CN107579241A - A kind of preparation method of three-dimensional tent type graphene metal oxide nano composite material - Google Patents
A kind of preparation method of three-dimensional tent type graphene metal oxide nano composite material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of three-dimensional tent type graphene metal oxide nano composite material, refer to first prepare three-D nano-porous graphene using sol-gal process；Then obtained three-D nano-porous graphene is immersed in the collosol and gel containing initiator and metal ion, products therefrom is handled through supercritical carbon dioxide drying and calcination or directly dried through supercritical carbon dioxide, produces the three-dimensional tent type graphene metal oxide nano composite material.Preparation method of the present invention have technique it is simple, without additionally adding additive, cost is cheap, is easy to large-scale production; products obtained therefrom has the advantages that appearance structure is good, electrochemical performance; loose structure especially in gained three-dimensional grapheme is not to occur at random; average pore size is less than 10nm, avoids three-dimensional grapheme in the phenomenon for easily collapsing and accumulating with metal oxide compound tense.
Description
Technical field
The present invention is to be related to a kind of three-dimensional tent type graphene-metal oxide that can be used as lithium ion battery electrode material
The preparation method of nano composite material, belongs to technical field of material.
Background technology
The advantages of lithium ion battery is due to energy density height, good cycle, oneself is through extensive since its commercialization
Applied to portable electronic products, electric car and electrical network field, in particular with highlighting for energy and environment problem, lithium-ion electric
Pond has obtained increasing attention in the development of New Energy Industry.Electrode material is the pass for improving performance of lithium ion battery
Key.Graphene, English name Graphene, there is the tightly packed bi-dimensional cellular shape crystal structure formed of single layer of carbon atom,
Unique two-dimensional structure makes it have larger specific surface area, excellent electric conductivity and good mechanical performance, so make its
Lithium has a good application prospect from battery material.But the presence of two-dimensional structure cause graphene layer by layer between have
Stronger Van der Waals force, easily reunite and be piled into graphite flake, this defects of accumulating of reuniting seriously hinders graphene in electrode
Application in terms of material.
Three-dimensional grapheme is to be integrated to assemble by two-dimensional graphene, has continued the excellent physics and power of two-dimensional graphene
Performance is learned, in addition, relative to two-dimensional graphene, the unique three-dimensional porous structure of three-dimensional grapheme makes to which obviate reunion accumulation now
The generation of elephant, there is broader practice prospect in electrode material.But three-dimensional grapheme is when being used for electrode material, although tool
Have higher power density and cyclical stability, but energy density is relatively low, thus generally by its with metal oxide (such as：Oxygen
Change manganese, iron oxide, cobalt oxide, nickel oxide etc.) carry out compound, prepare the three-dimensional graphite for lithium ion battery electrode material
Alkene-metal oxide nano composite material.
When three-dimensional grapheme-metal oxide nano composite material (GMOs) is applied to lithium ion battery, nanoscale
Metal oxide particle and the graphene of high conductivity can effectively shorten the diffusion path of lithium ion, so as to reduce at electrode
Ohmic polarization effect, obtains better performance；Meanwhile loose structure also can effectively solve metal oxide body during lithiumation
The shortcomings that high rate performance caused by product expansion and poor circulation；Moreover, GMOs also has higher electricity as electrode material
Conductance and mechanical strength, excellent chemical stability, meanwhile, also there is higher energy density, its capacitance is compared to tradition
Graphite electrode improve 2~5 times.Above-mentioned advantage causes three-dimensional grapheme-metal oxide nano composite material in lithium ion
Great potential that field of batteries has and attracted the attention of a large number of researchers.
Relevant report at present on three-dimensional grapheme-metal oxide nano composite material is a lot, such as：Dong etc.
(Dong X,Wang X,Wang J,et al.Synthesis of a MnO2-graphene foam hybrid with
controlled MnO2particle shape and its use as a supercapacitor electrode[J]
.Carbon,2012,50(13):4865.) three-dimensional grapheme is prepared using chemical vapour deposition technique, then by three-dimensional grapheme with
Potassium permanganate hydro-thermal reaction 6 hours at 150 DEG C, the acidity of solution grows the MnO of different-shape during by controlling hydro-thermal2,
Three-dimensional grapheme/MnO is made2Composite；(Wang C, Xu J, Yuen M F, the et al.Hierarchical such as Wang
composite electrodes of nickel oxidenanoflake3D grapheme for high-performance
pseudocapacitors[J].Adv Funct Mater,2014,24(40):6372.) using nickel foam as template, microwave is utilized
NiO nanometer sheets are grown in three-dimensional grapheme surface by plasma chemical vapor deposition and hydro-thermal method, prepare three-dimensional grapheme/
NiO nanosheet composite materials；(Dong C X, Xu H, Wang X W, the et al.3D grapheme cobatlt such as Dong
oxide electrode for high-performance supercapacitor and enzymeless glucose
detection[J],ACS Nano,2012,6(4):3206.) it is prepared for three-dimensional graphite using chemical vapor deposition and hydro-thermal method
Alkene/Co3O4Composite；(Yu X, Lu B, the Xu Z.Super Long-Life Supercapacitors Based on such as Yu
the Construction of Nanohoneycomb-Like Strongly Coupled CoMoO4–3D Graphene
Hybrid Electrodes[J].Advanced Materials,2014,26(7):1044-1051.) by Co (NO3)2·6H2O
And NaMoO4·7H2O mixed solution carries out compound under hydrothermal conditions with three-dimensional grapheme prepared by CVD, prepares honeycomb
Shape three-dimensional grapheme/CoMoO4Composite.
Although domestic and foreign scholars answering in lithium ion battery for three-dimensional grapheme/metal oxide nano composite material
It has been used as substantial amounts of research, but the preparation technology of three-dimensional grapheme/metal oxide nano composite material is complex at present,
Operate relatively complicated, also need to add various extra additives (conductive agent, binding agent etc.) in preparation process, not only production cost
It is higher, it is also easy to introduce impurity effect product quality, is unfavorable for large-scale production.In addition, at present to three-dimensional grapheme/gold
In the preparation process for belonging to oxidate nano composite, the loose structure of three-dimensional grapheme occurs at random mostly, the chi in hole
The very little size for depending on template occurs at random in self assembling process, and its diameter is generally at hundreds of nanometers to hundreds of microns
Between, its larger-diameter hole reduces the mechanical property of three-dimensional grapheme so that three-dimensional grapheme is answered with metal oxide
It is very easy to collapse and accumulate during conjunction, have impact on the property of the three-dimensional grapheme/metal oxide nano composite material finally prepared
Can, limit application of the three-dimensional grapheme/metal oxide nano composite material in electrode material.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the invention to provide one kind can be used as lithium ion cell electrode
The preparation method of three-dimensional tent type graphene-metal oxide nano composite material of material.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of three-dimensional tent type graphene-metal oxide nano composite material, comprises the following steps：
A) it is placed in after being uniformly mixed ammoniacal liquor and graphene oxide water solution in closed reactor, at 80~90 DEG C
Lower insulation reaction until forming Graphene gel, after washing with supercritical carbon dioxide dried, most passed through afterwards by gained Graphene gel
Calcination processing is crossed, three-D nano-porous graphene is made；
B) obtained three-D nano-porous graphene is immersed in the sol-gel containing initiator and metal ion, institute
Obtain product to handle through supercritical carbon dioxide drying and calcination or directly dry through supercritical carbon dioxide, produce the three-dimensional account
Paulin type graphene-metal oxide nano composite material.
Preferably, the concentration of graphene oxide water solution is 1~2wt% in step a).
Preferably, ammonium hydroxide in the mixed solution that ammoniacal liquor and graphene oxide water solution are formed in step a)
(NH4OH concentration) is 0.3~0.6wt%.
Preferably, Graphene gel removes the ammonia in surface and hole through deionized water and acetone washing in step a)
Dried after water with supercritical carbon dioxide.
Preferably, the calcination processing in step a) refers to that dried product is protected in inert gas (such as nitrogen)
Under shield, 2~5 hours are incubated in 1000~1100 DEG C.
Preferably, step b) comprises the following steps：The alcohol solution of metal ion presoma and initiator are existed
Stir to it and be well mixed at room temperature, form colloidal sol, then three-D nano-porous graphene is immersed in colloidal sol, then in 30
~70 DEG C of ageings to the colloidal sol in reaction system forms gel, and then reaction system is directly done with supercritical carbon dioxide
It is dry, or calcination processing is carried out after reaction system is directly dried with supercritical carbon dioxide, produce three-dimensional tent type graphite
Alkene-metal oxide nano composite material.
As further preferred scheme, alcohol solution is formed by ethanol and water in step b), in colloidal sol, metal ion
Concentration is 0.05~1.4M, and the mol ratio of initiator and metal ion is 15:1~1:1 (with 15:1~5:1 is preferred).
Preferably, the metal oxide is selected from Fe2O3、SnO2、TiO2At least one of.
As further preferred scheme, when metal oxide is Fe2O3Or TiO2When, the initiator in step b) is oxidation
Propylene (i.e. expoxy propane)；When metal oxide is SnO2, step b) initiator is oxetanes (i.e. 1,3- epoxies third
Alkane).
As further preferred scheme, when metal oxide is Fe2O3When, the calcination processing in step b) refers to after drying
Product inert gas (such as nitrogen) protection under, in 500~600 DEG C be incubated 2~5 hours.
As further preferred scheme, when metal oxide is TiO2When, the calcination processing in step b) refers to after drying
Product under normal atmosphere, in 300~400 DEG C be incubated 3~7 hours.
As further preferred scheme, when metal oxide is SnO2When, without calcination processing in step b).
Compared with prior art, the present invention has following conspicuousness beneficial effect：
The present invention is prepared three-D nano-porous using ammoniacal liquor and graphene oxide water solution as raw material using sol-gel process
Graphene, then three-D nano-porous graphene is immersed in the sol-gel containing initiator and metal ion, three-dimensional is made
Tent type graphene-metal oxide nano composite material, preparation technology is simple, (conductive agent, is glued without additionally adding additive
Knot agent etc.), the interference that avoids Contamination On Mechanical Properties of Composite Materials, production cost is relatively low, is easy to large-scale production；Three prepared
Dimension tent type graphene-metal oxide nano composite material avoids the reunion of crystal, electrochemistry preferable with appearance structure
The advantages that excellent performance, there are preferable use value and application prospect on lithium ion battery electrode material；Especially, this hair
Bright obtained three-D nano-porous graphite is not only preferable with appearance structure, and specific surface area is big, and electrochemical performance etc. is excellent
Point, and loose structure is not to occur at random, and repetition stability is good, and average pore size is less than 10nm, and mechanical property is good, avoids three
Graphene is tieed up in the phenomenon for easily collapsing and accumulating with metal oxide compound tense so that three in prepared composite
There is excellent synergy between dimension graphene and metal oxide, and then cause composite that there is excellent electrochemistry
Energy.
Brief description of the drawings
Fig. 1 is the process chart that the present invention prepares three-dimensional tent type graphene-metal oxide nano composite material；
Fig. 2 is the TEM figures of three-D nano-porous graphene prepared by embodiment 1；
Fig. 3 is the SEM figures of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment 2；
Fig. 4 is the TEM figures of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment 2；
Fig. 5 is the TEM of three-dimensional tent type graphene-ferric oxide nano composite another angle prepared by embodiment 2
Figure；
Fig. 6 is the high-resolution TEM figures of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment 2；
Fig. 7 is the macroscopic cross section signal of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment 2
Figure；
Fig. 8 is the grain size distribution of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment 2；
Fig. 9 is the diffraction pattern of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment 2；
Figure 10 is the TEM figures after three-dimensional tent type graphene-circulation of ferric oxide nano composite 30 times of lithiumation state；
Figure 11 is the TEM figures of three-dimensional tent type graphene-TiOx nano composite prepared by embodiment 3；
Figure 12 be embodiment 1 prepare three-D nano-porous graphene, embodiment 2 prepare three-dimensional tent type graphene-
The pore size distribution figure of three-dimensional grapheme-TiOx nano composite prepared by ferric oxide nano composite and embodiment 3；
Figure 13 is the TEM figures of three-dimensional tent type graphene-tin oxide nano composite material prepared by embodiment 4.
Embodiment
With reference to specific embodiment and comparative example, technical solution of the present invention is described in further detail and completely.
Embodiment 1
First, graphene oxide water solution is prepared
By graphene oxide ultrasonic disperse in deionized water, it is water-soluble to be configured to the graphene oxide that concentration is 1~2wt%
Liquid, it is stand-by.
2nd, three-D nano-porous graphene is prepared
Take 3.5g, the graphene oxide water solution that concentration is 1.5wt%, adding appropriate ammoniacal liquor thereto, (concentration is more than
25wt% high-purity ammoniacal liquor), be uniformly mixed, so as to get mixed solution in ammonium hydroxide (NH4OH concentration) is
0.5wt%, then mixed solution is placed in closed reactor, insulation reaction 7.5 hours at 85 DEG C, forms graphene and coagulate
Glue, terminate reaction, gained Graphene gel is successively washed with deionized water and acetone, to remove the ammonium hydroxide in surface and hole
(NH4OH), then dried with supercritical carbon dioxide, gained desiccant gel is last under nitrogen protection, small in 1050 DEG C of calcinings 4
When, produce three-D nano-porous graphene.Its preparation process can be found in shown in Fig. 1.
In the present embodiment, the concentration of graphene oxide water solution can be any value in 1~2wt%；Graphene oxide,
In the mixed solution of ammoniacal liquor, the concentration of ammonium hydroxide can be any value in 0.3~0.6wt%；Insulation reaction temperature can be with
It is 80~90 DEG C；The insulation reaction time can be 7~8 hours；Calcining heat can be 1000~1100 DEG C, and calcination time can be with
It is 3~5 hours.
Fig. 2 is the TEM figures of three-D nano-porous graphene manufactured in the present embodiment；It can be seen that prepared by the present embodiment
Graphene be three-dimensional porous structure.
After tested, three-D nano-porous graphene manufactured in the present embodiment, its density are 65~70mgcm-3, compare surface
Product is 1500~1600m2·g-1, there is preferable appearance structure.
In addition, three-D nano-porous graphene manufactured in the present embodiment, its loose structure is stable, and nonrandom appearance, and
And the size in hole is smaller, average pore size is about 3~8.5nm, less than 10nm, more traditional hundreds of nanometers to hundreds of micron pore sizes
For three-dimensional grapheme so that three-D nano-porous graphene manufactured in the present embodiment subsequently with during the Material cladding such as oxide not
Occur and collapse and packing phenomenon.
After tested, three-D nano-porous graphene manufactured in the present embodiment, electrical conductivity about 2Scm-1, the material is as lithium
Ion electrode materials are in use, its current density is 100mAg-1, electric discharge and charging capacity are respectively 2603mAhg first-1
And 633mAhg-1, coulombic efficiency about 24%, wherein discharge capacity are reduced to 850mAhg after being circulated at second-1And at 30 times
About 405mAhg is stable at after circulation-1(current density 100mAg-1), there is excellent chemical property, be follow-up three
There is dimension graphene-metal oxide nano composite material excellent electrochemical performance to have laid good basis.
The three-D nano-porous graphene that the present embodiment is prepared can carry out follow-up according to the technological process shown in Fig. 1
The preparation of three-dimensional tent type graphene-metal oxide nano composite material.
Embodiment 2
Three-dimensional tent type graphene-iron oxide (Fe2O3) nano composite material preparation
By 2.27gFeCl3(0.014mol) is dissolved in 10mL, 60wt% ethanol water, adds 0.89g
(0.015mol) propylene oxide, being stirred at room temperature makes it well mixed, colloidal sol is formed, then by three wieners made from 1g embodiments 1
Rice porous graphene is impregnated in containing Fe3+In the colloidal sol of initiator, then formed in 40 DEG C of ageing to colloidal sols in reaction system
Gel, then directly to three-dimensional grapheme and Fe3+Reaction system directly dried with supercritical carbon dioxide, gained desciccate
Then under nitrogen protection, calcined 3 hours in 550 DEG C, produce three-dimensional tent type graphene-ferric oxide nano composite.Its
Preparation process can be found in shown in Fig. 1.
Fig. 3 is the SEM figures of three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment；Fig. 4 is this
The TEM figures of three-dimensional tent type graphene-ferric oxide nano composite prepared by embodiment；Fig. 5 is manufactured in the present embodiment three
Tie up the TEM figures of another angle of tent type graphene-ferric oxide nano composite；Fig. 6 is three-dimensional account manufactured in the present embodiment
The high-resolution TEM figures of paulin type graphene-ferric oxide nano composite；Graphene in Fig. 6 refers to three-dimensional grapheme；From figure
3 to Fig. 6 is visible, in three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment, iron oxide crystal along
Three-dimensional graphene framework is uniformly fixed on graphene film layer surface, and no crystal agglomeration occurs, also existing without collapsing and accumulating
As occurring, there is preferable appearance structure；Especially, as can be seen from Fig. 5, three-dimensional grapheme-ferric oxide nano composite grain
Polygon state is presented in two-dimensional projection direction in son, can be with by taking the two composite examples sectioned out in Fig. 5 with straight line as an example
Find out that three-dimensional grapheme effectively wraps iron oxide particles, three-dimensional grapheme-ferric oxide nano composite of formation is overall
In tent type.
Fig. 7 is the macroscopic cross section signal of three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment
Figure；It can be seen that three-dimensional grapheme is wrapped in iron oxide particles, and iron oxide particles are uniform along three-dimensional graphene framework
Graphene film layer surface is fixed on, composite is in integrally tent type.It is visible with reference to Fig. 5 and Fig. 7, nanometer manufactured in the present embodiment
Composite is tent type.
Fig. 8 is the grain size distribution of three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment；From
Visible in figure, three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment, particle diameter is smaller, belongs to nanometer
Rank, average grain diameter are 12.5 ± 5.5nm, and distribution is more uniform.
Fig. 9 is the diffraction pattern of three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment；From figure
It can be seen that the Fe in composite2O3By α and γ phase compositions.
After tested, three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment is as lithium-ion electric
During the materials'use of pole, its current density is 100mAg-1, and it is respectively 1365mAhg that it discharges with charging capacity first-1With
740mAh·g-1, coulombic efficiency about 54%, reversible capacity is stable at 777mAhg after 30 circulations-1, there is excellent electrification
Learn performance.
Figure 10 is three-dimensional tent type graphene-ferric oxide nano composite manufactured in the present embodiment as li-ion electrode
TEM figures during materials'use after (three-dimensional tent type graphene-ferric oxide nano composite of lithiumation state) 30 circulations；Figure
In centre circle is three-dimensional grapheme-ferric oxide nano composite particles, clearly demarcated, the deep stain of the depth in single particle
Part represents iron oxide particles, it can be seen that after 30 circulations, although nanocomposite particles are by initial polygon
Form (as shown in Figure 5) becomes oval or rounded form, but agglomeration does not occur for lithiumation state composite particles, and this says
Three-dimensional grapheme can effectively enwrapping ferric oxide particle, and play the work for preventing nanoparticle agglomerates in the composite of bright tent type
With.
Embodiment 3
Three-dimensional tent type graphene-titanium oxide (TiO2) nano composite material preparation
1g butyl titanates (0.0029mol), the μ L of 37wt% hydrochloric acid 71.4 are dissolved in 5mL, 95wt% ethanol water,
Being stirred at room temperature makes it well mixed, then adds 0.357g propylene oxides (0.0061mol), and being stirred at room temperature makes it mixed
Close uniformly, form colloidal sol, then three-D nano-porous graphene made from 1g embodiments 1 is impregnated in containing Ti4+With initiator
In colloidal sol, gel then is formed in 40 DEG C of ageings to the colloidal sol in reaction system, then directly to three-dimensional grapheme and Ti4+It is anti-
System is answered directly to be dried with supercritical carbon dioxide, then gained desciccate is calcined 5 hours at 350 DEG C and (calcined in atmosphere
Carry out, protected without nitrogen), produce three-dimensional tent type graphene-TiOx nano composite.
Figure 11 is the TEM figures of three-dimensional tent type graphene-TiOx nano composite manufactured in the present embodiment；It is white in figure
It is titan oxide particles in circle, it can be seen that in three-dimensional grapheme manufactured in the present embodiment-TiOx nano composite, oxygen
Change titanium crystal and be uniformly fixed on graphene film layer surface along three-dimensional graphene framework, no crystal agglomeration occurs, also without
Collapse and occur with packing phenomenon, there is preferable appearance structure.Also, the same embodiment of nano composite material manufactured in the present embodiment
2 nano composite materials prepared are the same, and tent type.
After tested：Three-dimensional grapheme manufactured in the present embodiment-TiOx nano composite particle diameter is smaller, belongs to nanoscale
Not, average grain diameter is 5.5 ± 0.6nm, and distribution is more uniform.
It is prepared by the nano composite material and embodiment 1 that composite nano materials manufactured in the present embodiment are prepared with embodiment 2
Three-dimensional grapheme under the same conditions, using BJH methods carry out pore size distribution test, test result is as shown in figure 12, from Figure 12
It can be seen that by the attaching process of metal oxide particle (iron oxide particles, Titanium particles), the micropore diameter distribution in material becomes
Change it is little, also, the pore-size distribution of graphene-metal oxide (iron oxide, titanium oxide) composite relative to graphene more
To be uniform.
After tested, three-dimensional tent type graphene-TiOx nano composite manufactured in the present embodiment is as lithium-ion electric
During the materials'use of pole, its current density is 100mAg-1, and it is respectively 1472mAhg that it discharges with charging capacity first-1With
492mAh·g-1, coulombic efficiency about 31%, reversible capacity is stable at 241mAhg after 30 circulations-1, there is excellent electrification
Learn performance.
Embodiment 4
Three-dimensional tent type graphene-tin oxide (SnO2) nano composite material preparation
By 0.65g SnCl4(0.0025mol), 1.03g oxetanes (0.018mol) are dissolved in 14mL, 58wt% second
In alcohol solution, being stirred at room temperature makes it well mixed, forms colloidal sol, then that three-dimensional manometer made from 1g embodiments 1 is more
Hole graphene is impregnated in containing Sn4+In the colloidal sol of initiator, gel then is formed in 40 DEG C of ageings to the colloidal sol in reaction system,
Then directly to three-dimensional grapheme and Sn4+Reaction system directly dried with supercritical carbon dioxide, produce three-dimensional tent type stone
Black alkene-tin oxide nano composite material.
Figure 13 is the TEM figures of three-dimensional tent type graphene-tin oxide nano composite material manufactured in the present embodiment；From figure
It can be seen that tin oxide crystal is along three-dimensional grapheme bone in three-dimensional grapheme-tin oxide nano composite material manufactured in the present embodiment
Frame is uniformly fixed on graphene film layer surface, and no crystal agglomeration occurs, and also occurs with packing phenomenon without collapsing, with compared with
Good appearance structure.Also, nano composite material manufactured in the present embodiment is the same with nano composite material prepared by embodiment 2,
And tent type.
After tested：Three-dimensional tent type graphene-tin oxide nano composite material particle diameter manufactured in the present embodiment is smaller, belongs to
Nano grade, average grain diameter are 4.6 ± 0.5nm, and distribution is more uniform.Three-dimensional tent type graphene-oxygen manufactured in the present embodiment
Change sijna nano composite material as li-ion electrode materials in use, its current density is 100mAg-1, its discharge first with
Charging capacity is respectively 1875mAhg-1And 679mAhg-1, coulombic efficiency about 45%, reversible capacity is stable after 30 circulations
In 747mAhg-1, there is excellent chemical property.
In summary, the present invention first prepares three-D nano-porous graphene using sol-gel process, then by three-dimensional graphite
Alkene is immersed in the sol-gel containing initiator and metal ion, and three-dimensional grapheme-metal oxide nano composite wood is made
Material, have preparation technology it is simple, without additionally adding additive (conductive agent, binding agent etc.), production cost is relatively low, is easy to scale
The advantages that metaplasia is produced；Also, prepared three-dimensional grapheme-metal oxide nano composite material is in tent type, composite
Middle metal oxide particle is uniformly fixed on graphene film layer surface along three-dimensional graphene framework, and is effectively wrapped by graphene
Wrap up in, effectively prevent crystal agglomeration, there is the advantages that appearance structure is preferable, electrochemical performance, in lithium ion battery
There are preferable use value and application prospect on electrode material；Especially, obtained three-D nano-porous graphite not only has
Appearance structure is preferable, and specific surface area is big, and the advantages that electrochemical performance, and loose structure is not to occur at random, repeats steady
Qualitative good, average pore size is less than 10nm, and mechanical property is good, avoids three-dimensional grapheme and is easily sent out with metal oxide compound tense
The raw phenomenon for collapsing and accumulating, for follow-up three-dimensional grapheme-metal oxide nano composite material preparation provide it is good
Basis；Compared to prior art, there are conspicuousness progress and industrial applications to be worth.
Finally need it is pointed out here that be：It the above is only the part preferred embodiment of the present invention, it is impossible to be interpreted as to this hair
The limitation of bright protection domain, those skilled in the art according to the present invention the above make some it is nonessential improvement and
Adjustment belongs to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of three-dimensional tent type graphene-metal oxide nano composite material, it is characterised in that including such as
Lower step：
A) it is placed in after being uniformly mixed ammoniacal liquor and graphene oxide water solution in closed reactor, is protected at 80~90 DEG C
Temperature reaction is until form Graphene gel, and gained Graphene gel is dried after washing with supercritical carbon dioxide, finally by forging
Burning processing, is made three-D nano-porous graphene；
B) obtained three-D nano-porous graphene is immersed in the sol-gel containing initiator and metal ion, gained production
Thing is handled through supercritical carbon dioxide drying and calcination or directly dried through supercritical carbon dioxide, produces the three-dimensional tent type
Graphene-metal oxide nano composite material.
2. preparation method according to claim 1, it is characterised in that：The concentration of graphene oxide water solution is in step a)
1~2wt%.
3. preparation method according to claim 1, it is characterised in that：Ammoniacal liquor and graphene oxide water solution shape in step a)
Into mixed solution in the concentration of ammonium hydroxide be 0.3~0.6wt%.
4. preparation method according to claim 1, it is characterised in that：Calcination processing in step a) refers to dried production
Thing is incubated 2~5 hours under inert gas shielding, in 1000~1100 DEG C.
5. preparation method according to claim 1, it is characterised in that step b) comprises the following steps：Before metal ion
The alcohol solution of drive body is stirred at room temperature to it with initiator to be well mixed, and colloidal sol is formed, then by three-D nano-porous stone
Black alkene is immersed in colloidal sol, then gel is formed in 30~70 DEG C of ageings to the colloidal sol in reaction system, then to reaction system
Directly it is dried with supercritical carbon dioxide, or is forged after reaction system is directly dried with supercritical carbon dioxide
Burning processing, produces three-dimensional tent type graphene-metal oxide nano composite material.
6. preparation method according to claim 1, it is characterised in that：The metal oxide is selected from Fe2O3、SnO2、TiO2
At least one of.
7. preparation method according to claim 6, it is characterised in that：When metal oxide is Fe2O3Or TiO2When, step
B) initiator in is propylene oxide；When metal oxide is SnO2When, step b) initiator is oxetanes.
8. preparation method according to claim 6, it is characterised in that：When metal oxide is Fe2O3When, in step b)
Calcination processing refers to dried product under inert gas shielding, and 2~5 hours are incubated in 500~600 DEG C.
9. preparation method according to claim 6, it is characterised in that：When metal oxide is TiO2When, forging in step b)
Burning processing refers to dried product under normal atmosphere, and 3~7 hours are incubated in 300~400 DEG C.
10. preparation method according to claim 6, it is characterised in that：When metal oxide is SnO2When, nothing in step b)
Need calcination processing.
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