CN103346301B - The preparation method of the graphene-based metal oxide composite of three-dimensional structure and application thereof - Google Patents

The preparation method of the graphene-based metal oxide composite of three-dimensional structure and application thereof Download PDF

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CN103346301B
CN103346301B CN201310256496.4A CN201310256496A CN103346301B CN 103346301 B CN103346301 B CN 103346301B CN 201310256496 A CN201310256496 A CN 201310256496A CN 103346301 B CN103346301 B CN 103346301B
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graphene
metal oxide
dimensional
crosslinking agent
composite
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CN103346301A (en
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冯新亮
黄燕山
吴东清
张帆
李爽
肖丽
王金钻
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上海交通大学
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of preparation method and application thereof of graphene-based metal oxide composite of three-dimensional structure.Preparation method of the present invention adopts the Graphene of monolayer carbon atomic structure as carrier, and some high molecular polymers are as auxiliary crosslinking agent, prepares the graphene-based metal oxide composite of three-dimensional structure by the method for hydro-thermal freeze-drying.The three-dimensional aeroge obtained by the method has higher metal oxide supported amount.Prove through electro-chemical test, the three-dimensional aerogel graphene-base metal oxide composite that preparation method of the present invention obtains has excellent cyclical stability and high rate performance.Experiment proves at 100mAg -1charging or discharging current under, tin dioxide material discharge capacity can reach 1050mAhg -1; At 50mAg -1charging or discharging current under, titania meterial discharge capacity can reach 150mAhg -1.

Description

The preparation method of the graphene-based metal oxide composite of three-dimensional structure and application thereof

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 day by day highlighting of energy and environment problem, New Energy Industry obtains increasing attention.Rapidly, lithium ion battery is widely used as wherein important energy storage device for hybrid vehicle and electric automobile industry development.Lithium ion battery has energy density high, some excellent performances such as good cycle, is also considered to one of the most effective energy storage mode at present, and therefore, its energy density of raising and cycle performance are also the difficult point and focus instantly studied further.

The negative pole of lithium ion battery is the important component part of battery, and its Structure and Properties directly affects capacity and the cycle performance of lithium ion battery.The lithium ion battery negative material of current commercialization is based on graphite, and graphite cost is low, and wide material sources are suitable for commercialization; But its capacity is lower, and theoretical capacity is only 372mAhg -1, be restricted when applying in the field exported needing high-energy.

Metal oxide is 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 -1; But most of metal oxide, especially SnO 2as electrode material, in charge and discharge process, change in volume is up to 200-300%, and this change in volume can cause the efflorescence of electrode, causes the open circuit of active material and collector.Therefore, most metals oxide is as all there is capacity attenuation problem rapidly during lithium ion cell electrode.TiO 2owing to there is higher embedding lithium and the voltage that moves lithium is 1.7V, the forming process of SEI film effectively can be alleviated.But TiO 2the conductivity of itself is poor, so for improving the bulk effect of metal oxide and improving conductivity, be the 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, these problems that researchers exist for metal oxide conduct in-depth research, such as modification is carried out to electrode material, comprise the preparation of coated, doping, compound and nano material, improved 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 research at present.

Material with carbon element has the premium properties of its uniqueness: stability, good conductivity, light weight; Make it as the carrier of good metal oxide, by absorbing the change in volume stress of metal oxide in lithium ion battery charge and discharge process, thus the cycle performance of metal oxide can be strengthened.Therefore, material with carbon element and metal oxide are carried out the negative material of composite material as lithium ion battery of the novel nano structure that combined structure goes out, be expected to the performance significantly improving lithium ion battery, and also there is far reaching significance for its expansive approach.

Summary of the invention

Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide 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 the application thereof with the 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, as tin source presoma, prepares the graphene-based metal tin dioxide composite material of three-dimensional structure.

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 the graphene-based metal oxide composite of three-dimensional structure.

Preparation method of the present invention adopts two step synthesis to have the graphene-based metal oxide composite of three-dimensional structure.First, adopt metal oxide precursor to be hydrolyzed at graphenic surface, obtain graphene-based metal oxide nano-sheet by situ synthesis; Secondly, nanometer sheet is assembled into the graphene-based metal oxide of three-dimensional structure under the effect of auxiliary crosslinking agent by hydro-thermal; Finally, 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 grapheme metal oxide.

In the present invention, prepare the concrete grammar with the graphene-based metal oxide composite of three-dimensional structure to comprise the steps:

Step one, prepare graphene-based metal oxide nano-sheet:

First, be graphene oxide (GO) dimethyl formamide (DMF) solution of 1mg/mL by concentration, ultrasonicly mix;

Secondly, add metal oxide precursor in above-mentioned solution after, mix, 60-90 DEG C of insulation 12 hours;

Finally, undertaken centrifugal by above-mentioned reacted solution, deionized water washs, and the concentrated deionized water dispersion liquid obtained is stand-by.

The graphene-based oxide silica aerogel of step 2, preparation three-dimensional structure:

First, the dispersion liquid to above-mentioned graphene-based metal oxide nano-sheet is placed in the vial of 10mL, adds the auxiliary crosslinking agent of a certain amount of concentration known, after mixing, and vial is placed in the water heating kettle Direct Hydrothermal process of 80mL;

Secondly, by the block freeze drying obtained after 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 2or butyl titanate (TBT) O); 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 add presoma in dispersion liquid, first in dispersion liquid, add hydrochloric acid, regulate pH value of solution to 3, then after adding stannic chloride pentahydrate under intense agitation, then 60 ~ 90 DEG C of insulations 12 hours; If TBT then adds the concentrated sulfuric acid, after pH value of solution is adjusted to 1, under ice-water bath condition, add TBT, after TBT dissolves completely, then 60 ~ 90 DEG C of insulations 12 hours.

In the specific implementation, the stannic chloride pentahydrate added in step one and the mass ratio of graphene oxide are preferably 2.27:1 in the present invention; The mass ratio of TBT and graphene oxide is 1.5:1.

In a preferred embodiment of the invention, the concentration of graphene-based metal oxide nano-sheet dispersion liquid is in deionized water preferably 5mg/mL.

In the preparation process in accordance with the present invention, time in step 2 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), graphene oxide (GO) or expoxy propane (PO).

When auxiliary crosslinking agent is PVA, in the viscous fluid of graphene-based metal oxide nano-sheet, add 1mL, Homogeneous phase mixing 5min after the aqueous solution of the PVA of requirement, then at 180 DEG C of Water Under heat treatment 12-18h.

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, in the viscous fluid of graphene-based metal oxide nano-sheet, add 1mL, Homogeneous phase mixing 5min after the aqueous solution of the F127 of requirement, then at 180 DEG C of Water Under heat treatment 12-18h.

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, in the viscous fluid of graphene-based metal oxide nano-sheet, add 1mL, Homogeneous phase mixing 5min after the aqueous solution of the GO of requirement, then at 180 DEG C of Water Under heat treatment 12-18h.

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, in the viscous fluid of graphene-based metal oxide nano-sheet, add 1mL, Homogeneous phase mixing 5min after the aqueous solution of the PVA of requirement, then at 180 DEG C of Water Under heat treatment 12-18h.

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 DEG C of calcining carbonization 1-3 hour under protection, graphene oxide is reduced, and becomes the graphene oxide (RGO) of reduction, i.e. Graphene.

In the preparation process in accordance with the present invention, by metal oxide particle load at graphenic surface, inhibit the reunion of its particle to a certain extent, increase specific area, thus improve the capacity of material.The material of this two dimension is carried out three-dimensional to construct simultaneously, effectively can absorb metal oxide as the change in volume of stannic oxide particle in charge and discharge process, suppress the pulverizing of its particle and come off, thus improve the cyclical stability of material greatly.The conductivity of material can be improved simultaneously, realize the quick transmission of electronics, thus make material have high high rate performance.

On the other hand, present invention also offers a kind of application with the graphene-based metal oxide composite of three-dimensional structure.

The graphene-based metal oxide composite with three-dimensional structure of the present invention is preferably applied in lithium ion battery negative material.When the composite material of three-dimensional structure of the present invention is as lithium ion battery negative material, can also strengthen its cycle performance while raising negative material capacity.

In specific embodiment of the invention scheme, the button-shaped half-cell of lithium ion is to have the graphene-based metal oxide composite of three-dimensional structure as mentioned above for negative material, just very lithium metal, electrolyte is ethyl carbonate or the dimethyl carbonate solution of lithium hexafluorophosphate solution.

The present invention adopts the two-dimensional graphene of monolayer carbon atomic structure as carrier uniform load metal oxide, some crosslinking agents auxiliary under, prepared the graphene-based metal oxide nano composite material of three-dimensional structure by simple two-step method.The advantages such as the method has technique simple, mild condition, with low cost.The metal oxide nanoparticles obtained by the inventive method equably load, on Graphene skeleton, obtains the three-dimensional structure that aperture size is more unified simultaneously.Prove through electro-chemical test, obtained composite material has excellent cyclical stability and high rate performance; Experiment proves, at 200mAg -1charging or discharging current under, the discharge capacity of obtained tin dioxide material can reach 950mAhg -1, at 50mAg -1charging or discharging current under, titania meterial discharge capacity can reach 150mAhg -1.Therefore, the present invention is that metal oxide provides good experimental data and theories integration at the investigation and 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 object of the present invention, characteristic sum effect fully.

Accompanying drawing explanation

Fig. 1 is that the pattern TEM of the graphene-based metal oxide nano-sheet of embodiments of the invention 1 schemes.

Fig. 2 is the shape appearance figure of the three-dimensional grapheme Base Metal tin ash aeroge of embodiments of the invention 1; Wherein, the SEM figure of embodiment 1 a), b) is respectively, c) for the TEM of embodiment 1 schemes.

Fig. 3 is pattern and the structure chart of the three-dimensional grapheme based metal oxide titanium aeroge of embodiments of the invention 2; Wherein, a) for the SEM of embodiment 2 schemes, b) for the XRD of embodiment 2 schemes.

Fig. 4 is embodiments of the invention 3, the pattern of the three-dimensional grapheme Base Metal tin ash aeroge of 4,5 and structure chart; Wherein, a), b), embodiment 3 c) is respectively, 4, the SEM figure of 5.

Fig. 5 is the cycle performance figure of three-dimensional graphite thiazolinyl tin dioxide composite material as lithium ion battery negative material of embodiments of the invention 1.

Fig. 6 is the graphene-based tin ash of embodiments of the invention 1 and the three-dimensional graphite thiazolinyl tin dioxide composite material high rate performance figure as lithium ion battery negative material.

Fig. 7 is the graphene-based titanium oxide of embodiments of the invention 2 and the three-dimensional grapheme based titanium dioxide composite material cycle performance figure as lithium ion battery negative material.

Fig. 8 is the graphene-based titanium oxide of embodiments of the invention 2 and the three-dimensional grapheme based titanium dioxide composite material high rate performance figure as lithium ion battery negative material.

Fig. 9 is embodiments of the invention 3, and the graphene-based tin ash of 4,5 and the three-dimensional graphite thiazolinyl tin dioxide composite material of different crosslinking agent are as the high rate performance figure of lithium ion battery negative material.

Embodiment

Embodiment 1

The first step, prepare graphene-based stannic oxide nanometer sheet:

(1) by ultrasonic for the dimethyl formamide solution (100mL) of 1mg/mL graphene oxide, the dispersion liquid mixed is formed;

(2) in above-mentioned dispersion liquid, add water and the hydrochloric acid of 25mL, regulate pH value of solution to 3; Add butter of tin (SnCl with vigorous stirring 45H 2o), add at 80 DEG C 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 deionized 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) get the PVA aqueous solution adding 1mL in the viscous fluid of the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 DEG C;

Wherein, the consumption mass ratio of graphene oxide and PVA is 1:0.0021;

(2) by the above-mentioned reacted block obtained, after freeze drying 48h, through N 2protect lower 300 DEG C of calcining carbonization 2h, finally obtain the graphene-based tin dioxide composite material of three-dimensional structure, SEM and the TEM photo of this material is as a)-c of Fig. 2) shown in.

Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) using gained composite material as lithium ion battery negative material, carry out electro-chemical test to the button-shaped half-cell of this lithium ion, its cycle performance figure, high rate performance figure are respectively as shown in Figure 5,6.

Wherein, RGO/SnO 2for assisting crosslinked graphene-based tin ash as charge and discharge curve, the RGO/SnO of lithium ion battery negative material without crosslinking agent 2/ PVA assists crosslinked obtaining to have the charge and discharge curve of three-dimensional graphene-based tin dioxide composite material as lithium ion battery negative material through PVA.As can be seen from Figure 5 the composite material of this three-dimensional structure shows higher capacity (1000mAhg -1), and very superior cycle performance.It still remains 950mAhg after 80 circle circulations -1capacity, do not carry out the 900mAhg that PVA assists crosslinked material capacity then in the past ten circles -1drop to only 500mAhg -1.As shown in Figure 6, there is three-dimensional material at 8Ag -1big current under still maintain 100mAhg -1capacity, this is very excellent high rate performance concerning tin dioxide material.

Embodiment 2

The first step, prepare three-dimensional grapheme based titanium dioxide

(1) by ultrasonic for the dimethyl formamide solution (100mL) of 1mg/mL graphene oxide, the dispersion liquid mixed is formed;

(2) in above-mentioned dispersion liquid, add water and the concentrated sulfuric acid of 25mL, regulate pH value of solution to 1; Add butyl titanate (TBT) under ice-water bath and vigorous stirring, add at 80 DEG C of insulation 12h, cooling;

Wherein, the TBT of interpolation and the quality amount ratio of graphene oxide are 1.5:1.

(3) undertaken centrifugal by above-mentioned reacted solution, spend deionized water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL, is graphene-based titanium dioxide nanometer sheet.

The graphene-based titanium dioxide aeroge of second step, preparation three-dimensional structure:

(1) get the PVA aqueous solution adding 1mL in the viscous fluid of the graphene-based titanium dioxide nanometer sheet of the above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 DEG C;

Wherein, the consumption mass ratio of graphene oxide and PVA is 1:0.0021;

(2) block will obtained after above-mentioned reaction, after freeze drying 48h, through N 2protect lower 300 DEG C 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 as Fig. 3 a), b).

Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) using gained composite material as lithium ion battery negative material, carry out electro-chemical test to the button-shaped half-cell of this lithium ion, its cycle performance figure, high rate performance figure are respectively as shown in Figure 7,8.Wherein, RGO/TiO 2/ PVA and RGO/TiO 2be respectively PVA to assist the graphene-based titanium oxide composite material of crosslinked three-dimensional, do not have PVA to assist the crosslinked graphene-based titanium oxide obtained as the charge/discharge curve of lithium ion battery negative material.As can be seen from Figure 7, obtained three-dimensional composite material demonstrates higher capacity (150mAhg -1) and very superior cycle performance.It still remains 150mAhg after 150 circle circulations -1capacity, and do not carry out PVA and assist the capacity of crosslinked material to be 121mAhg -1.As shown in Figure 8, three-dimensional composite material is at 5000mAg -1big current under still maintain 50mAhg -1capacity.

Embodiment 3

The first step, prepare graphene-based stannic oxide nanometer sheet:

(1) by ultrasonic for the dimethyl formamide solution (100mL) of 1mg/mL graphene oxide, the dispersion liquid mixed is formed;

(2) in above-mentioned dispersion liquid, add water and the hydrochloric acid of 25mL, regulate pH value of solution to 3; Add butter of tin (SnCl with vigorous stirring 45H 2o), add at 80 DEG C 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 deionized water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL, be graphene-based stannic oxide nanometer sheet.

The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:

(1) get the F127 aqueous solution adding 1mL in the viscous fluid of the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 DEG C;

Wherein, the consumption mass ratio of graphene oxide and F127 is 1:0.0021;

(2) by the above-mentioned reacted block obtained, after freeze drying 48h, through N 2protect lower 300 DEG C of calcining carbonization 2h, finally obtain the graphene-based tin dioxide 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) using gained composite material as lithium ion battery negative material, carry out electro-chemical test to the button-shaped half-cell of this lithium ion, its high rate performance figure as shown in Figure 9.Wherein, RGO/SnO 2/ F127 is the discharge curve of graphene-based tin dioxide composite material as lithium ion battery negative material that F127 assists crosslinked three-dimensional.As can be seen from Figure 9 the composite material of this three-dimensional structure shows higher capacity (700mAhg -1), and very superior multiplying power and cycle performance.As shown in Figure 9, there is three-dimensional material and still maintain 231mAhg under the big current of 8A/g -1capacity, and do not have crosslinking agent to assist crosslinked RGO/SnO 2material then only has 26mAhg -1capacity; When large current density after-current returns to 0.2A/g, after 140 circle charge and discharge circulations, capacity is also stabilized in 500mAhg -1, the material not carrying out being cross-linked then is decayed comparatively serious, and after 140 circle charge and discharge circulations, capacity attenuation is to 278mAhg -1, therefore three-dimensional structure shows very excellent high rate performance and stability concerning tin dioxide material.

Embodiment 4

The first step, prepare graphene-based stannic oxide nanometer sheet:

(1) by ultrasonic for the dimethyl formamide solution (100mL) of 1mg/mL graphene oxide, the dispersion liquid mixed is formed;

(2) in above-mentioned dispersion liquid, add water and the hydrochloric acid of 25mL, regulate pH value of solution to 3; Add butter of tin (SnCl with vigorous stirring 45H 2o), add at 80 DEG C 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 deionized water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL, be graphene-based stannic oxide nanometer sheet.

The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:

(1) get the GO solution adding 1mL in the viscous fluid of the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 DEG C;

Wherein, the consumption mass ratio of graphene oxide and GO is 1:1;

(2) by the above-mentioned reacted block obtained, after freeze drying 48h, through N 2protect lower 300 DEG C of calcining carbonization 2h, finally obtain the graphene-based tin dioxide 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) using gained composite material as lithium ion battery negative material, carry out electro-chemical test to the button-shaped half-cell of this lithium ion, its high rate performance figure as shown in Figure 9.Wherein, RGO/SnO 2/ GO is the discharge curve of graphene-based tin dioxide composite material as lithium ion battery negative material that GO assists crosslinked three-dimensional.As can be seen from Figure 9 the composite material of this three-dimensional structure shows very superior multiplying power and cycle performance.As shown in Figure 9, there is three-dimensional material and have 120mAhg under the big current of 8A/g -1capacity, when and do not have crosslinking agent to assist crosslinked RGO/SnO 2material then only has 26mAhg -1capacity; When large current density after-current returns to 0.2A/g, after 140 circle charge and discharge circulations, RGO/SnO 2/ GO capacity is also stabilized in 558mAhg -1, the material not carrying out being cross-linked then is decayed comparatively serious, and after 140 circle charge and discharge circulations, capacity attenuation is to 278mAhg -1, therefore the tin dioxide material of three-dimensional structure shows very excellent high rate performance and stability.

Embodiment 5

The first step, prepare graphene-based stannic oxide nanometer sheet:

(1) by ultrasonic for the dimethyl formamide solution (100mL) of 1mg/mL graphene oxide, the dispersion liquid mixed is formed;

(2) in above-mentioned dispersion liquid, add water and the hydrochloric acid of 25mL, regulate pH value of solution to 3; Add butter of tin (SnCl with vigorous stirring 45H 2o), add at 80 DEG C 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 deionized water, repeated centrifugation, washing operation three times, the thick liquid of simmer down to 5mg/mL, be graphene-based stannic oxide nanometer sheet.

The graphene-based tin ash aeroge of second step, preparation three-dimensional structure:

(1) get the PO solution adding 1mL in the viscous fluid of the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 DEG C;

Wherein, the consumption mass ratio of graphene oxide and PO is 1:1;

(2) by the above-mentioned reacted block obtained, after freeze drying 48h, through N 2protect lower 300 DEG C of calcining carbonization 2h, finally obtain the graphene-based tin dioxide 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) using gained composite material as lithium ion battery negative material, carry out electro-chemical test to the button-shaped half-cell of this lithium ion, its high rate performance figure as shown in Figure 9.Wherein, RGO/SnO 2/ PO is the discharge curve of graphene-based tin dioxide composite material as lithium ion battery negative material that PO assists crosslinked three-dimensional.As can be seen from Figure 9 the composite material of this three-dimensional structure shows higher capacity (900mAhg -1), and very superior multiplying power and cycle performance.As shown in Figure 9, there is three-dimensional material and still maintain 120mAhg under the big current of 8A/g -1capacity, and do not have crosslinking agent to assist crosslinked RGO/SnO 2material then only has 26mAhg -1capacity; When large current density after-current returns to 0.2A/g, after 140 circle charge and discharge circulations, RGO/SnO 2/ PO capacity is also stabilized in 900mAhg -1, the material not carrying out being cross-linked then is decayed comparatively serious, and after 140 circle charge and discharge circulations, capacity attenuation is to 278mAhg -1, therefore the tin dioxide material of three-dimensional structure shows very excellent high rate performance and stability.

More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of 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 (5)

1. a preparation method for the graphene-based metal oxide composite of three-dimensional structure, is characterized in that, comprise the following steps:
Step one, prepare graphene-based metal oxide nano-sheet:
First, be the graphene oxide dimethyl formamide solution of 1mg/mL by concentration, ultrasonic disperse is even;
Secondly, add metal oxide precursor in above-mentioned finely dispersed solution after, reaction is carried out 12 hours 60-90 DEG C of insulation;
Finally, undertaken centrifugal by above-mentioned reacted dispersion liquid, deionized water washs, the dispersion liquid of the concentrated graphene-based metal oxide nano-sheet obtained;
The graphene-based metal oxide aerogel of step 2, preparation three-dimensional structure:
First, dispersion liquid to above-mentioned graphene-based metal oxide nano-sheet is placed in the vial of 20mL, add a certain amount of auxiliary crosslinking agent, described auxiliary crosslinking agent is polyvinyl alcohol, polyethers F127 or expoxy propane, and graphene oxide and described auxiliary crosslinking agent are than being 1:0.0021 ~ 1:1; After mixing, vial is placed in the water heating kettle Direct Hydrothermal process of 150mL;
Secondly, by the block freeze drying that obtains after above-mentioned hydrothermal treatment consists and calcination processing, finally obtain the graphene-based metal oxide composite of three-dimensional structure.
2. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 1, it is characterized in that, described metal oxide precursor is stannic chloride pentahydrate or butyl titanate; 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.
3. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 1, is characterized in that, when auxiliary crosslinking agent be polyvinyl alcohol or polyethers F127 time, graphene oxide and described auxiliary crosslinking agent are than being 1:0.0021.
4. the preparation method of the graphene-based metal oxide composite of three-dimensional structure as claimed in claim 1, is characterized in that, when auxiliary crosslinking agent is expoxy propane, graphene oxide and described auxiliary crosslinking agent are than being 1:1.
5. the application of graphene-based metal oxide composite in lithium ion battery of the three-dimensional structure that the preparation method according to any one of Claims 1-4 obtains.
CN201310256496.4A 2013-06-25 2013-06-25 The preparation method of the graphene-based metal oxide composite of three-dimensional structure and application thereof CN103346301B (en)

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