CN105140469B - A kind of egg yolk structure transition metal oxide/graphene composite material and preparation method and application - Google Patents
A kind of egg yolk structure transition metal oxide/graphene composite material and preparation method and application Download PDFInfo
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Abstract
The invention belongs to inorganic non-metallic material and electrochemical field, a kind of egg yolk structure transition metal oxide/graphene composite material and preparation method and application is disclosed.Methods described is：(1) transition metal oxide particle and deionized water are added in alcohol, ultrasonic disperse, add tetraethyl orthosilicate and ammonia spirit, 3~8h is reacted in 20~50 DEG C, 3 aminopropyl triethoxysilanes is added, stirs and evenly mixs, it is placed in water heating kettle and carries out hydro-thermal reaction, washing, is dried, and obtains the transition metal oxide of surface modification；(2) transition metal oxide that surface is modified is scattered in deionized water, under conditions of stirring, the pH of dispersion liquid is adjusted, graphene oxide solution is added, stirs and evenly mixs, it is placed in water heating kettle and carries out hydro-thermal reaction, it is placed in strong base solution, stirring reaction, centrifuge washing, dry, obtain egg yolk structure transition metal oxide/graphene composite material.Prepared material has preferable chemical property.
Description
Technical field
The invention belongs to inorganic non-metallic material and electrochemical field, it is related to a kind of graphene composite material, more particularly to
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
With being continuously increased for portable electric appts demand, high-energy and the lithium ion of high power density are designed and prepared
The research of battery is increasingly paid close attention to by scientific worker.The performance of lithium ion battery depends primarily on electrode used therein material
Performance.Transition metal oxide, due to its high theoretical capacity, is a kind of potential li-ion electrode materials.But due to transition gold
Category oxide material electric conductivity itself is relatively low, and Volume Changes are larger in lithium ion charge and discharge cycles in addition, and this is severely impacted
Transition metal oxide is used as the performance of lithium ion battery electrode material and the cyclical stability of battery.Research discovery, mistake
Cross state metal oxide and poor chemical property is typically exhibited out as the lithium ion battery of negative material.It is above-mentioned in order to solve
Problem, conventional method is in transition metal oxide Surface coating one layer of conductive material (e.g., carbon, polyaniline, graphene
Deng).The cladding of conductive material can effectively improve the electric conductivity of transition metal oxide electrode material, thus the lithium of gained
Ion battery often shows higher chemical property.Even if the cladding of conductive material can improve transition metal oxide
The performance of electrode material, the transition metal oxide closely coated easily causes deformation because of Volume Changes meeting, so as to cause electricity
Pole material comes off from current collector.Therefore, the close cladding of conductive material can not fundamentally solve transiting state metal
The problem of oxide electrode material is present.
Improving electrode material electric conductivity simultaneously, how to carry out conductive material and transition metal effectively coating and improving
The stability of electrode material turns into one of the problem of people need to solve.
The content of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the invention is to provide a kind of egg yolk structure transition
The preparation method of metal oxide/graphene composite material.
Another object of the present invention is to provide the egg yolk structure transiting metal oxidation prepared by above-mentioned preparation method
Thing/graphene composite material.
It is still another object of the present invention to provide answering for above-mentioned egg yolk structure transition metal oxide/graphene composite material
With.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of surface modified transition metal oxide
Transition metal oxide particle and deionized water are added in alcohol, ultrasonic disperse obtains dispersion liquid；Into dispersion liquid
Tetraethyl orthosilicate and ammonia spirit are added, 3~8h is reacted in 20~50 DEG C, obtains reaction product；Then, add into reaction product
Enter 3- aminopropyl triethoxysilanes, stir and evenly mix, be placed in water heating kettle and carry out hydro-thermal reaction, wash, dry, obtain to surface and change
The transition metal oxide particle of property；
(2) synthesis of egg yolk structure transition metal oxide/graphene composite material
The transition metal oxide particle that surface in step (1) is modified is scattered in deionized water, obtains dispersion liquid；
Under conditions of stirring, the pH of dispersion liquid is adjusted to 1~4, graphene oxide solution is added, stirs and evenly mixs, obtain mixture；Will
Mixture, which is placed in water heating kettle, carries out hydro-thermal reaction, the product of hydro-thermal reaction is placed in strong base solution after having reacted, stirring is anti-
Should, centrifuge washing is dried, obtains egg yolk structure transition metal oxide/graphene composite material.
Transition metal oxide in step (1)：Tetraethyl orthosilicate：Ammonia spirit：The matter of 3- aminopropyl triethoxysilanes
Amount volume ratio is (50~100) mg：(0.1~1.0) mL：(0.5~5) mL：(0.05~0.2) mL.Ammoniacal liquor described in step (1)
Mass percent concentration be 25%.
Transition metal oxide described in step (1) is in iron oxide, ferroso-ferric oxide, manganese dioxide or cobaltosic oxide
More than one；The alcohol is methanol, ethanol or isopropanol, 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.
Hydrothermal temperature is 50~120 DEG C in step (1), and the reaction time is 10~30h；It is ultrasonic described in step (1)
Scattered condition is 100~500W of power, 20~80KHz of frequency, and the time of ultrasonic disperse is 10~30min.
Mixing speed described in step (1) is 500~2000r/min, and the mixing time is 1~3h；Institute in step (1)
State wash conditions and be washed with deionized to adopt to neutrality；Drying temperature described in step (1) is 50~100 DEG C, drying time
For 6~10h.
The transition metal oxide that surface described in step (2) is modified：The mass ratio of graphene oxide is (0.2~5)：1；
The transition metal oxide particle and the mass volume ratio of deionized water that surface described in step (2) is modified are (10~200) mg：
(10~40) mL.
The material that dispersion liquid pH is adjusted described in step (2) is dilute hydrochloric acid solution, and the mass percent of the watery hydrochloric acid is dense
Spend for 3~10%.
500~the 2000r/min of rotating speed stirred and evenly mixed described in step (2), the time stirred and evenly mixed be 0.5~
2h；The time of stirring reaction described in step (2) is 5~12h, and the rotating speed of the stirring reaction is 500~2000r/min.
The temperature of hydro-thermal reaction described in step (2) is 150~200 DEG C, and the hydro-thermal reaction time is 10~24h；
The mass volume ratio of the product of hydro-thermal reaction and strong base solution described in step (2) is (100~400) mg：(50~
200)mL。
The condition washed described in step (2) is washed with deionized to neutrality to adopt；Drying temperature described in step (2)
For 50~100 DEG C, drying time is 10~20h；Strong base solution described in step (2) is 1~5M KOH solution.
Graphene oxide solution is that graphene oxide is scattered in deionized water to prepare described in step (2), its
Middle graphene oxide and the mass volume ratio of deionized water are (50~100) mg：(50~200) mL；The graphene oxide leads to
Cross what improved Hummers methods were prepared from.
The preparation method of the graphene oxide, is concretely comprised the following steps：
Under condition of ice bath, it is 95~98% that mass percent is added into the container equipped with sodium nitrate and graphite mixture
The concentrated sulfuric acid, 0.5~1h of stirring reaction (rotating speed of stirring is 500~1000r/min), is then gradually added potassium permanganate (number of times
For 5~20 times), within 6~20 DEG C of controlling reaction temperature, then room temperature reaction 10~24h of time, is warming up to 90~100 DEG C,
Deionized water is added, 2~24h is reacted；It is 30~35% hydrogen peroxide reduction residual oxide 1h to add mass percent, successively
It is that the washing of 3~10% hydrochloric acid solutions and deionized water are washed to faintly acid (pH is 3~4) to use mass percent, is freezed standby.
Described graphite, described sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the mistake
The mass volume ratio of hydrogen oxide 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.
Oxygen atomicity content accounts for the 20~50% of total atom number in the graphene oxide.
A kind of egg yolk structure transition metal oxide/graphene composite material is prepared by above-mentioned preparation method.
The egg yolk structure transition metal oxide/graphene composite material is used for field of lithium ion battery.
Transition metal oxide is modified by the present invention by surface makes it positively charged in an acidic solution, and graphite oxide
Alkene solution surface in weakly acidic solution is negatively charged, and two kinds of materials are combined by electrostatic attraction, are then gone by KOH solution
Except the SiO of transition metal oxide particle surface2Layer, has obtained transition metal oxide/graphene composite wood of egg yolk structure
Material.
The present invention forms a kind of material of egg yolk structure among transition metal oxide to be placed in the shell of conductive material, should
Continuous conductive material shell can effectively improve the electric conductivity of electrode in material, the space between transition metal oxide and shell
The Volume Changes that can be transition metal oxide in charge and discharge cycles provide space；The present invention regard graphene as yolk knot
The shell of structure, can more effectively improve transiting state metal oxide as the performance of lithium ion battery negative material.Test knot
Electrode material of the fruit display with such a structure has an excellent electro-chemical activity, including high charge/discharge capacity, good circulation
Stability and stable high rate performance.Such a electrode material is in terms of lithium ion battery energy density and power density is improved
With great potentiality.
The invention has the advantages that and beneficial effect：
The technique of the present invention is simple, and raw material is cheap, and egg yolk structure transition metal oxide/stone prepared by such a method
Black alkene composite, the transition metal oxide material prepared compared to other methods is high with chemical property, and structure is steady
It is fixed, the advantages of specific surface area is big.
Brief description of the drawings
Fig. 1 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 13O4@void@RGO)
Scanning electron microscope (SEM) photograph be SEM figure；
Fig. 2 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 13O4@void@RGO)
Transmission electron microscope picture be TEM figure；
Fig. 3 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 13O4@void@RGO)
X-ray photoelectron energy spectrum diagram；
Fig. 4 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 13O4@void@RGO)
Infrared spectrum；
Fig. 5 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 13O4@void@RGO)
It is cycle performance curve for the performance of lithium ion battery test chart of electrode；
Fig. 6 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 13O4@void@RGO)
For the lithium ion battery coulombic efficiency figure of electrode；
Fig. 7 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 23O4@void@RGO)
Electric performance test curve is cycle performance curve during for lithium ion battery electrode material；
Fig. 8 is egg yolk structure ferroso-ferric oxide/graphene composite material (i.e. Fe prepared by embodiment 33O4@void@RGO)
Electric performance test curve is cycle performance curve during for lithium ion battery electrode material；
Electrical property is surveyed when Fig. 9 is used for lithium ion battery electrode material for the composite prepared by embodiment 1 and embodiment 4
It is cycle performance curve to try curve；
Figure 10 is egg yolk structure sesquioxide/graphene composite material (i.e. Fe prepared by embodiment 62O3@void@RGO)
Electric performance test curve is cycle performance curve during for lithium ion battery electrode material；
Figure 11 is egg yolk structure manganese dioxide/graphene composite material (i.e. MnO prepared by embodiment 72@void@rGO) use
Electric performance test curve is cycle performance curve when lithium ion battery electrode material；
Figure 12 is egg yolk structure cobalt oxide/graphene composite (i.e. Co prepared by embodiment 83O4@void@RGO)
Electric performance test curve is cycle performance curve during for lithium ion battery electrode material.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared by improved Hummers methods, idiographic flow is as follows：Under condition of ice bath, to filling 5g nitre
The 300mL concentrated sulfuric acids (mass percent concentration is 98%) are added in the 1000mL flasks of sour sodium and 2g graphite mixture, stirring is anti-
Answer 1h (rotating speed of stirring be 1000r/min), be then gradually added 30g potassium permanganate points for 10 times, 10 DEG C of controlling reaction temperature with
It is interior, 24h is then reacted at room temperature, then flask is transferred to oil bath heating, 98 DEG C of keeping temperature adds 300mL deionized waters, reaction
24h, solution colour is from black transitions into brown color；The hydrogen peroxide that 100mL mass percents are 35% is added, 1h, reduction is reacted
Residual oxide, it is that the washing of 5% hydrochloric acid solution and deionized water are washed to faintly acid (pH is 4) to use mass percent concentration,
It is lyophilized in -50 DEG C of temperature, obtain graphene oxide；Graphene oxide is made into graphene oxide solution with deionized water, it is standby；
(2) synthesis of surface improved ferroferric oxide nano particle
80mg ferroferric oxide nano granules and 16mL deionized waters is taken to be scattered in 64mL ethanol, ultrasonic disperse 30min
(power 500W, frequency 80KHz), obtains dispersion liquid；Under 50 DEG C of water bath conditions, the positive silicic acid second of 0.5mL is added into dispersion liquid
Ester and 1mL mass percents are 25% ammonia spirit, react 6h；Then, 0.1mL 3- aminopropyl triethoxysilanes are added, with
1000r/min rotating speed stirring 3h, is placed in water heating kettle, in 100 DEG C of hydro-thermal reaction 24h, then is washed with deionized 5 times, in
60 DEG C of vacuum drying 10h, obtain the ferroferric oxide nano granules of surface modification；
(3) synthesis of egg yolk structure ferroso-ferric oxide/graphene composite material
The ferriferrous oxide particles for taking the above-mentioned surfaces of 50mg to be modified are scattered in 20mL deionized waters, obtain dispersion liquid；
Under stirring condition (rotating speed of stirring be 1000r/min), dilute hydrochloric acid solution is added into dispersion liquid, and (mass percent concentration is
5%) regulation adds the graphene oxide solution that 50mL concentration is 1mg/mL, stirs 30min, obtain mixture to pH=2.5；
Then mixture is placed in water heating kettle, in 180 DEG C of hydro-thermal reaction 12h, the product of hydro-thermal reaction is obtained；100mg hydro-thermals is anti-
It is stirring reaction 10h in 5M KOH solution that the product answered, which adds 50mL concentration, and centrifugation is washed to neutrality, then in 60 DEG C of vacuum
10h is dried in drying box, egg yolk structure ferroso-ferric oxide/graphene composite material is obtained.The structural characterization of the composite is such as
Shown in Fig. 1~4；The composite as lithium ion battery electrode material when, electrochemical property test is as shown in Fig. 5,6,9.
Fig. 1 schemes for the SEM of egg yolk structure ferroso-ferric oxide/graphene composite material manufactured in the present embodiment, and Fig. 2 is this reality
Apply the TEM figures of egg yolk structure ferroso-ferric oxide/graphene composite material of example preparation.It can be seen that the present embodiment system
Standby ferroso-ferric oxide/graphene composite material has egg yolk structure.
Fig. 3 is the x-ray photoelectron power spectrum of egg yolk structure ferroso-ferric oxide/graphene composite material manufactured in the present embodiment
Figure.It can be seen that, contain in composite manufactured in the present embodiment and comprise only carbon, oxygen and ferro element, be practically free of other miscellaneous
Matter.The percentage contents of each element atomicity can be drawn by the conversion to peak intensity, wherein oxygen atomicity accounts for total atom
Several 47.8%, iron atom number accounts for the 18.8% of total atom number, and carbon number accounts for the 33.4% of total atom number.Fig. 4 is this implementation
The infrared spectrum of egg yolk structure ferroso-ferric oxide/graphene composite material prepared by example.
Fig. 5 and Fig. 6 are respectively that the circulation of egg yolk structure ferroso-ferric oxide/graphene composite material prepared by embodiment 1 is bent
Line and coulombic efficiency curve.As shown in Figure 5, electric specific capacity is by initial 1900mAhg-1Drop to 1280mAhg-1And protect
It is fixed to keep steady, and after the circulation of 250 circles, prepared battery charging and discharging specific capacity, which remains unchanged, is maintained at 1273.4mAhg-1.By scheming
6 understand, coulombic efficiency then maintains more than 95% by initial 67% rapid rising.
Embodiment 2
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared by improved Hummers methods, idiographic flow is as follows：Under condition of ice bath, to filling 1g nitre
The concentrated sulfuric acid that 100mL mass fractions are 98%, stirring reaction (stirring are added in the 1000mL flasks of sour sodium and 3g graphite mixture
Speed is 500r/min, and mixing time is 0.5h), then progressively add 15g potassium permanganate points for 5 times, 6 DEG C of controlling reaction temperature with
Interior, then room temperature reaction time 10h, oil bath heating is transferred to by flask, and 90 DEG C of keeping temperature adds 100mL deionized waters, instead
Answer 2h, solution colour is from black transitions into brown color；The hydrogen peroxide that 50mL mass percent concentrations are 35% is added, 1h is reacted,
Residual oxide is reduced, it is that the washing of 3% hydrochloric acid solution and deionized water are washed to pH=3 to use mass fraction, in -50 DEG C of temperature
Degree is lower lyophilized, obtains graphene oxide；Graphene oxide is made into graphene oxide solution with deionized water, it is standby；
(2) synthesis of surface improved ferroferric oxide nano particle
80mg ferroferric oxide nano granules and 16mL deionized waters is taken to be scattered in 120mL ethanol, ultrasonic disperse 20min
(power 100W, frequency 20KHz), obtains dispersion liquid；Under 20 DEG C of water bath conditions, the positive silicic acid second of 0.5mL is added into dispersion liquid
Ester and the ammonia spirit that 1mL mass percents are 25%, react 3h；Then, 0.1mL 3- aminopropyl-triethoxy silicon is added
Alkane, stirring 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 production
Thing；Product is adopted and is washed with deionized 3 times, 10h is dried in vacuo in 50 DEG C, the ferriferrous oxide nano of surface modification is obtained
Grain；
(3) synthesis of egg yolk structure ferroso-ferric oxide/graphene composite material
The ferriferrous oxide particles for taking the above-mentioned surfaces of 10mg to be modified are scattered in 10mL deionized waters, obtain dispersion liquid；
Under stirring condition (rotating speed is 500r/min), add mass concentration and adjust dispersion liquid to pH=4 for 3% dilute hydrochloric acid solution, plus
Enter the graphene oxide solution that 50mL concentration is 1mg/mL, stir 0.5h, obtain mixture；Mixture is then placed in water heating kettle
In in 150 DEG C of hydro-thermal reaction 10h, obtain hydro-thermal reaction product；Hydro-thermal reaction product (needing not move through calcination processing) is added dense
Spend in the KOH solution for 1M that (wherein hydro-thermal reaction product and the mass volume ratio of KOH solution are 250mg：130mL), stir anti-
5h (rotating speed is 500r/min) is answered, centrifugation is washed to neutrality, and gained solid is placed in 50 DEG C of vacuum drying chamber and dries 15h,
Obtain egg yolk structure ferroso-ferric oxide/graphene composite material.Composite manufactured in the present embodiment is used for lithium ion battery
During electrode material, electrical performance testing result is as shown in Figure 7.
As seen from the figure, it is high and stably as the battery specific capacity of electrode material using egg yolk structure ferroso-ferric oxide/graphene.By
This explainable material structure is stable, and chemical property is high.
Embodiment 3
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared by improved Hummers methods, idiographic flow is as follows：Under condition of ice bath, to filling 6g nitre
The concentrated sulfuric acid that 500mL mass fractions are 98%, stirring 0.7h (stirrings are added in the 1000mL flasks of sour sodium and 6g graphite mixture
Speed is 800r/min), then divide 15 times and progressively add within 35g potassium permanganate, 20 DEG C of controlling reaction temperature, subsequent room temperature is anti-
17h between seasonable, oil bath heating is transferred to by flask, and 100 DEG C of keeping temperature adds 400mL deionized waters, reacts 12h, solution face
Color is from black transitions into brown color；It is 35% hydrogen peroxide reaction 1h to add 150mL mass percents, reduces residual oxide,
It is that the washing of 10% hydrochloric acid solution and deionized water are washed to pH=3.5 to use mass fraction, freezes, obtains at a temperature of -50 DEG C
To graphene oxide；Graphene oxide is made into graphene oxide solution with deionized water, it is standby；
(2) synthesis of surface improved ferroferric oxide nano particle
80mg ferroferric oxide nano granules and 16mL deionized waters is taken to be scattered in 20mL ethanol, ultrasonic disperse 30min
(power 250W, frequency 50KHz), obtains dispersion liquid；Under 35 DEG C of water bath conditions, the positive silicic acid second of 0.5mL is added into dispersion liquid
Ester and the ammonia spirit that 1mL mass percents are 25%, react 8h；Then, 0.1mL 3- aminopropyl-triethoxy silicon is added
Alkane, stirring 2h (mixing speed is 800r/min), is placed in water heating kettle in 100 DEG C of hydro-thermal reaction 24h, obtains hydro-thermal reaction production
Thing；Product is adopted and is washed with deionized 4 times, 10h is dried in vacuo in 75 DEG C, the ferriferrous oxide nano of surface modification is obtained
Grain；
(3) synthesis of egg yolk structure ferroso-ferric oxide/graphene composite material
The ferriferrous oxide particles for taking the above-mentioned surfaces of 200mg to be modified are scattered in 40mL deionized waters, obtain dispersion liquid；
Under stirring condition (rotating speed 800r/min), add mass concentration and adjust dispersion liquid to pH=1 for 10% dilute hydrochloric acid solution, add
50mL concentration is 1mg/mL graphene oxide solution, stirs 1h, obtains mixture；Then by mixture be placed in water heating kettle in
180 DEG C of hydro-thermal reaction 18h (needing not move through calcination processing), obtain hydro-thermal reaction product；It is by hydro-thermal reaction product addition concentration
(wherein hydro-thermal reaction product and the mass volume ratio of KOH solution are 400mg in 1M KOH solution：200mL), stirring reaction 12h
(rotating speed 800r/min), centrifugation is washed to neutrality, and gained solid is placed in 50 DEG C of vacuum drying chamber and dries 20h, egg is obtained
Yellow structure ferroso-ferric oxide/graphene composite material.Composite manufactured in the present embodiment is used for lithium ion cell electrode material
During material, electrical performance testing result is as shown in Figure 8.
As seen from the figure, it is high and stably as the battery specific capacity of electrode material using egg yolk structure ferroso-ferric oxide/graphene.By
This explainable material structure is stable, and chemical property is high.
Embodiment 4 (comparative example)
A kind of preparation method of transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide：Preparation method is same as Example 1；Graphene oxide is made into deionized water
Graphene oxide solution, it is standby；
(2) synthesis of silica surface modified ferroferric oxide nano granules
Take the ferroferric oxide nano granules and 16mL deionized waters of the modification of 80mg surfaces to be scattered in 64mL ethanol, obtain
Dispersion liquid；Under 50 DEG C of water bath conditions, it is 25% ammonia that 0.5mL tetraethyl orthosilicates and 1mL mass percents are added into dispersion liquid
The aqueous solution, reacts 5h, then is placed in water heating kettle in 100 DEG C of hydro-thermal reaction 24h, obtains hydro-thermal reaction product；Hydro-thermal reaction is produced
Thing is washed 3 times by deionized water, and 60 DEG C of vacuum drying 10h obtain silica surface modified ferriferrous oxide nano
Grain；
(3) synthesis of ferroso-ferric oxide/graphene composite material
The ferriferrous oxide particles for taking the above-mentioned surfaces of 50mg to be modified are scattered in 20mL deionized waters, obtain dispersion liquid；
Under stirring condition (rotating speed is 1000r/min), add mass concentration and adjust dispersion liquid to pH=2.5 for 5% dilute hydrochloric acid solution,
The graphene oxide solution that 50mL concentration is 1mg/mL is added, 1h is stirred, obtains mixture；Mixture is then placed in water heating kettle
In in 180 DEG C of hydro-thermal reaction 12h, obtain hydro-thermal reaction product；Hydro-thermal reaction product is added into concentration in 5M KOH solution
(wherein hydro-thermal reaction product and the mass volume ratio of KOH solution are 100mg：50mL), (rotating speed is 1000r/ to stirring reaction 10h
Min), centrifugation be washed to neutrality, by gained solid be placed in 60 DEG C of vacuum drying chamber dry 10h, produce ferroso-ferric oxide/
Graphene composite material.When composite manufactured in the present embodiment is used for into lithium ion battery electrode material, electrical performance testing
As a result it is as shown in Figure 9.
As seen from the figure, using ferroso-ferric oxide/graphene composite material of this example preparation as the battery specific volume of electrode material
Amount is low and has capacity attenuation.Thus can be explained compared to embodiment 1 prepare product, this embodiment prepare ferroso-ferric oxide/
Graphene composite material structural stability is poor, and chemical property is low.
Ferroso-ferric oxide/graphene composite material of preparation is shown using X-ray photoelectron spectroscopic analysis, prepared
Product Fe2O3 doping amount (iron atom number accounts for the percentage of total atom number, its in the following embodiments implication it is identical) be
18.8%, oxygen content (oxygen atomicity accounts for the percentage of total atom number, its in the following embodiments implication it is identical) be 47.8%.
Embodiment 6
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide：Preparation method is same as Example 1；Graphene oxide is made into deionized water
Graphene oxide solution, it is standby；
(2) synthesis of silica surface modified di-iron trioxide nano particle：Di-iron trioxide is replaced into four oxidations three
Iron, other conditions are same as Example 1；
(3) the di-iron trioxide nano particle for taking the above-mentioned surfaces of 50mg to be modified is scattered in 20mL deionized waters, is divided
Dispersion liquid；Under agitation (rotating speed is 1000r/min), add mass concentration for 5% dilute hydrochloric acid solution adjust dispersion liquid to
PH=2.5, adds the GO solution that 50mL concentration is 1mg/mL, stirs 1h, obtain mixture；Mixture is then placed in water heating kettle
In in 180 DEG C of hydro-thermal reaction 12h, obtain hydro-thermal reaction product；Hydro-thermal reaction product is added into concentration in 5M KOH solution
(wherein hydro-thermal reaction product and the mass volume ratio of KOH solution are 100mg：50mL), (rotating speed is 1000r/ to stirring reaction 10h
Min), centrifugation is washed to neutrality, and gained solid is placed in 60 DEG C of vacuum drying chamber and fully dries 10h, egg yolk structure is obtained
Sesquioxide/graphene composite material.When composite manufactured in the present embodiment is used for into lithium ion battery electrode material,
Electrical performance testing result is as shown in Figure 10.As seen from the figure, using egg yolk structure sesquioxide/graphene composite material as electrode
The battery specific capacity of material is high and stably.Thus material structure can be explained stable, chemical property height.
Embodiment 7
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide：Preparation method is same as Example 1；Graphene oxide is made into deionized water
Graphene oxide solution, it is standby；
(2) synthesis of silica surface modified manganese dioxide nano particle：Manganese dioxide is replaced into ferroso-ferric oxide, its
His condition is same as Example 1；
(3) the manganese dioxide nano particle for taking the above-mentioned surfaces of 50mg to be modified is scattered in 20mL deionized waters, is disperseed
Liquid；Under agitation (rotating speed is 1000r/min), add mass concentration and adjust dispersion liquid to pH for 5% dilute hydrochloric acid solution
=2.5, the GO solution that 50mL concentration is 1mg/mL is added, 1h is stirred, obtains mixture；Gained mixture is then placed in hydro-thermal
In 180 DEG C of hydro-thermal reaction 12h in kettle, hydro-thermal reaction product is obtained；Hydro-thermal reaction product is added into concentration in 5M KOH solution
(wherein hydro-thermal reaction product and the mass volume ratio of KOH solution are 100mg：50mL), (rotating speed is 1000r/ to stirring reaction 10h
Min), centrifugation is washed to neutrality, and gained solid is placed in 60 DEG C of vacuum drying chamber and dries 10h, the two of egg yolk structure are produced
Manganese oxide/graphene composite material.When composite manufactured in the present embodiment is used for into lithium ion battery electrode material, electrical property
Energy test result is as shown in figure 11.As seen from the figure, using egg yolk structure manganese dioxide/graphene composite material as the electricity of electrode material
Pond specific capacity is high and stably.Thus material structure can be explained stable, chemical property height.
Embodiment 8
A kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, specifically includes following steps：
(1) synthesis of graphene oxide：Preparation method is same as Example 1；Graphene oxide is made into deionized water
Graphene oxide solution, it is standby；
(2) synthesis of silica surface modified cobaltosic oxide nano particle：Cobaltosic oxide is replaced into four oxidations three
Iron, other conditions are same as Example 1；
(3) the cobaltosic oxide nano particle for taking the above-mentioned surfaces of 50mg to be modified is scattered in 20mL deionized waters, is divided
Dispersion liquid；Under agitation (rotating speed is 1000r/min), add mass concentration for 5% dilute hydrochloric acid solution adjust dispersion liquid to
PH=2.5, adds the GO solution (graphene oxide solution) that 50mL concentration is 1mg/mL, stirs 1h, obtain mixture；Then will
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 is added into concentration
For (wherein hydro-thermal reaction product and the mass volume ratio of KOH solution are 100mg in 5M KOH solution：50mL), stirring reaction
10h (rotating speed is 1000r/min), centrifugation is washed to neutrality, and gained solid is placed in 60 DEG C of vacuum drying chamber and fully dried
10h, produces the cobalt oxide/graphene composite of egg yolk structure.By composite manufactured in the present embodiment be used for lithium from
During sub- battery electrode material, electrical performance testing result is as shown in figure 12.As seen from the figure, with egg yolk structure cobaltosic oxide/stone
Black alkene composite is high and stably for the battery specific capacity of electrode material.Thus material structure can be explained stable, chemical property
It is high.
Electrode is prepared and battery assembling：
Active material, 2mg acetylene blacks and the 1mg Kynoar for taking 16mg embodiments to prepare are added to N- crassitudes
In ketone, stirring forms paste liquid.Gained liquid is coated on copper foil, 120 DEG C are dried in vacuo 12 hours, are then cut into circle
Piece.Gained pole piece is packaged into battery in the glove box of argon atmosphere, wherein with Celgard 2400 as barrier film, 1M's
LiPF6As electrolyte, lithium piece is as to electrode.The battery shell of the types of CR 2032 is packaged test.
Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；Although with reference to foregoing each reality
Example is applied the present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each
Technical scheme described in embodiment is modified, or carries out equivalent substitution to which part or all technical characteristic；And
These modifications are replaced, and the essence of appropriate technical solution is departed from the scope of various embodiments of the present invention technical scheme.
Claims (9)
1. a kind of preparation method of egg yolk structure transition metal oxide/graphene composite material, it is characterised in that：Specifically include
Following steps：
(1) synthesis of surface modified transition metal oxide：
Transition metal oxide particle and deionized water are added in alcohol, ultrasonic disperse obtains dispersion liquid；Added into dispersion liquid
Tetraethyl orthosilicate and ammonia spirit, react 3~8h in 20~50 DEG C, obtain reaction product；Then, 3- is added into reaction product
Aminopropyl triethoxysilane, is stirred and evenly mixed, and is placed in water heating kettle and is carried out hydro-thermal reaction, is washed, and is dried, and obtains surface modification
Transition metal oxide particle；
(2) synthesis of egg yolk structure transition metal oxide/graphene composite material：
The transition metal oxide particle that surface in step (1) is modified is scattered in deionized water, obtains dispersion liquid；In stirring
Under conditions of, the pH of dispersion liquid is adjusted to 1~4, is added graphene oxide solution, is stirred and evenly mixed, obtains mixture；Will mixing
Thing, which is placed in water heating kettle, carries out hydro-thermal reaction, the product of hydro-thermal reaction is placed in strong base solution after having reacted, stirring reaction, from
The heart is washed, and is dried, is obtained egg yolk structure transition metal oxide/graphene composite material；
Hydrothermal temperature described in step (1) is 50~120 DEG C, and 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.
2. the preparation method of egg yolk structure transition metal oxide/graphene composite material, its feature according to claim 1
It is：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)：Tetraethyl orthosilicate：Ammonia spirit：The amount ratio of 3- aminopropyl triethoxysilanes
For (50~100) mg：(0.1~1.0) mL：(0.5~5) mL：(0.05~0.2) mL；
The transition metal oxide is one or more of iron oxide, ferroso-ferric oxide, manganese dioxide or cobaltosic oxide；Step
Suddenly (1) described alcohol is methanol, ethanol or isopropanol.
3. the preparation method of egg yolk structure transition metal oxide/graphene composite material, its feature according to claim 1
It is：Surface described in step (2) be modified transition metal oxide particle and deionized water mass volume ratio for (10~
200)mg：(10~40) mL；
The material that dispersion liquid pH is adjusted described in step (2) is dilute hydrochloric acid solution, and the mass percent concentration of the watery hydrochloric acid is 3
~10%；
The quality of graphene oxide in transition metal oxide and graphene oxide solution that surface described in step (2) is modified
Than for (0.2~5)：1；
The mass volume ratio of the product of hydro-thermal reaction and strong base solution described in step (2) is (100~400) mg：(50~200)
mL；The 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, its feature according to claim 1
It is：Graphene oxide solution is that graphene oxide is scattered in deionized water to obtain described in step (2), the oxidation stone
Black alkene and the mass volume ratio of deionized water are (50~100) mg：(50~200) mL；
The preparation method of the graphene oxide is：Under condition of ice bath, add into the container equipped with sodium nitrate and graphite mixture
Enter the concentrated sulfuric acid that mass percent is 95~98%, with 500~1000r/min rotating speed 0.5~1h of stirring reaction, then progressively
Potassium permanganate is added, within 6~20 DEG C of controlling reaction temperature, 10~24h is then reacted at room temperature, is warming up to 90~100 DEG C, plus
Enter deionized water, react 2~24h；The hydrogen peroxide reduction reaction 1h that mass percent is 30~35% is added, successively using matter
Amount percentage is that to wash to pH be 3~4 for the washing of 3~10% hydrochloric acid solutions and deionized water, is freezed, standby.
5. the preparation method of egg yolk structure transition metal oxide/graphene composite material, its feature according to claim 4
It is：The 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 the potassium permanganate is added for 5~
20 times.
6. the preparation method of egg yolk structure transition metal oxide/graphene composite material, its feature according to claim 1
It is：The mass percent concentration of ammonia spirit described in step (1) is 25%；The power of ultrasonic disperse described in step (1)
For 100~500W, the frequency of ultrasonic disperse is 20~80KHz, and the time of ultrasonic disperse is 1-~30min；
Mixing speed described in step (1) is 500~2000r/min, and the mixing time is 1~3h；
Wash conditions described in step (1) are washed with deionized to neutrality to adopt；The drying temperature is 50~100 DEG C, is done
The dry time is 6~10h.
7. the preparation method of egg yolk structure transition metal oxide/graphene composite material, its feature according to claim 1
It is：500~2000r/min of speed of agitator described in step (2), the time stirred and evenly mixed is 0.5~2h；
The time of stirring reaction described in step (2) be 5~12h, the rotating speed of stirring reaction described in step (2) be 500~
2000r/min；
The condition washed described in step (2) is washed with deionized to neutrality to adopt；Drying temperature described in step (2) is 50
~100 DEG C, drying time is 10~20h.
8. a kind of preparation method as described in any one of claim 1~7 prepares egg yolk structure transition metal oxide/stone
Black alkene composite.
9. the application of yellow structural transition metal oxide/graphene composite material according to claim 8, it is characterised in that：
The egg yolk structure transition metal oxide/graphene composite material is used for field of lithium ion battery.
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| CN105140469B (en) * | 2015-06-30 | 2017-10-20 | 华南理工大学 | A kind of egg yolk structure transition metal oxide/graphene composite material and preparation method and application |
| CN105964256B (en) * | 2016-05-12 | 2018-07-13 | 广东石油化工学院 | A kind of preparation method of hud typed ferroso-ferric oxide/graphene oxide composite nano catalyst |
| CN106252617A (en) * | 2016-08-03 | 2016-12-21 | 深圳市微纳集成电路与***应用研究院 | A kind of composite and preparation method thereof |
| CN106564892B (en) * | 2016-11-04 | 2018-08-21 | 华中科技大学 | A method of intrinsic modified introducing Lacking oxygen is carried out to transition metal oxide |
| CN106848338B (en) * | 2017-01-16 | 2019-12-13 | 济南大学 | preparation method of graphene-supported Ni-based oxide catalyst |
| CN107200361A (en) * | 2017-06-29 | 2017-09-26 | 济南大学 | A kind of rGO/Fe2O3The preparation method of nano composite material |
| CN107628591B (en) * | 2017-10-12 | 2019-07-09 | 北京科技大学 | A kind of yolk-shell structure Co9Se8The preparation method of nano particle |
| US11420258B2 (en) * | 2018-05-11 | 2022-08-23 | Lg Electronics Inc. | Method for manufacture of transition metal oxide fine particles |
| CN108722413B (en) * | 2018-05-15 | 2020-10-30 | 江苏理工学院 | Preparation method and application of yolk-eggshell structure graphitized carbon-coated transition metal material |
| CN110034294A (en) * | 2019-05-17 | 2019-07-19 | 浙江卡波恩新材料有限公司 | A kind of preparation method of the carbon coating graphene as lithium cell cathode material |
| CN110391052B (en) * | 2019-06-27 | 2021-01-08 | 惠科股份有限公司 | Flexible composite conductive film, preparation method thereof and display panel |
| CN112582183B (en) * | 2020-02-18 | 2022-04-08 | 宿州学院 | Fe3O4Composite material of/Ni/N-RGO solar cell efficient electrode and preparation method thereof |
| CN111790387B (en) * | 2020-08-07 | 2021-11-26 | 福州大学 | Transition metal hydroxide-graphene composite material for efficient photocatalytic reduction of carbon dioxide and preparation method and application thereof |
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