CN103346301A - Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material - Google Patents
Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material Download PDFInfo
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- CN103346301A CN103346301A CN2013102564964A CN201310256496A CN103346301A CN 103346301 A CN103346301 A CN 103346301A CN 2013102564964 A CN2013102564964 A CN 2013102564964A CN 201310256496 A CN201310256496 A CN 201310256496A CN 103346301 A CN103346301 A CN 103346301A
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Abstract
The invention discloses a preparation method and application of a three-dimensional-structure graphene-base metal oxide composite material. According to the preparation method disclosed by the invention, the three-dimensional-structure graphene-base metal oxide composite material is prepared by a hydrothermal freeze-drying method by using single-layer carbon-atom-structure graphene as a carrier and some high molecular polymers as an auxiliary crosslinking agent. The three-dimensional aerogel obtained by the method has high metal oxide carrying capacity. The electrochemical test proves that the three-dimensional aerogel graphene-base metal oxide composite material obtained by the preparation method has excellent loop stability and rate capability. The experiment proves that the discharge capacity of the tin dioxide material can reach 1050 mAhg<-1> under the charging/discharging current of 100 mAg<-1>, and the discharge capacity of the titanium oxide material can reach 150 mAhg<-1> under the charging/discharging current of 50 mAg<-1>.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of graphene-based metal oxide composite of three-dimensional structure, belong to material science and technical field of electrochemistry.
Background technology
Along with highlighting day by day of energy and environment problem, the new forms of energy industry has obtained increasing attention.Hybrid vehicle and electric automobile industry development are rapid, and lithium ion battery is widely used as wherein important energy storage device.Lithium ion battery has the energy density height, and some good performances such as good cycle also are considered to one of the most effective energy storage mode at present, and therefore, further improving its energy density and cycle performance also is difficult point and the focus of studying instantly.
The negative pole of lithium ion battery is the important component part of battery, and its structure and performance directly influence capacity and the cycle performance of lithium ion battery.Commercial at present lithium ion battery negative material is based on graphite, and the graphite cost is low, and wide material sources are suitable for commercialization; But its capacity is lower, and theoretical capacity only is 372mAhg
-1, be restricted when in the field that needs high-energy output, using.
Metal oxide such as Fe
3O
4, SnO
2Have very high specific capacity Deng as lithium ion battery negative material, its specific capacity is up to 700-1000mAhg
-1But most of metal oxide, especially SnO
2Change in volume is up to 200-300% in charge and discharge process as electrode material, and this change in volume can cause the efflorescence of electrode, causes opening circuit of active material and collector.All there is capacity attenuation problem rapidly when therefore, most of metal oxides are as lithium ion cell electrode.TiO
2Because having higher embedding lithium is 1.7V with the voltage that moves lithium, can effectively alleviate the forming process of SEI film.But TiO
2The conductivity of itself is relatively poor, so for the bulk effect that improves metal oxide and raising conductivity, be a heat subject studying lithium ion battery negative material this year.
At present, for expanding the application of metal oxide in lithium ion battery negative material, researchers have carried out deep research at these problems that metal oxide exists, for example electrode material is carried out modification, comprise the preparation of coating, doping, compound and nano material, improve the performance of electrode material by these methods, particularly carry out the compound of nanoscale at metal oxide and material with carbon element, prepare the focus that novel nanostructure aspect has become present research.
Material with carbon element has its unique premium properties: stability, good conductivity, light weight; Make its carrier that can be used as the good metal oxide, by the change in volume stress of absorption metal oxide in the lithium ion battery charge and discharge process, thus the cycle performance of enhancing metal oxide.Therefore, material with carbon element and metal oxide are carried out the composite material of the novel nano structure that combined structure goes out as the negative material of lithium ion battery, be expected to significantly improve the performance of lithium ion battery, and expand to use for it and also have far reaching significance.
Summary of the invention
Because the above-mentioned defective of prior art, technical problem to be solved by this invention provides a kind of composite material that can strengthen the three-dimensional structure of metal oxide cycle performance.
For achieving the above object, the invention provides a kind of preparation method and application thereof with graphene-based metal oxide composite of three-dimensional structure.Particularly, adopt the Graphene of monolayer carbon atomic structure as three-dimensional framework, stannic chloride pentahydrate prepares the graphene-based metal tin ash composite material of three-dimensional structure as tin source presoma.
The present invention solves above-mentioned technical problem by the following technical programs:
On the one hand, the invention provides a kind of preparation method with graphene-based metal oxide composite of three-dimensional structure.
Preparation method of the present invention adopts the synthetic graphene-based metal oxide composite with three-dimensional structure of two-step method.At first, adopt metal oxide precursor at the Graphene surface hydrolysis, obtain graphene-based metal oxide nano-sheet by the growth in situ method; Secondly, under the effect of auxiliary crosslinking agent, nanometer sheet is assembled into the graphene-based metal oxide of three-dimensional structure by hydro-thermal; At last, by freeze drying, calcining obtains the composite material of three-dimensional structure.
On the other hand, the invention solves the low metal oxide-loaded problem of three-dimensional Graphene metal oxide.
In the present invention, the concrete grammar of graphene-based metal oxide composite of preparation with three-dimensional structure comprises the steps:
At first, be graphene oxide (GO) dimethyl formamide (DMF) solution of 1mg/mL with concentration, ultrasonic mixing;
Secondly, add metal oxide precursor in the above-mentioned solution after, mix, 60-90 ℃ of insulation 12 hours;
At last, above-mentioned reacted solution is carried out centrifugal, deionized water washing, the deionized water dispersion liquid that concentrates that obtains is stand-by.
The graphene-based oxide silica aerogel of step 2, preparation three-dimensional structure:
At first, place the vial of 10mL to the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet, add the auxiliary crosslinking agent of a certain amount of concentration known, after mixing, and the direct hydrothermal treatment consists of the water heating kettle that vial is placed 80mL;
Secondly, with the block freeze drying that obtains after the above-mentioned reaction, calcination processing finally obtains the graphene-based metal oxide composite of three-dimensional structure.
Wherein, described metal oxide precursor is stannic chloride pentahydrate (SnCl
45H
2O) or butyl titanate (TBT); Auxiliary crosslinking agent is polyvinyl alcohol (PVA), polyethers F127(F127), graphene oxide (GO) or expoxy propane (PO).
In the specific embodiment of the present invention, when metal oxide precursor is stannic chloride pentahydrate, preferably before in dispersion liquid, adding presoma, in dispersion liquid, add hydrochloric acid earlier, regulator solution pH to 3, after under intense agitation, adding stannic chloride pentahydrate then, again 60～90 ℃ of insulations 12 hours; If TBT then adds the concentrated sulfuric acid, pH value of solution is adjusted to 1 after, under the ice-water bath condition, add TBT, treat that TBT dissolves fully after, again 60～90 ℃ of insulations 12 hours.
The present invention in the specific implementation, the stannic chloride pentahydrate that adds in the step 1 and the mass ratio of graphene oxide are preferably 2.27:1; The mass ratio of TBT and graphene oxide is 1.5:1.
In preferred implementation of the present invention, the concentration of the dispersion liquid of graphene-based metal oxide nano-sheet in deionized water is preferably 5mg/mL.
In preparation method of the present invention, during to the self assembly of nanometer sheet hydro-thermal, it is polyvinyl alcohol (PVA), polyethers F127(F127 that auxiliary crosslinking agent can be auxiliary crosslinking agent in the step 2), graphene oxide (GO) or expoxy propane (PO).
When auxiliary crosslinking agent is PVA, add 1mL behind the aqueous solution of PVA of requirement in the viscous fluid of graphene-based metal oxide nano-sheet, evenly mix 5min, then hydrothermal treatment consists 12-18h under 180 ℃ of conditions.
Preferably, graphene-based metal oxide nano-sheet (in graphene oxide) is 1:0.0021 with the mass ratio of PVA.
When auxiliary crosslinking agent is F127, add 1mL behind the aqueous solution of F127 of requirement in the viscous fluid of graphene-based metal oxide nano-sheet, evenly mix 5min, then hydrothermal treatment consists 12-18h under 180 ℃ of conditions.
Preferably, graphene-based metal oxide nano-sheet (in graphene oxide) is 1:0.0021 with the mass ratio of F127.
When auxiliary crosslinking agent is GO, add 1mL behind the aqueous solution of GO of requirement in the viscous fluid of graphene-based metal oxide nano-sheet, evenly mix 5min, then hydrothermal treatment consists 12-18h under 180 ℃ of conditions.
Preferably, graphene-based metal oxide nano-sheet (in graphene oxide) is 1:1 with the mass ratio of GO.When auxiliary crosslinking agent is PO, add 1mL behind the aqueous solution of PVA of requirement in the viscous fluid of graphene-based metal oxide nano-sheet, evenly mix 5min, then hydrothermal treatment consists 12-18h under 180 ℃ of conditions.
Preferably, graphene-based metal oxide nano-sheet (in graphene oxide) is 1:1 with the mass ratio of PO.
In a preferred embodiment of the invention, the product freeze drying 48h that step 2 obtains, and through N
2In 300 ℃ of calcining carbonizations 1-3 hour, graphene oxide was reduced, and becomes the graphene oxide (RGO) of reduction, i.e. Graphene down in protection.
In preparation method of the present invention, metal oxide particle is loaded on the Graphene surface, suppressed the reunion of its particle to a certain extent, increase specific area, thereby improve the capacity of material.Simultaneously the material of this two dimension is carried out three-dimensional and construct, can effectively absorb metal oxide such as the change in volume of stannic oxide particle in charge and discharge process, suppress the pulverizing of its particle and come off, thereby improved the cyclical stability of material greatly.Can improve simultaneously the conductivity of material, realize the quick transmission of electronics, thereby make material have high high rate performance.
On the other hand, the present invention also provides a kind of application with graphene-based metal oxide composite of three-dimensional structure.
Of the present invention have the graphene-based metal oxide composite advantageous applications of three-dimensional structure in lithium ion battery negative material.The composite material of three-dimensional structure of the present invention can also strengthen its cycle performance during as lithium ion battery negative material when improving the negative material capacity.
In specific embodiments of the present invention, the button-shaped half-cell of lithium ion is negative material with the graphene-based metal oxide composite that has three-dimensional structure as mentioned above, lithium metal just very, electrolyte is ethyl carbonate or the dimethyl carbonate solution of lithium hexafluoro phosphate solution.
The present invention adopts the two-dimentional Graphene of monolayer carbon atomic structure as carrier uniform load metal oxide, assisting down of some crosslinking agents, prepares the graphene-based metal oxide nano composite material of three-dimensional structure by simple two-step method.This method has technology simple, mild condition, advantage such as with low cost.The metal oxide nanoparticles that obtains by the inventive method loads on the Graphene skeleton equably, obtains the more unified three-dimensional structure of aperture size simultaneously.Prove that through electro-chemical test prepared composite material has excellent cyclical stability and high rate performance; Experiment showed, at 200mAg
-1Charging or discharging current under, the discharge capacity of the tin dioxide material that makes can reach 950mAhg
-1, at 50mAg
-1Charging or discharging current under, the titania meterial discharge capacity can reach 150mAhg
-1Therefore, the present invention provides good experimental data and theoretical the support for metal oxide in research and the application of electrochemical field.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand purpose of the present invention, feature and effect fully.
Description of drawings
Fig. 1 is the pattern TEM figure of the graphene-based metal oxide nano-sheet of embodiments of the invention 1.
Fig. 2 is the shape appearance figure of the three-dimensional graphene-based metal tin ash aeroge of embodiments of the invention 1; Wherein, a), b) be respectively the SEM figure of embodiment 1, c) be that the TEM of embodiment 1 schemes.
Fig. 3 is pattern and the structure chart of the three-dimensional graphene-based burning titanium aeroge of embodiments of the invention 2; Wherein, a) being the SEM figure of embodiment 2, b) is the XRD figure of embodiment 2.
Fig. 4 is embodiments of the invention 3,4, pattern and the structure chart of 5 three-dimensional graphene-based metal tin ash aeroge; Wherein, a), b), c) be respectively embodiment 3,4,5 SEM figure.
Fig. 5 is that the three-dimensional graphene-based tin ash composite material of embodiments of the invention 1 is as the cycle performance figure of lithium ion battery negative material.
Fig. 6 is that the graphene-based tin ash of embodiments of the invention 1 and three-dimensional graphene-based tin ash composite material are as the high rate performance figure of lithium ion battery negative material.
Fig. 7 is that the graphene-based titanium oxide of embodiments of the invention 2 and three-dimensional graphene-based titanium dioxide composite material are as the cycle performance figure of lithium ion battery negative material.
Fig. 8 is that the graphene-based titanium oxide of embodiments of the invention 2 and three-dimensional graphene-based titanium dioxide composite material are as the high rate performance figure of lithium ion battery negative material.
Fig. 9 is embodiments of the invention 3,4, and the three-dimensional graphene-based tin ash composite material of 5 graphene-based tin ash and different crosslinking agents is as the high rate performance figure of lithium ion battery negative material.
Embodiment
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) dimethyl formamide solution (100mL) of 1mg/mL graphene oxide is ultrasonic, form the dispersion liquid that mixes;
(2) add water and the hydrochloric acid of 25mL in the above-mentioned dispersion liquid, regulator solution pH to 3; Under vigorous stirring, add butter of tin (SnCl
45H
2O), add in 80 ℃ of insulation 12h, cooling;
Wherein, the SnCl of interpolation
45H
2The quality amount ratio of O and graphene oxide is 2.26:1.
(3) carry out above-mentioned reacted solution centrifugal, spend deionised water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL, be graphene-based stannic oxide nanometer sheet, this graphene-based stannic oxide nanometer sheet TEM photo respectively as shown in Figure 1.
The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:
(1) gets the PVA aqueous solution that adds 1mL in the viscous fluid of graphene-based stannic oxide nanometer sheet of the above-mentioned above-mentioned preparation that concentrates good 5mg/mL, after mixing, place hydro-thermal 12-18h under 180 ℃ the condition;
Wherein, the consumption mass ratio of graphene oxide and PVA is 1:0.0021;
(2) with the above-mentioned reacted block that obtains, behind the freeze drying 48h, through N
2Protect following 300 ℃ of calcining carbonization 2h, finally obtain the graphene-based tin ash composite material of three-dimensional structure, the SEM of this material and TEM photo as Fig. 2 a)-c) shown in.
Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) with the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, its cycle performance figure, high rate performance figure are respectively shown in Fig. 5,6.
Wherein, RGO/SnO
2For not assisting crosslinked graphene-based tin ash as charge and discharge curve, the RGO/SnO of lithium ion battery negative material through crosslinking agent
2/ PVA is for obtaining having three-dimensional graphene-based tin ash composite material as the charge and discharge curve of lithium ion battery negative material through PVA is auxiliary crosslinked.As can be seen from Figure 5 the composite material of this three-dimensional structure has demonstrated higher capacity (1000mAhg
-1), and very superior cycle performance.It is still keeping 950mAhg after 80 circle circulations
-1Capacity, do not carry out the then 900mAhg of ten circles in the past of the auxiliary crosslinked material capacity of PVA
-1Dropped to only 500mAhg
-1As shown in Figure 6, has three-dimensional material at 8Ag
-1Big electric current under still maintain 100mAhg
-1Capacity, this is very excellent high rate performance concerning tin dioxide material.
The first step, prepare three-dimensional graphene-based titanium dioxide
(1) dimethyl formamide solution (100mL) of 1mg/mL graphene oxide is ultrasonic, form the dispersion liquid that mixes;
(2) add water and the concentrated sulfuric acid of 25mL in the above-mentioned dispersion liquid, regulator solution pH to 1; Add butyl titanate (TBT) under ice-water bath and the vigorous stirring, add in 80 ℃ of insulation 12h, cooling;
Wherein, the quality amount ratio of the TBT of interpolation and graphene oxide is 1.5:1.
(3) above-mentioned reacted solution is carried out centrifugal, spend deionised water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL is the graphene-based titanium dioxide nanometer sheet.
The graphene-based titanium dioxide aeroge of second step, preparation three-dimensional structure:
(1) gets the PVA aqueous solution that adds 1mL in the viscous fluid of graphene-based titanium dioxide nanometer sheet of the above-mentioned above-mentioned preparation that concentrates good 5mg/mL, after mixing, place hydro-thermal 12-18h under 180 ℃ the condition;
Wherein, the consumption mass ratio of graphene oxide and PVA is 1:0.0021;
(2) with the block that obtains after the above-mentioned reaction, behind the freeze drying 48h, through N
2Protect following 300 ℃ of calcining carbonization 2h, finally obtain the graphene-based titanium dioxide composite material of three-dimensional structure, the SEM photo of this material and XRD such as Fig. 3 a), b) shown in.
Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) with the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, its cycle performance figure, high rate performance figure are respectively shown in Fig. 7,8.Wherein, RGO/TiO
2/ PVA and RGO/TiO
2Be respectively the auxiliary crosslinked three-dimensional of PVA graphene-based titanium oxide composite material, the auxiliary crosslinked graphene-based titanium oxide that obtains of PVA is not arranged as the charge/discharge curve of lithium ion battery negative material.As can be seen from Figure 7, the three-dimensional composite material that makes demonstrates higher capacity (150mAhg
-1) and very superior cycle performance.It is still keeping 150mAhg after 150 circle circulations
-1Capacity, and the capacity that does not carry out the auxiliary crosslinked material of PVA is 121mAhg
-1As shown in Figure 8, San Wei composite material is at 5000mAg
-1Big electric current under still maintain 50mAhg
-1Capacity.
Embodiment 3
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) dimethyl formamide solution (100mL) of 1mg/mL graphene oxide is ultrasonic, form the dispersion liquid that mixes;
(2) add water and the hydrochloric acid of 25mL in the above-mentioned dispersion liquid, regulator solution pH to 3; Under vigorous stirring, add butter of tin (SnCl
45H
2O), add in 80 ℃ of insulation 12h, cooling;
Wherein, the SnCl of interpolation
45H
2The quality amount ratio of O and graphene oxide is 2.26:1.
(3) above-mentioned reacted solution is carried out centrifugal, spend deionised water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL is graphene-based stannic oxide nanometer sheet.
The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:
(1) gets the F127 aqueous solution that adds 1mL in the viscous fluid of graphene-based stannic oxide nanometer sheet of the above-mentioned above-mentioned preparation that concentrates good 5mg/mL, after mixing, place hydro-thermal 12-18h under 180 ℃ the condition;
Wherein, the consumption mass ratio of graphene oxide and F127 is 1:0.0021;
(2) with the above-mentioned reacted block that obtains, behind the freeze drying 48h, through N
2Protect following 300 ℃ of calcining carbonization 2h, finally obtain the graphene-based tin ash composite material of three-dimensional structure, the SEM photo of this material as Fig. 4 a) shown in.
Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) with the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, its high rate performance figure as shown in Figure 9.Wherein, RGO/SnO
2/ F127 is that the graphene-based tin ash composite material of the auxiliary crosslinked three-dimensional of F127 is as the discharge curve of lithium ion battery negative material.As can be seen from Figure 9 the composite material of this three-dimensional structure has demonstrated higher capacity (700mAhg
-1), and very superior multiplying power and cycle performance.As shown in Figure 9, have three-dimensional material and under the big electric current of 8A/g, still maintain 231mAhg
-1Capacity, and do not have crosslinking agent to assist crosslinked RGO/SnO
2Material then has only 26mAhg
-1Capacity; When the large current density after-current returned to 0.2A/g, after 140 circles charged and discharged circulation, capacity also was stabilized in 500mAhg
-1, do not carry out crosslinked material then decay more serious, 140 the circle charge and discharge circulation after, capacity attenuation is to 278mAhg
-1So three-dimensional structure has shown very excellent high rate performance and stability concerning tin dioxide material.
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) dimethyl formamide solution (100mL) of 1mg/mL graphene oxide is ultrasonic, form the dispersion liquid that mixes;
(2) add water and the hydrochloric acid of 25mL in the above-mentioned dispersion liquid, regulator solution pH to 3; Under vigorous stirring, add butter of tin (SnCl
45H
2O), add in 80 ℃ of insulation 12h, cooling;
Wherein, the SnCl of interpolation
45H
2The quality amount ratio of O and graphene oxide is 2.26:1.
(3) above-mentioned reacted solution is carried out centrifugal, spend deionised water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL is graphene-based stannic oxide nanometer sheet.
The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:
(1) gets the GO solution that adds 1mL in the viscous fluid of graphene-based stannic oxide nanometer sheet of the above-mentioned above-mentioned preparation that concentrates good 5mg/mL, after mixing, place hydro-thermal 12-18h under 180 ℃ the condition;
Wherein, the consumption mass ratio of graphene oxide and GO is 1:1;
(2) with the above-mentioned reacted block that obtains, behind the freeze drying 48h, through N
2Protect following 300 ℃ of calcining carbonization 2h, finally obtain the graphene-based tin ash composite material of three-dimensional structure, the SEM photo of this material is as Fig. 4 b) shown in.
Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) with the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, its high rate performance figure as shown in Figure 9.Wherein, RGO/SnO
2/ GO is that the graphene-based tin ash composite material of the auxiliary crosslinked three-dimensional of GO is as the discharge curve of lithium ion battery negative material.As can be seen from Figure 9 the composite material of this three-dimensional structure has demonstrated very superior multiplying power and cycle performance.As shown in Figure 9, have three-dimensional material and under the big electric current of 8A/g, 120mAhg is arranged
-1Capacity, when and do not have crosslinking agent to assist crosslinked RGO/SnO
2Material then has only 26mAhg
-1Capacity; When the large current density after-current returns to 0.2A/g, after 140 circles charge and discharge circulation, RGO/SnO
2/ GO capacity also is stabilized in 558mAhg
-1, do not carry out crosslinked material then decay more serious, 140 the circle charge and discharge circulation after, capacity attenuation is to 278mAhg
-1So the tin dioxide material of three-dimensional structure has shown very excellent high rate performance and stability.
Embodiment 5
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) dimethyl formamide solution (100mL) of 1mg/mL graphene oxide is ultrasonic, form the dispersion liquid that mixes;
(2) add water and the hydrochloric acid of 25mL in the above-mentioned dispersion liquid, regulator solution pH to 3; Under vigorous stirring, add butter of tin (SnCl
45H
2O), add in 80 ℃ of insulation 12h, cooling;
Wherein, the SnCl of interpolation
45H
2The quality amount ratio of O and graphene oxide is 2.26:1.
(3) above-mentioned reacted solution is carried out centrifugal, spend deionised water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL is graphene-based stannic oxide nanometer sheet.
The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:
(1) gets the PO solution that adds 1mL in the viscous fluid of graphene-based stannic oxide nanometer sheet of the above-mentioned above-mentioned preparation that concentrates good 5mg/mL, after mixing, place hydro-thermal 12-18h under 180 ℃ the condition;
Wherein, the consumption mass ratio of graphene oxide and PO is 1:1;
(2) with the above-mentioned reacted block that obtains, behind the freeze drying 48h, through N
2Protect following 300 ℃ of calcining carbonization 2h, finally obtain the graphene-based tin ash composite material of three-dimensional structure, the SEM photo of this material is as Fig. 4 c) shown in.
Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) with the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, its high rate performance figure as shown in Figure 9.Wherein, RGO/SnO
2/ PO is that the graphene-based tin ash composite material of the auxiliary crosslinked three-dimensional of PO is as the discharge curve of lithium ion battery negative material.As can be seen from Figure 9 the composite material of this three-dimensional structure has demonstrated higher capacity (900mAhg
-1), and very superior multiplying power and cycle performance.As shown in Figure 9, have three-dimensional material and under the big electric current of 8A/g, still maintain 120mAhg
-1Capacity, and do not have crosslinking agent to assist crosslinked RGO/SnO
2Material then has only 26mAhg
-1Capacity; When the large current density after-current returns to 0.2A/g, after 140 circles charge and discharge circulation, RGO/SnO
2/ PO capacity also is stabilized in 900mAhg
-1, do not carry out crosslinked material then decay more serious, 140 the circle charge and discharge circulation after, capacity attenuation is to 278mAhg
-1So the tin dioxide material of three-dimensional structure has shown very excellent high rate performance and stability.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variations.Therefore, all technical staff in the art all should be in the determined protection range by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. the preparation method of the graphene-based metal oxide composite of a three-dimensional structure is characterized in that, may further comprise the steps:
Step 1, prepare graphene-based metal oxide nano-sheet;
The graphene-based metal oxide aerogel of step 2, preparation three-dimensional structure.
2. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 1 is characterized in that, prepares graphene-based metal oxide nano-sheet and may further comprise the steps:
At first, be the graphene oxide dimethyl formamide solution of 1mg/mL with concentration, ultrasonic being uniformly dispersed;
Secondly, add metal oxide precursor in the above-mentioned finely dispersed solution after, 60-90 ℃ of insulation 12 hours;
At last, above-mentioned reacted dispersion liquid is carried out centrifugal, deionized water washing, the deionized water dispersion liquid that concentrates that obtains.
3. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 1 is characterized in that, the graphene-based metal oxide aerogel of preparation three-dimensional structure may further comprise the steps:
At first, place the vial of 20mL to the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet, add the auxiliary crosslinking agent of a certain amount of concentration known, after mixing, the water heating kettle that vial is placed 150mL is hydrothermal treatment consists directly;
Secondly, with block freeze drying and the calcination processing that obtains after the above-mentioned reaction, finally obtain the graphene-based metal oxide composite of three-dimensional structure.
4. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 2 is characterized in that, described metal oxide precursor is stannic chloride pentahydrate or butyl titanate.
5. the graphene-based metal oxide composite preparation method of three-dimensional structure as claimed in claim 4 is characterized in that, the consumption mass ratio of graphene oxide and described stannic chloride pentahydrate is 1:2.27; The mass ratio of graphene oxide and described butyl titanate is 1:1.5.
6. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 3 is characterized in that, described auxiliary crosslinking agent is polyvinyl alcohol, polyethers F127, expoxy propane or graphene oxide.
7. the graphene-based metal oxide composite preparation method of three-dimensional structure as claimed in claim 6, it is characterized in that, when auxiliary crosslinking agent was polyvinyl alcohol, polyethers F127, expoxy propane or graphene oxide, graphene oxide and described auxiliary crosslinking agent were than being 1:0.0021～1:1.
8. the graphene-based metal oxide composite preparation method of three-dimensional structure as claimed in claim 6 is characterized in that, when auxiliary crosslinking agent was polyvinyl alcohol or polyethers F127, graphene oxide was 1:0.0021 with described auxiliary crosslinking agent ratio.
9. the graphene-based metal oxide composite preparation method of three-dimensional structure as claimed in claim 6 is characterized in that, when auxiliary crosslinking agent was expoxy propane or graphene oxide, graphene oxide was 1:1 with described auxiliary crosslinking agent ratio.
10. as the application of graphene-based metal oxide composite in lithium ion battery of each described three-dimensional structure in the claim 1 to 9.
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| CN103606662A (en) * | 2013-11-12 | 2014-02-26 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based tin dioxide composite material |
| CN103904313A (en) * | 2014-04-15 | 2014-07-02 | 山东省科学院能源研究所 | Preparation method and application of tin oxide-aza graphene aerosol composite material |
| CN104143631A (en) * | 2014-05-12 | 2014-11-12 | 上海大学 | Method for preparing graphene aerogel loaded tin dioxide composite material |
| CN104392843A (en) * | 2014-11-20 | 2015-03-04 | 上海电力学院 | Three-dimensional lamellar metal hydroxide nanosheet/graphene aerogel composite and preparation method thereof |
| CN104401979A (en) * | 2014-10-31 | 2015-03-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Phase-transfer preparation method of graphene-based composite aerogel |
| CN104907018A (en) * | 2015-05-25 | 2015-09-16 | 齐鲁工业大学 | Three-dimensional titanic acid/graphene oxide composite gel, and preparation method thereof |
| CN105742642A (en) * | 2016-03-28 | 2016-07-06 | 上海应用技术学院 | Preparation method for negative electrode material of lithium ion battery |
| CN105819440A (en) * | 2016-06-08 | 2016-08-03 | 东南大学 | Method for preparing block graphene aerogel |
| CN106099061A (en) * | 2016-07-14 | 2016-11-09 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene/silicon composite, its preparation method and lithium ion battery |
| CN106129329A (en) * | 2016-07-08 | 2016-11-16 | 中国工程物理研究院材料研究所 | A kind of graphene-based used as negative electrode of Li-ion battery combination electrode and preparation method thereof |
| CN106299309A (en) * | 2016-09-30 | 2017-01-04 | 上海交通大学 | Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof |
| CN106744896A (en) * | 2017-01-20 | 2017-05-31 | 哈尔滨工业大学 | A kind of preparation method of closed pore graphene oxide sponge |
| CN106941176A (en) * | 2017-05-18 | 2017-07-11 | 广东工业大学 | A kind of SnO as lithium ion battery negative2/ C nano medicine ball and preparation method thereof |
| CN107090274A (en) * | 2017-04-28 | 2017-08-25 | 哈尔滨工业大学 | Graphene-based heat sink material containing Argent grain and preparation method thereof |
| CN107579241A (en) * | 2017-09-22 | 2018-01-12 | 上海工程技术大学 | A kind of preparation method of three-dimensional tent type graphene metal oxide nano composite material |
| CN108899550A (en) * | 2018-07-19 | 2018-11-27 | 桑德集团有限公司 | Compound coating positive electrode active materials and preparation method thereof, anode material for lithium-ion batteries and solid lithium ion battery |
| CN109243847A (en) * | 2018-10-25 | 2019-01-18 | 上海应用技术大学 | Three-dimensional ordered macroporous carbon-coated NiMoO4/ redox graphene nanocomposite of one kind and preparation method thereof |
| CN112421005A (en) * | 2020-11-19 | 2021-02-26 | 北京航空航天大学 | Three-dimensional graphene-C3N4Composite material, preparation method and application thereof, and half cell |
| CN112646300A (en) * | 2020-12-22 | 2021-04-13 | 蜂巢能源科技有限公司 | Battery cell buffer material, preparation method and application thereof |
| CN112661142A (en) * | 2021-01-12 | 2021-04-16 | 大连海洋大学 | Nano TiN/N-rGO three-dimensional porous carbon aerogel and preparation method thereof |
| CN113782734A (en) * | 2021-08-24 | 2021-12-10 | 南昌大学 | Preparation method of silicon monoxide negative pole piece |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
-
2013
- 2013-06-25 CN CN201310256496.4A patent/CN103346301B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI XIAO ET AL: "Self-Assembled Fe2O3/Graphene Aerogel with High Lithium Storage Performance", 《ACS APPL. MATER. INTERFACES》 * |
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| CN103606662A (en) * | 2013-11-12 | 2014-02-26 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based tin dioxide composite material |
| CN103904313A (en) * | 2014-04-15 | 2014-07-02 | 山东省科学院能源研究所 | Preparation method and application of tin oxide-aza graphene aerosol composite material |
| CN103904313B (en) * | 2014-04-15 | 2016-01-20 | 山东省科学院能源研究所 | The preparation method of a kind of tin oxide-nitrogen-doped graphene aerosol composite material and application thereof |
| CN104143631A (en) * | 2014-05-12 | 2014-11-12 | 上海大学 | Method for preparing graphene aerogel loaded tin dioxide composite material |
| CN104401979A (en) * | 2014-10-31 | 2015-03-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Phase-transfer preparation method of graphene-based composite aerogel |
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| CN104907018A (en) * | 2015-05-25 | 2015-09-16 | 齐鲁工业大学 | Three-dimensional titanic acid/graphene oxide composite gel, and preparation method thereof |
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| CN105742642B (en) * | 2016-03-28 | 2018-03-30 | 上海应用技术学院 | A kind of preparation method of lithium ion battery negative material |
| CN105819440A (en) * | 2016-06-08 | 2016-08-03 | 东南大学 | Method for preparing block graphene aerogel |
| CN106129329A (en) * | 2016-07-08 | 2016-11-16 | 中国工程物理研究院材料研究所 | A kind of graphene-based used as negative electrode of Li-ion battery combination electrode and preparation method thereof |
| CN106099061B (en) * | 2016-07-14 | 2018-10-09 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene/silicon composite, preparation method and lithium ion battery |
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| CN106744896A (en) * | 2017-01-20 | 2017-05-31 | 哈尔滨工业大学 | A kind of preparation method of closed pore graphene oxide sponge |
| CN106744896B (en) * | 2017-01-20 | 2018-09-07 | 哈尔滨工业大学 | A kind of preparation method of closed pore graphene oxide sponge |
| CN107090274A (en) * | 2017-04-28 | 2017-08-25 | 哈尔滨工业大学 | Graphene-based heat sink material containing Argent grain and preparation method thereof |
| CN107090274B (en) * | 2017-04-28 | 2019-10-25 | 哈尔滨工业大学 | Graphene-based heat sink material containing Argent grain and preparation method thereof |
| CN106941176A (en) * | 2017-05-18 | 2017-07-11 | 广东工业大学 | A kind of SnO as lithium ion battery negative2/ C nano medicine ball and preparation method thereof |
| CN106941176B (en) * | 2017-05-18 | 2019-09-27 | 广东工业大学 | A kind of SnO as negative electrode of lithium ion battery2/ C nano medicine ball and preparation method thereof |
| CN107579241B (en) * | 2017-09-22 | 2021-04-09 | 上海工程技术大学 | Preparation method of three-dimensional tent type graphene-metal oxide nano composite material |
| CN107579241A (en) * | 2017-09-22 | 2018-01-12 | 上海工程技术大学 | A kind of preparation method of three-dimensional tent type graphene metal oxide nano composite material |
| CN108899550A (en) * | 2018-07-19 | 2018-11-27 | 桑德集团有限公司 | Compound coating positive electrode active materials and preparation method thereof, anode material for lithium-ion batteries and solid lithium ion battery |
| CN109243847A (en) * | 2018-10-25 | 2019-01-18 | 上海应用技术大学 | Three-dimensional ordered macroporous carbon-coated NiMoO4/ redox graphene nanocomposite of one kind and preparation method thereof |
| CN112421005A (en) * | 2020-11-19 | 2021-02-26 | 北京航空航天大学 | Three-dimensional graphene-C3N4Composite material, preparation method and application thereof, and half cell |
| CN112646300A (en) * | 2020-12-22 | 2021-04-13 | 蜂巢能源科技有限公司 | Battery cell buffer material, preparation method and application thereof |
| CN112646300B (en) * | 2020-12-22 | 2023-01-03 | 蜂巢能源科技有限公司 | Battery cell buffer material, preparation method and application thereof |
| CN112661142A (en) * | 2021-01-12 | 2021-04-16 | 大连海洋大学 | Nano TiN/N-rGO three-dimensional porous carbon aerogel and preparation method thereof |
| CN112661142B (en) * | 2021-01-12 | 2022-08-05 | 大连海洋大学 | Nano TiN/N-rGO three-dimensional porous carbon aerogel and preparation method thereof |
| CN113782734A (en) * | 2021-08-24 | 2021-12-10 | 南昌大学 | Preparation method of silicon monoxide negative pole piece |
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