CN105140469A - Yolk-structured transition metal oxide/graphene composite material and preparation method and application thereof - Google Patents
Yolk-structured transition metal oxide/graphene composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of an inorganic non-metallic material and electrochemistry, and discloses a yolk-structured transition metal oxide/graphene composite material and a preparation method and application thereof. The method comprises the following steps of: (1) adding transition metal oxide particles and deionized water into an alcohol, carrying out ultrasonic dispersion, adding tetraethoxysilane and an ammonia solution, reacting for 3 to 8 hours at 20-50 DEG C, adding 3-aminopropyltriethoxysilane, stirring and uniformly mixing, placing in a hydrothermal kettle for hydrothermal reaction, washing and drying to obtain a surface-modified transition metal oxide; and (2) dispersing the surface-modified transition metal oxide in the deionized water, adjusting the pH of a dispersion liquid under a condition of stirring, adding a graphene oxide solution, stirring and uniformly mixing, placing in the hydrothermal kettle for hydrothermal reaction, placing in a strong alkali solution, stirring and reacting, centrifugally washing and drying to obtain the yolk-structured transition metal oxide/graphene composite material. The prepared material has relatively favorable electrochemical performance.
Description
Technical field
The invention belongs to Inorganic Non-metallic Materials and electrochemical field, relate to a kind of graphene composite material, particularly a kind of egg yolk structure transition metal oxide/graphene composite material and preparation method thereof and the application in lithium ion battery.
Background technology
Along with the continuous increase of portable electric appts demand, to design and the research of lithium ion battery of preparing high-energy and high power density more and more receives the concern of scientific worker.The performance of lithium ion battery depends primarily on the performance of electrode used therein material.Transition metal oxide, due to its high theoretical capacity, is a kind of potential li-ion electrode materials.But because the conductivity of transition metal oxide material own is lower, in this external lithium ion charge and discharge cycles, change in volume is comparatively large, and this seriously have impact on the performance of transition metal oxide as lithium ion battery electrode material and the cyclical stability of battery.Research finds, transiting state metal oxide presents poor chemical property usually as the lithium ion battery of negative material.In order to solve the problem, conventional method is at transition metal oxide Surface coating one deck conductive material (e.g., carbon, polyaniline, Graphene etc.).The coated electric conductivity that effectively can improve transition metal oxide electrode material of conductive material, the lithium ion battery of gained often presents higher chemical property thus.Even if but the coated performance that can improve transition metal oxide electrode material of conductive material, closely coated transition metal oxide easily causes deformation because of change in volume meeting, thus causes electrode material to come off from current collector.Therefore, the closely coated of conductive material fundamentally cannot solve transiting state metal oxide electrode material Problems existing.
At raising electrode material electric conductivity simultaneously, how electric conducting material and transition metal are carried out the effectively coated stability with improving electrode material to become people and need one of problem solved.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of egg yolk structure transition metal oxide/graphene composite material.
Another object of the present invention is to provide the egg yolk structure prepared by above-mentioned preparation method transition metal oxide/graphene composite material.
Another object of the present invention is the application providing above-mentioned egg yolk structure transition metal oxide/graphene composite material.
Object of the present invention is achieved through the following technical solutions:
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of surface modification transition metal oxide
Transition metal oxide particle and deionized water are added in alcohol, ultrasonic disperse, obtain dispersion liquid; In dispersion liquid, add tetraethoxysilane and ammonia spirit, in 20 ~ 50 DEG C of reaction 3 ~ 8h, obtain product; Then, in product, add 3-aminopropyl triethoxysilane, stir and evenly mix, be placed in water heating kettle and carry out hydro-thermal reaction, washing, dry, obtain the transition metal oxide particle of surface modification;
(2) synthesis of egg yolk structure transition metal oxide/graphene composite material
By the transition metal oxide Granular composite of surface modification in step (1) in deionized water, obtain dispersion liquid; Under the condition stirred, regulate pH to 1 ~ 4 of dispersion liquid, then add graphene oxide solution, stir and evenly mix, obtain mixture; Mixture is placed in water heating kettle and carries out hydro-thermal reaction, after having reacted, the product of hydro-thermal reaction is placed in strong base solution, stirring reaction, centrifuge washing, dry, obtain egg yolk structure transition metal oxide/graphene composite material.
Transition metal oxide in step (1): tetraethoxysilane: ammonia spirit: the mass volume ratio of 3-aminopropyl triethoxysilane is (50 ~ 100) mg:(0.1 ~ 1.0) mL:(0.5 ~ 5) mL:(0.05 ~ 0.2) mL.Described in step (1), the mass percent concentration of ammoniacal liquor is 25%.
Transition metal oxide described in step (1) is more than one in iron oxide, tri-iron tetroxide, manganese dioxide or cobaltosic oxide; Described alcohol is methyl alcohol, ethanol or isopropyl alcohol, preferred alcohol.
Transition metal oxide particle described in step (1): deionized water: the mass volume ratio of alcohol is (50 ~ 100) mg:(10 ~ 200) mL:(20 ~ 120) mL.
In step (1), hydrothermal temperature is 50 ~ 120 DEG C, and the reaction time is 10 ~ 30h; Described in step (1), the condition of ultrasonic disperse is power 100 ~ 500W, frequency 20 ~ 80KHz, and the time of ultrasonic disperse is 10 ~ 30min.
Described in step (1), mixing speed is 500 ~ 2000r/min, and described mixing time is 1 ~ 3h; Wash conditions described in step (1) is for adopting deionized water washing to neutral; Described in step (1), baking temperature is 50 ~ 100 DEG C, and drying time is 6 ~ 10h.
The transition metal oxide of surface modification described in step (2): the mass ratio of graphene oxide is (0.2 ~ 5): 1; The transition metal oxide particle of surface modification described in step (2) and the mass volume ratio of deionized water are (10 ~ 200) mg:(10 ~ 40) mL.
Regulate the material of dispersion liquid pH to be dilute hydrochloric acid solution described in step (2), the mass percent concentration of described watery hydrochloric acid is 3 ~ 10%.
Rotating speed 500 ~ the 2000r/min stirred and evenly mixed described in step (2), described in time of stirring and evenly mixing be 0.5 ~ 2h; The time of stirring reaction described in step (2) is 5 ~ 12h, and the rotating speed of described stirring reaction is 500 ~ 2000r/min.
Described in step (2), the temperature of hydro-thermal reaction is 150 ~ 200 DEG C, and the hydro-thermal reaction time is 10 ~ 24h;
The product of hydro-thermal reaction described in step (2) and the mass volume ratio of strong base solution are (100 ~ 400) mg:(50 ~ 200) mL.
The condition of washing described in step (2) is for adopting deionized water washing to neutral; Described in step (2), baking temperature is 50 ~ 100 DEG C, and drying time is 10 ~ 20h; Described in step (2), strong base solution is the KOH solution of 1 ~ 5M.
Graphene oxide solution described in step (2) is scattered in deionized water by graphene oxide to prepare, and wherein the mass volume ratio of graphene oxide and deionized water is (50 ~ 100) mg:(50 ~ 200) mL; Described graphene oxide is prepared from by the Hummers method improved.
The preparation method of described graphene oxide, concrete steps are:
Under condition of ice bath, the concentrated sulfuric acid that mass percent is 95 ~ 98% is added in the container that sodium nitrate and graphite mixture is housed, stirring reaction 0.5 ~ 1h (rotating speed of stirring is 500 ~ 1000r/min), progressively add potassium permanganate (number of times is 5 ~ 20 times) subsequently, within controlling reaction temperature 6 ~ 20 DEG C, room temperature reaction time 10 ~ 24h, is warming up to 90 ~ 100 DEG C subsequently, add deionized water, reaction 2 ~ 24h; Add the hydrogen peroxide reduction residual oxide 1h that mass percent is 30 ~ 35%, adopt mass percent to be that 3 ~ 10% hydrochloric acid solution washings and deionized water wash to faintly acid (pH is 3 ~ 4) successively, freeze-drying is for subsequent use.
The mass volume ratio of described graphite, described sodium nitrate, the described concentrated sulfuric acid, described potassium permanganate, described deionized water and described hydrogen peroxide is (1 ~ 6) g:(2 ~ 6) g:(100 ~ 500) mL:(15 ~ 35) g:(100 ~ 400) mL:(50 ~ 150) mL.
Described graphite is native graphite or expanded graphite.
In described graphene oxide, oxygen atomicity content accounts for 20 ~ 50% of total atom number.
A kind of egg yolk structure transition metal oxide/graphene composite material is prepared by above-mentioned preparation method.
Described egg yolk structure transition metal oxide/graphene composite material is used for field of lithium ion battery.
Transition metal oxide makes it positively charged in an acidic solution by surface modification by the present invention, and graphene oxide solution surface band negative electrical charge in weakly acidic solution, two kinds of materials are combined by electrostatic attraction, are removed the SiO of transition metal oxide particle surface subsequently by KOH solution
2layer, obtains the transition metal oxide/graphene composite material of egg yolk structure.
A kind of material of egg yolk structure is formed among the shell that transition metal oxide is placed in conductive material by the present invention, in this material, continuous print conductive material shell effectively can improve the conductivity of electrode, and the space between transition metal oxide and shell can provide space for the change in volume of transition metal oxide in charge and discharge cycles; The present invention, using the shell of Graphene as egg yolk structure, more effectively can improve the performance of transiting state metal oxide as lithium ion battery negative material.The electrode material that test result display has this kind of structure has excellent electro-chemical activity, comprises high charge/discharge capacity, good cyclical stability and stable high rate performance.This kind of electrode material has great potentiality in raising lithium ion battery energy density and power density etc.
Tool of the present invention has the following advantages and beneficial effect:
Technique of the present invention is simple, cheaper starting materials, and egg yolk structure transition metal oxide/graphene composite material prepared by this kind of method, compared to transition metal oxide material prepared by other method, there is chemical property high, Stability Analysis of Structures, the advantages such as specific area is large.
Accompanying drawing explanation
Fig. 1 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 1
3o
4voidRGO) scanning electron microscope (SEM) photograph and SEM figure;
Fig. 2 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 1
3o
4voidRGO) transmission electron microscope picture and TEM figure;
Fig. 3 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 1
3o
4void RGO) x-ray photoelectron energy spectrogram;
Fig. 4 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 1
3o
4voidRGO) infrared spectrum;
Fig. 5 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 1
3o
4voidRGO) be the performance of lithium ion battery resolution chart of electrode and cycle performance curve;
Fig. 6 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 1
3o
4voidRGO) be the lithium ion battery coulombic efficiency figure of electrode;
Fig. 7 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 2
3o
4voidRGO) for electric performance test curve during lithium ion battery electrode material and cycle performance curve;
Fig. 8 is egg yolk structure tri-iron tetroxide/graphene composite material (i.e. Fe prepared by embodiment 3
3o
4voidRGO) for electric performance test curve during lithium ion battery electrode material and cycle performance curve;
The composite material of Fig. 9 prepared by embodiment 1 and embodiment 4 is for electric performance test curve during lithium ion battery electrode material and cycle performance curve;
Figure 10 is egg yolk structure sesquioxide/graphene composite material (i.e. Fe prepared by embodiment 6
2o
3voidRGO) for electric performance test curve during lithium ion battery electrode material and cycle performance curve;
Figure 11 is egg yolk structure manganese dioxide/graphene composite material (i.e. MnO prepared by embodiment 7
2voidrGO) for electric performance test curve during lithium ion battery electrode material and cycle performance curve;
Figure 12 is egg yolk structure cobalt oxide/graphene composite material (i.e. Co prepared by embodiment 8
3o
4voidRGO) for electric performance test curve during lithium ion battery electrode material and cycle performance curve.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide
By improve Hummers legal system for graphene oxide, idiographic flow is as follows: under condition of ice bath, the 300mL concentrated sulfuric acid (mass percent concentration is 98%) is added in the 1000mL flask filling 5g sodium nitrate and 2g graphite mixture, stirring reaction 1h (rotating speed of stirring is 1000r/min), divide 10 times subsequently and progressively add 30g potassium permanganate, within controlling reaction temperature 10 DEG C, room temperature reaction 24h subsequently, again flask is transferred to oil bath heating, keep temperature 98 DEG C, add 300mL deionized water, reaction 24h, solution colour becomes brown color from black transitions; Add the hydrogen peroxide that 100mL mass percent is 35%, reaction 1h, reduction residual oxide, adopts mass percent concentration to be that 5% hydrochloric acid solution washing and deionized water wash to faintly acid (pH is 4), in-50 DEG C of temperature freeze-drying, obtain graphene oxide; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of surface modification ferroferric oxide nano granules
Get 80mg ferroferric oxide nano granules and 16mL deionized water is scattered in 64mL ethanol, ultrasonic disperse 30min (power 500W, frequency 80KHz), obtains dispersion liquid; Under 50 DEG C of water bath condition, in dispersion liquid, add 0.5mL tetraethoxysilane and 1mL mass percent is 25% ammonia spirit, reaction 6h; Then, add 0.1mL3-aminopropyl triethoxysilane, stir 3h with the rotating speed of 1000r/min, be placed in water heating kettle, in 100 DEG C of hydro-thermal reaction 24h, then spend deionized water 5 times, in 60 DEG C of vacuumize 10h, obtain the ferroferric oxide nano granules of surface modification;
(3) synthesis of egg yolk structure tri-iron tetroxide/graphene composite material
The ferriferrous oxide particles getting the above-mentioned surface modification of 50mg is scattered in 20mL deionized water, obtains dispersion liquid; Under agitation (rotating speed of stirring is 1000r/min), in dispersion liquid, add dilute hydrochloric acid solution (mass percent concentration is 5%) be adjusted to pH=2.5, add the graphene oxide solution that 50mL concentration is 1mg/mL, stir 30min, obtain mixture; Subsequently mixture is placed in water heating kettle, in 180 DEG C of hydro-thermal reaction 12h, obtains the product of hydro-thermal reaction; The product of 100mg hydro-thermal reaction being added 50mL concentration is stirring reaction 10h in the KOH solution of 5M, and centrifugal water is washed till neutrality, then in the vacuum drying chamber of 60 DEG C dry 10h, obtain egg yolk structure tri-iron tetroxide/graphene composite material.The structural characterization of this composite material as shown in figures 1-4; During the electrode material of this composite material as lithium ion battery, electrochemical property test is as shown in Fig. 5,6,9.
Fig. 1 is the SEM figure of egg yolk structure tri-iron tetroxide/graphene composite material prepared by the present embodiment, Fig. 2 is that the TEM of egg yolk structure tri-iron tetroxide/graphene composite material prepared by the present embodiment schemes.As can be seen from the figure, tri-iron tetroxide/graphene composite material that prepared by the present embodiment has egg yolk structure.
Fig. 3 is the x-ray photoelectron energy spectrogram of egg yolk structure tri-iron tetroxide/graphene composite material prepared by the present embodiment.Can see, contain in composite material prepared by the present embodiment and only containing carbon, oxygen and ferro element, contain other impurity hardly.By can draw the percentage contents of each pantogen subnumber to the conversion of peak intensity, wherein oxygen atomicity accounts for 47.8% of total atom number, and iron atom number accounts for 18.8% of total atom number, and carbon number accounts for 33.4% of total atom number.Fig. 4 is the infrared spectrum of egg yolk structure tri-iron tetroxide/graphene composite material prepared by the present embodiment.
Fig. 5 and Fig. 6 is respectively cyclic curve and the coulombic efficiency curve of egg yolk structure tri-iron tetroxide/graphene composite material prepared by embodiment 1.As shown in Figure 5, electric specific capacity is by initial 1900mAhg
-1drop to 1280mAhg
-1and keep stable, after the circulation of 250 circles, prepared battery charging and discharging specific capacity still remains on 1273.4mAhg
-1.As shown in Figure 6, coulombic efficiency rises rapidly by initial 67%, maintains more than 95% subsequently.
Embodiment 2
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide
By improve Hummers legal system for graphene oxide, idiographic flow is as follows: under condition of ice bath, the concentrated sulfuric acid that 100mL mass fraction is 98% is added in the 1000mL flask filling 1g sodium nitrate and 3g graphite mixture, (mixing speed is 500r/min to stirring reaction, mixing time is 0.5h), divide subsequently and progressively add 15g potassium permanganate 5 times, within controlling reaction temperature 6 DEG C, room temperature reaction time 10h subsequently, flask is transferred to oil bath heating, keeps temperature 90 DEG C, add 100mL deionized water, reaction 2h, solution colour becomes brown color from black transitions; Add the hydrogen peroxide that 50mL mass percent concentration is 35%, reaction 1h, reduction residual oxide, adopt mass fraction to be that 3% hydrochloric acid solution washing and deionized water wash to pH=3, freeze-drying at-50 DEG C of temperature, obtains graphene oxide; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of surface modification ferroferric oxide nano granules
Get 80mg ferroferric oxide nano granules and 16mL deionized water is scattered in 120mL ethanol, ultrasonic disperse 20min (power 100W, frequency 20KHz), obtains dispersion liquid; Under 20 DEG C of water bath condition, in dispersion liquid, add 0.5mL tetraethoxysilane and 1mL mass percent is the ammonia spirit of 25%, reaction 3h; Then, add the 3-aminopropyl triethoxysilane of 0.1mL, stir 1h (mixing speed is 500r/min), then be placed in water heating kettle in 100 DEG C of hydro-thermal reaction 24h, obtain hydro-thermal reaction product; Adopted by product deionized water to wash 3 times, in 50 DEG C of vacuumize 10h, obtain the ferroferric oxide nano granules of surface modification;
(3) synthesis of egg yolk structure tri-iron tetroxide/graphene composite material
The ferriferrous oxide particles getting the above-mentioned surface modification of 10mg is scattered in 10mL deionized water, obtains dispersion liquid; Under agitation (rotating speed is 500r/min), add mass concentration be 3% dilute hydrochloric acid solution regulate dispersion liquid to pH=4, add the graphene oxide solution that 50mL concentration is 1mg/mL, stir 0.5h, obtain mixture; Subsequently mixture is placed in water heating kettle in 150 DEG C of hydro-thermal reaction 10h, obtains hydro-thermal reaction product; Hydro-thermal reaction product (without the need to through calcination process) being added concentration is (wherein the mass volume ratio of hydro-thermal reaction product and KOH solution is 250mg:130mL) in the KOH solution of 1M, stirring reaction 5h (rotating speed is 500r/min), centrifugal water is washed till neutrality, gained solid is placed in the dry 15h of vacuum drying chamber of 50 DEG C, obtains egg yolk structure tri-iron tetroxide/graphene composite material.When the composite material prepared by the present embodiment is used for lithium ion battery electrode material, electrical performance testing result as shown in Figure 7.
As seen from the figure, being electrode material with egg yolk structure tri-iron tetroxide/Graphene, battery specific capacity is high and stable.Thus can illustrative material Stability Analysis of Structures, chemical property is high.
Embodiment 3
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide
By improve Hummers legal system for graphene oxide, idiographic flow is as follows: under condition of ice bath, the concentrated sulfuric acid that 500mL mass fraction is 98% is added in the 1000mL flask filling 6g sodium nitrate and 6g graphite mixture, stir 0.7h (mixing speed is 800r/min), divide subsequently and progressively add 35g potassium permanganate 15 times, within controlling reaction temperature 20 DEG C, room temperature reaction time 17h subsequently, flask is transferred to oil bath heating, keep temperature 100 DEG C, add 400mL deionized water, reaction 12h, solution colour becomes brown color from black transitions; Add the hydrogen peroxide reaction 1h that 150mL mass percent is 35%, reduction residual oxide, adopt mass fraction to be that 10% hydrochloric acid solution washing and deionized water wash to pH=3.5, freeze-drying at-50 DEG C of temperature, obtains graphene oxide; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of surface modification ferroferric oxide nano granules
Get 80mg ferroferric oxide nano granules and 16mL deionized water is scattered in 20mL ethanol, ultrasonic disperse 30min (power 250W, frequency 50KHz), obtains dispersion liquid; Under 35 DEG C of water bath condition, in dispersion liquid, add 0.5mL tetraethoxysilane and 1mL mass percent is the ammonia spirit of 25%, reaction 8h; Then, add the 3-aminopropyl triethoxysilane of 0.1mL, stir 2h (mixing speed is 800r/min), be placed in water heating kettle in 100 DEG C of hydro-thermal reaction 24h, obtain hydro-thermal reaction product; Adopted by product deionized water to wash 4 times, in 75 DEG C of vacuumize 10h, obtain the ferroferric oxide nano granules of surface modification;
(3) synthesis of egg yolk structure tri-iron tetroxide/graphene composite material
The ferriferrous oxide particles getting the above-mentioned surface modification of 200mg is scattered in 40mL deionized water, obtains dispersion liquid; Under agitation (rotating speed 800r/min), add mass concentration be 10% dilute hydrochloric acid solution regulate dispersion liquid to pH=1, add the graphene oxide solution that 50mL concentration is 1mg/mL, stir 1h, obtain mixture; Subsequently mixture is placed in water heating kettle in 180 DEG C of hydro-thermal reaction 18h (without the need to through calcination process), obtains hydro-thermal reaction product; Hydro-thermal reaction product being added concentration is (wherein the mass volume ratio of hydro-thermal reaction product and KOH solution is 400mg:200mL) in the KOH solution of 1M, stirring reaction 12h (rotating speed 800r/min), centrifugal water is washed till neutrality, gained solid is placed in the dry 20h of vacuum drying chamber of 50 DEG C, obtains egg yolk structure tri-iron tetroxide/graphene composite material.When the composite material prepared by the present embodiment is used for lithium ion battery electrode material, electrical performance testing result as shown in Figure 8.
As seen from the figure, being electrode material with egg yolk structure tri-iron tetroxide/Graphene, battery specific capacity is high and stable.Thus can illustrative material Stability Analysis of Structures, chemical property is high.
Embodiment 4 (comparative example)
A preparation method for transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide: preparation method is identical with embodiment 1; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of silica surface modified ferroferric oxide nano granules
Ferroferric oxide nano granules and the 16mL deionized water of getting 80mg surface modification are scattered in 64mL ethanol, obtain dispersion liquid; Under 50 DEG C of water bath condition, in dispersion liquid, add 0.5mL tetraethoxysilane and 1mL mass percent is the ammonia spirit of 25%, reaction 5h, then be placed in water heating kettle in 100 DEG C of hydro-thermal reaction 24h, obtain hydro-thermal reaction product; Hydro-thermal reaction product is washed 3 times by deionized water, and 60 DEG C of vacuumize 10h, obtain silica surface modified ferroferric oxide nano granules;
(3) synthesis of tri-iron tetroxide/graphene composite material
The ferriferrous oxide particles getting the above-mentioned surface modification of 50mg is scattered in 20mL deionized water, obtains dispersion liquid; Under agitation (rotating speed is 1000r/min), add mass concentration be 5% dilute hydrochloric acid solution regulate dispersion liquid to pH=2.5, add the graphene oxide solution that 50mL concentration is 1mg/mL, stir 1h, obtain mixture; Subsequently mixture is placed in water heating kettle in 180 DEG C of hydro-thermal reaction 12h, obtains hydro-thermal reaction product; Hydro-thermal reaction product being added concentration is (wherein the mass volume ratio of hydro-thermal reaction product and KOH solution is 100mg:50mL) in the KOH solution of 5M, stirring reaction 10h (rotating speed is 1000r/min), centrifugal water is washed till neutrality, gained solid is placed in the dry 10h of vacuum drying chamber of 60 DEG C, obtains tri-iron tetroxide/graphene composite material.When the composite material prepared by the present embodiment is used for lithium ion battery electrode material, electrical performance testing result as shown in Figure 9.
As seen from the figure, the battery specific capacity that the tri-iron tetroxide/graphene composite material prepared with this example is electrode material is low and have capacity attenuation.The product prepared compared to embodiment 1 can be described thus, and tri-iron tetroxide/graphene composite material structural stability prepared by this embodiment is poor, and chemical property is low.
X-ray photoelectron spectroscopic analysis is utilized to show to the tri-iron tetroxide/graphene composite material of preparation, (iron atom number accounts for the percentage of total atom number to the Fe2O3 doping amount of the product prepared, implication is identical in the following embodiments for it) be 18.8%, oxygen content (oxygen atomicity accounts for the percentage of total atom number, and implication is identical in the following embodiments for it) is 47.8%.
Embodiment 6
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide: preparation method is identical with embodiment 1; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of silica surface modified di-iron trioxide nano particle: di-iron trioxide is replaced tri-iron tetroxide, and other conditions are identical with embodiment 1;
(3) the di-iron trioxide nanoparticulate dispersed of getting the above-mentioned surface modification of 50mg, in 20mL deionized water, obtains dispersion liquid; Under agitation (rotating speed is 1000r/min), add mass concentration be 5% dilute hydrochloric acid solution regulate dispersion liquid to pH=2.5, add the GO solution that 50mL concentration is 1mg/mL, stir 1h, obtain mixture; Subsequently mixture is placed in water heating kettle in 180 DEG C of hydro-thermal reaction 12h, obtains hydro-thermal reaction product; Hydro-thermal reaction product being added concentration is (wherein the mass volume ratio of hydro-thermal reaction product and KOH solution is 100mg:50mL) in the KOH solution of 5M, stirring reaction 10h (rotating speed is 1000r/min), centrifugal water is washed till neutrality, gained solid is placed in the abundant dry 10h of vacuum drying chamber of 60 DEG C, obtains the sesquioxide/graphene composite material of egg yolk structure.When the composite material prepared by the present embodiment is used for lithium ion battery electrode material, electrical performance testing result as shown in Figure 10.As seen from the figure, being electrode material with egg yolk structure sesquioxide/graphene composite material, battery specific capacity is high and stable.Thus can illustrative material Stability Analysis of Structures, chemical property is high.
Embodiment 7
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide: preparation method is identical with embodiment 1; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of silica surface modified manganese dioxide nano particle: manganese dioxide is replaced tri-iron tetroxide, and other conditions are identical with embodiment 1;
(3) the manganese dioxide nano Granular composite getting the above-mentioned surface modification of 50mg, in 20mL deionized water, obtains dispersion liquid; Under agitation (rotating speed is 1000r/min), add mass concentration be 5% dilute hydrochloric acid solution regulate dispersion liquid to pH=2.5, add the GO solution that 50mL concentration is 1mg/mL, stir 1h, obtain mixture; Subsequently gained mixture is placed in water heating kettle in 180 DEG C of hydro-thermal reaction 12h, obtains hydro-thermal reaction product; Hydro-thermal reaction product being added concentration is (wherein the mass volume ratio of hydro-thermal reaction product and KOH solution is 100mg:50mL) in the KOH solution of 5M, stirring reaction 10h (rotating speed is 1000r/min), centrifugal water is washed till neutrality, gained solid is placed in the dry 10h of vacuum drying chamber of 60 DEG C, obtains the manganese dioxide/graphene composite material of egg yolk structure.When the composite material prepared by the present embodiment is used for lithium ion battery electrode material, electrical performance testing result as shown in figure 11.As seen from the figure, being electrode material with egg yolk structure manganese dioxide/graphene composite material, battery specific capacity is high and stable.Thus can illustrative material Stability Analysis of Structures, chemical property is high.
Embodiment 8
A preparation method for egg yolk structure transition metal oxide/graphene composite material, specifically comprises the following steps:
(1) synthesis of graphene oxide: preparation method is identical with embodiment 1; Graphene oxide deionized water is made into graphene oxide solution, for subsequent use;
(2) synthesis of silica surface modified cobaltosic oxide nano particle: cobaltosic oxide is replaced tri-iron tetroxide, and other conditions are identical with embodiment 1;
(3) the cobaltosic oxide nano Granular composite getting the above-mentioned surface modification of 50mg, in 20mL deionized water, obtains dispersion liquid; Under agitation (rotating speed is 1000r/min), adding mass concentration is that the dilute hydrochloric acid solution adjustment dispersion liquid of 5% is to pH=2.5, add the GO solution (graphene oxide solution) that 50mL concentration is 1mg/mL, stir 1h, obtain mixture; Subsequently mixture is placed in water heating kettle in 180 DEG C of hydro-thermal reaction 12h, obtains hydro-thermal reaction product; Hydro-thermal reaction product being added concentration is (wherein the mass volume ratio of hydro-thermal reaction product and KOH solution is 100mg:50mL) in the KOH solution of 5M, stirring reaction 10h (rotating speed is 1000r/min), centrifugal water is washed till neutrality, gained solid is placed in the abundant dry 10h of vacuum drying chamber of 60 DEG C, obtains the cobalt oxide/graphene composite material of egg yolk structure.When the composite material prepared by the present embodiment is used for lithium ion battery electrode material, electrical performance testing result as shown in figure 12.As seen from the figure, being electrode material with egg yolk structure cobalt oxide/graphene composite material, battery specific capacity is high and stable.Thus can illustrative material Stability Analysis of Structures, chemical property is high.
Electrode preparation and battery assembling:
Getting active material, 2mg acetylene black and 1mg Kynoar prepared by 16mg embodiment joins in 1-METHYLPYRROLIDONE, stirs and forms paste liquid.Be coated on Copper Foil by gained liquid, 120 DEG C of vacuumize 12 hours, is then cut into disk.Gained pole piece is packaged into battery in the glove box of argon atmosphere, wherein uses Celgard2400 as barrier film, the LiPF of 1M
6as electrolyte, lithium sheet is as to electrode.The battery shell of CR2032 type carries out packaging and testing.
Each embodiment is only in order to illustrate technical scheme of the present invention above, is not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a preparation method for egg yolk structure transition metal oxide/graphene composite material, is characterized in that: specifically comprise the following steps:
(1) synthesis of surface modification transition metal oxide:
Transition metal oxide particle and deionized water are added in alcohol, ultrasonic disperse, obtain dispersion liquid; In dispersion liquid, add tetraethoxysilane and ammonia spirit, in 20 ~ 50 DEG C of reaction 3 ~ 8h, obtain product; Then, in product, add 3-aminopropyl triethoxysilane, stir and evenly mix, be placed in water heating kettle and carry out hydro-thermal reaction, washing, dry, obtain the transition metal oxide particle of surface modification;
(2) synthesis of egg yolk structure transition metal oxide/graphene composite material:
By the transition metal oxide Granular composite of surface modification in step (1) in deionized water, obtain dispersion liquid; Under the condition stirred, regulate pH to 1 ~ 4 of dispersion liquid, then add graphene oxide solution, stir and evenly mix, obtain mixture; Mixture is placed in water heating kettle and carries out hydro-thermal reaction, after having reacted, the product of hydro-thermal reaction is placed in strong base solution, stirring reaction, centrifuge washing, dry, obtain egg yolk structure transition metal oxide/graphene composite material.
2. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 1, is characterized in that: transition metal oxide particle described in step (1): deionized water: the amount ratio of alcohol is (50 ~ 100) mg:(10 ~ 200) mL:(20 ~ 120) mL;
Transition metal oxide in step (1): tetraethoxysilane: ammonia spirit: the amount ratio of 3-aminopropyl triethoxysilane is (50 ~ 100) mg:(0.1 ~ 1.0) mL:(0.5 ~ 5) mL:(0.05 ~ 0.2) mL;
Described transition metal oxide is more than one in iron oxide, tri-iron tetroxide, manganese dioxide or cobaltosic oxide; Step (1) described alcohol is methyl alcohol, ethanol or isopropyl alcohol.
3. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 1, is characterized in that: the transition metal oxide particle of surface modification described in step (2) and the mass volume ratio of deionized water are (10 ~ 200) mg:(10 ~ 40) mL;
Regulate the material of dispersion liquid pH to be dilute hydrochloric acid solution described in step (2), the mass percent concentration of described watery hydrochloric acid is 3 ~ 10%;
The mass ratio of the graphene oxide in the transition metal oxide of surface modification described in step (2) and graphene oxide solution is (0.2 ~ 5): 1;
The product of hydro-thermal reaction described in step (2) and the mass volume ratio of strong base solution are (100 ~ 400) mg:(50 ~ 200) mL; Described strong base solution is KOH solution, and the concentration of KOH solution is 1 ~ 5M.
4. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 1, it is characterized in that: described in step (1), hydrothermal temperature is 50 ~ 120 DEG C, the hydro-thermal reaction time is 10 ~ 30h; Described in step (2), the temperature of hydro-thermal reaction is 150 ~ 200 DEG C, and the hydro-thermal reaction time is 10 ~ 24h.
5. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 1, it is characterized in that: graphene oxide solution described in step (2) is scattered in deionized water by graphene oxide to obtain, the mass volume ratio of described graphene oxide and deionized water is (50 ~ 100) mg:(50 ~ 200) mL;
The preparation method of described graphene oxide is: under condition of ice bath, the concentrated sulfuric acid that mass percent is 95 ~ 98% is added in the container that sodium nitrate and graphite mixture is housed, with the rotating speed stirring reaction 0.5 ~ 1h of 500 ~ 1000r/min, progressively add potassium permanganate subsequently, within controlling reaction temperature 6 ~ 20 DEG C, room temperature reaction 10 ~ 24h subsequently, is warming up to 90 ~ 100 DEG C, add deionized water, reaction 2 ~ 24h; Add the hydrogen peroxide reduction reaction 1h that mass percent is 30 ~ 35% again, adopting mass percent to be 3 ~ 10% hydrochloric acid solution washings and deionized water washing is successively 3 ~ 4 to pH, and freeze-drying is for subsequent use.
6. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 5, is characterized in that: described graphite: sodium nitrate: the concentrated sulfuric acid: potassium permanganate: deionized water: the amount ratio of hydrogen peroxide is (1 ~ 6) g:(2 ~ 6) g:(100 ~ 500) mL:(15 ~ 35) g:(100 ~ 400) mL:(50 ~ 150) mL; The number of times that described potassium permanganate adds is 5 ~ 20 times.
7. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 1, is characterized in that: described in step (1), the mass percent concentration of ammonia spirit is 25%; Described in step (1), the power of ultrasonic disperse is 100 ~ 500W, and the frequency of ultrasonic disperse is 20 ~ 80KHz, and the time of ultrasonic disperse is 1-~ 30min;
Described in step (1), mixing speed is 500 ~ 2000r/min, and described mixing time is 1 ~ 3h;
Wash conditions described in step (1) is for adopting deionized water washing to neutral; Described baking temperature is 50 ~ 100 DEG C, and drying time is 6 ~ 10h.
8. the preparation method of egg yolk structure transition metal oxide/graphene composite material according to claim 1, is characterized in that: speed of agitator 500 ~ 2000r/min described in step (2), described in time of stirring and evenly mixing be 0.5 ~ 2h;
The time of stirring reaction described in step (2) is 5 ~ 12h, and described in step (2), the rotating speed of stirring reaction is 500 ~ 2000r/min;
The condition of washing described in step (2) is for adopting deionized water washing to neutral; Described in step (2), baking temperature is 50 ~ 100 DEG C, and drying time is 10 ~ 20h.
9. one kind prepares egg yolk structure transition metal oxide/graphene composite material by the preparation method described in any one of claim 1 ~ 8.
10. the application of yellow structural transition metal oxide/graphene composite material according to claim 9, is characterized in that: described egg yolk structure transition metal oxide/graphene composite material is used for field of lithium ion battery.
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