second step: the hollow bowl-shape sulfonated polystyrene microballoon taking the above-mentioned preparation of 100mg, join in 750mL deionized water, ultrasonic disperse 10 minutes, add 145mg natrium citricum successively again, 750mg hexamethylene diamine, 1500mg nickel nitrate and cobalt nitrate salt-mixture, wherein nickel nitrate 750mg, cobalt nitrate 750mg, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape nickel cobalt composite material.
3rd step: by product in second step in inert atmosphere stove 600 DEG C calcining 3 hours, heating rate is 1 DEG C of min
-1, the product obtained is hollow bowl-shape carbon back cobalt nickel O compoiste material.
The present embodiment through this product of X-ray diffractogram analysis of spectrum be carbon back cobalt nickel O compoiste material---sub-cobalt acid nickel, under the current density of 400mA g-1, through 200 circulations, its capacity still remains on 850mA h g-1, illustrates that its capacity and cycle performance are better than the sub-cobalt acid nickel composite of other structures.
Embodiment five
The present embodiment comprises the following steps:
The first step: take the hollow bowl-shape polystyrene spheres of 2g and put into flask, the mass concentration adding 80mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 60 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m.
Second step: the sulfonated polystyrene ball taking the above-mentioned preparation of 500mg, join in 4000mL deionized water, ultrasonic disperse 10 minutes, then add 725mg natrium citricum successively, 3550mg hexamethylenetetramine, 7500mg zinc sulfate and cobalt chloride, wherein zinc sulfate 3750mg, cobalt chloride 3750mg, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape zinc cobalt oxygen.
3rd step: by product in second step in inert atmosphere stove 800 DEG C calcining 6 hours, heating rate is 0.5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon back zinc cobalt O compoiste material.
Claims (7)
1. a preparation method for hollow bowl-shape carbon based metal oxide composite, is characterized in that, comprise the following steps:
The first step: take hollow bowl-shape polystyrene microsphere and put into round-bottomed flask, adding its mass ratio is 1:(10 ~ 100) mass concentration be the concentrated sulfuric acid of 98%, ultrasonic disperse 1 ~ 60 minute, then stirring reaction 0 ~ 24 hour at 20 ~ 80 DEG C, the hollow bowl-shape sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby; Described ultrasonic power is 250W; Mixing speed is 400r/min;
Second step: the hollow bowl-shape sulfonated polystyrene ball taking the preparation of 10 ~ 500mg step one, join in the mercaptoacetic acid solution of the 10 ~ 100mM of 10 ~ 100mL, ultrasonic disperse 1 ~ 60 minute, described ultrasonic power is 250W; Then 10 ~ 1000mg SnCl is added successively
22H
2the hydrochloric acid of O, 100 ~ 1000mg urea and 0.1 ~ 2mL mass concentration 37%, then stirring reaction 2 ~ 24 hours at 40 ~ 80 DEG C, mixing speed is 400r/m; By the product centrifugation obtained, then use ethanol eccentric cleaning 1 ~ 10 time, obtain hollow bowl-shape tin dioxide composite material presoma, drying for standby;
3rd step: by the product in second step in inert atmosphere stove 350 ~ 800 DEG C calcining 1 ~ 12 hour, heating rate is 0.5 ~ 5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon based metal oxide composite.
2. a preparation method for hollow bowl-shape carbon based metal oxide composite, is characterized in that, comprise the following steps:
The first step: take hollow bowl-shape polystyrene microsphere and put into round-bottomed flask, adding its mass ratio is 1:(10 ~ 100) mass concentration be the concentrated sulfuric acid of 98%, ultrasonic disperse 1 ~ 60 minute, then stirring reaction 0 ~ 24 hour at 20 ~ 80 DEG C, obtain hollow bowl-shape sulfonated polystyrene microballoon, and with ethanol washing to neutral, drying for standby; Described ultrasonic power is 250W; Mixing speed is 400r/min;
Second step: the hollow bowl-shape sulfonated polystyrene microballoon taking the preparation of 10 ~ 500mg step one, join in 40 ~ 4000mL deionized water, ultrasonic disperse 10 minutes, add 7.2 ~ 725mg citrate successively again, 35.5 ~ 3550mg hexamethylenetetramine, the salt of 75 ~ 7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape metal oxide composite; Metal ion contained by the salt of described metal ion comprises zinc, nickel, cobalt, iron and manganese; Described hexamethylenetetramine can substitute with hexamethylene diamine or six methine triamines;
3rd step: by the product in second step in inert atmosphere stove 350 ~ 800 DEG C calcining 1 ~ 12 hour, heating rate is 0.5 ~ 5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon based metal oxide composite.
3. the preparation method of a kind of hollow bowl-shape carbon based metal oxide composite according to claim 1, is characterized in that, comprise the following steps:
The first step: take the hollow bowl-shape polystyrene microsphere of 0.1g and put into flask, the mass concentration adding 40mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 4 hours at 40 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby; Described ultrasonic power is 250W; Mixing speed is 400r/m;
Second step: get the hollow bowl-shape sulfonated polystyrene microballoon of 10mg, join in the mercaptoacetic acid solution of the 35mM of 30mL, ultrasonic disperse 10 minutes, described ultrasonic power is 250W; Then 30mg SnCl is added successively
2, 30mg urea and 0.3mL strong acid, then stirring reaction 4 hours at 40 DEG C, mixing speed is 400r/m; By the product centrifugation obtained, then use ethanol eccentric cleaning 6 times, obtain hollow bowl-shape tin dioxide composite material presoma, drying for standby;
3rd step: by the product in second step in inert atmosphere stove 350 DEG C calcining 3 hours, heating rate is 0.5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon back tin dioxide composite material.
4. the preparation method of a kind of hollow bowl-shape carbon based metal oxide composite according to claim 2, is characterized in that, comprise the following steps:
The first step: take the hollow bowl-shape polystyrene microsphere of 0.5g and put into flask, the mass concentration adding 40mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 80 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is to neutral, drying for standby, described ultrasonic power is 250W; Mixing speed is 400r/m;
Second step: the hollow bowl-shape sulfonated polyphenyl second microballoon taking the above-mentioned preparation of 10mg joins in 120mL deionized water, ultrasonic disperse 10 minutes, add 36.2mg natrium citricum successively again, 177.5mg hexamethylenetetramine, 177.5mg zinc nitrate, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape sulfoxidation zinc composite material;
3rd step: by the product in second step in inert atmosphere stove 400 DEG C calcining 6 hours, heating rate is 0.5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon back zinc oxide composite.
5. the preparation method of a kind of hollow bowl-shape carbon based metal oxide composite according to claim 2, is characterized in that, comprise the following steps:
The first step: take the hollow bowl-shape polystyrene spheres of 1g and put into flask, the mass concentration adding 50mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 80 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m;
Second step: take the hollow bowl-shape sulfonated polystyrene microballoon of 50mg, join in 400mL deionized water, ultrasonic disperse 10 minutes, add 72.5mg natrium citricum successively again, 355mg six methine triamine, 750mg nickelous sulfate, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape nickel oxide composite material;
3rd step: by product in second step in inert atmosphere stove 500 DEG C calcining 6 hours, heating rate is 1 DEG C of min
-1, the product obtained is hollow bowl-shape carbon back nickel oxide composite material.
6. the preparation method of a kind of hollow bowl-shape carbon based metal oxide composite according to claim 2, is characterized in that, comprise the following steps:
The first step: take the hollow bowl-shape polystyrene microsphere of 2g and put into flask, the mass concentration adding 50mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 80 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m;
Second step: the hollow bowl-shape sulfonated polystyrene microballoon taking the above-mentioned preparation of 100mg, join in 750mL deionized water, ultrasonic disperse 10 minutes, add 145mg natrium citricum successively again, 750mg hexamethylene diamine, 1500mg nickel nitrate and cobalt nitrate salt-mixture, wherein nickel nitrate 750mg, cobalt nitrate 750mg, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape nickel cobalt composite material;
3rd step: by product in second step in inert atmosphere stove 600 DEG C calcining 3 hours, heating rate is 1 DEG C of min
-1, the product obtained is hollow bowl-shape carbon back cobalt nickel O compoiste material.
7. the preparation method of a kind of hollow bowl-shape carbon based metal oxide composite according to claim 2, is characterized in that, comprise the following steps:
The first step: take the hollow bowl-shape polystyrene spheres of 2g and put into flask, the mass concentration adding 80mL is the concentrated sulfuric acid of 98%, ultrasonic disperse 15 minutes, then stirring reaction 6 hours at 60 DEG C, the sulfonated polystyrene microballoon ethanol washing obtained is extremely neutral, drying for standby.Described ultrasonic power is 250W; Mixing speed is 400r/m;
Second step: the sulfonated polystyrene ball taking the above-mentioned preparation of 500mg, join in 4000mL deionized water, ultrasonic disperse 10 minutes, then add 725mg natrium citricum successively, 3550mg hexamethylenetetramine, 7500mg zinc sulfate and cobalt chloride, wherein zinc sulfate 3750mg, cobalt chloride 3750mg, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom ethanol washs 5 times, obtains the presoma of hollow bowl-shape zinc cobalt oxygen;
3rd step: by product in second step in inert atmosphere stove 800 DEG C calcining 6 hours, heating rate is 0.5 DEG C of min
-1; The product obtained is hollow bowl-shape carbon back zinc cobalt O compoiste material.
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