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 PDF

Info

Publication number
CN107579241A
CN107579241A CN201710863464.9A CN201710863464A CN107579241A CN 107579241 A CN107579241 A CN 107579241A CN 201710863464 A CN201710863464 A CN 201710863464A CN 107579241 A CN107579241 A CN 107579241A
Authority
CN
China
Prior art keywords
graphene
metal oxide
dimensional
nano composite
tent type
Prior art date
Application number
CN201710863464.9A
Other languages
Chinese (zh)
Other versions
CN107579241B (en
Inventor
潘宇飞
何博
陆敏
李九霄
兰亮
Original Assignee
上海工程技术大学
常州阿德凡斯新材料科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海工程技术大学, 常州阿德凡斯新材料科技有限公司 filed Critical 上海工程技术大学
Priority to CN201710863464.9A priority Critical patent/CN107579241B/en
Priority claimed from CN201710863464.9A external-priority patent/CN107579241B/en
Publication of CN107579241A publication Critical patent/CN107579241A/en
Application granted granted Critical
Publication of CN107579241B publication Critical patent/CN107579241B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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

A kind of preparation of three-dimensional tent type graphene-metal oxide nano composite material Method
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.
CN201710863464.9A 2017-09-22 Preparation method of three-dimensional tent type graphene-metal oxide nano composite material Active CN107579241B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710863464.9A CN107579241B (en) 2017-09-22 Preparation method of three-dimensional tent type graphene-metal oxide nano composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710863464.9A CN107579241B (en) 2017-09-22 Preparation method of three-dimensional tent type graphene-metal oxide nano composite material

Publications (2)

Publication Number Publication Date
CN107579241A true CN107579241A (en) 2018-01-12
CN107579241B CN107579241B (en) 2021-04-09

Family

ID=

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103346301A (en) * 2013-06-25 2013-10-09 上海交通大学 Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material
CN103496693A (en) * 2013-09-23 2014-01-08 郑州大学 Method for preparing Fe3O4 nanoparticle/graphene composite material by sol electrostatic self-assembly process and application thereof
CN103540291A (en) * 2013-08-09 2014-01-29 牡丹江师范学院 Layered three-dimensional graphene/gamma-ferric oxide ferromagnetic nanosheet array and synthetic method thereof
CN103787326A (en) * 2014-03-06 2014-05-14 南开大学 Preparation method of grapheme material with three-dimensional network structure
US20150280217A1 (en) * 2013-03-11 2015-10-01 William Marsh Rice University Three-dimensional graphene-backboned architectures and methods of making the same
CN105000886A (en) * 2015-07-13 2015-10-28 郑州大学 Macroscopic three-dimensional ultralight Fe3O4 doped graphene aerogel composite material and preparation method
CN105355866A (en) * 2015-10-16 2016-02-24 上海应用技术学院 Preparation method of cobaltosic oxide composite graphene three-dimensional aerogel
CN105826541A (en) * 2016-06-14 2016-08-03 中科探能(北京)科技有限公司 Graphene-doped stannic-oxide-based lithium nano battery cathode material and preparation method
CN106252607A (en) * 2016-08-11 2016-12-21 郑州大学 Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof
CN106848233A (en) * 2017-02-20 2017-06-13 中国地质大学(北京) A kind of redox graphene mangano-manganic oxide three-dimensional composite material preparation method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150280217A1 (en) * 2013-03-11 2015-10-01 William Marsh Rice University Three-dimensional graphene-backboned architectures and methods of making the same
CN103346301A (en) * 2013-06-25 2013-10-09 上海交通大学 Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material
CN103540291A (en) * 2013-08-09 2014-01-29 牡丹江师范学院 Layered three-dimensional graphene/gamma-ferric oxide ferromagnetic nanosheet array and synthetic method thereof
CN103496693A (en) * 2013-09-23 2014-01-08 郑州大学 Method for preparing Fe3O4 nanoparticle/graphene composite material by sol electrostatic self-assembly process and application thereof
CN103787326A (en) * 2014-03-06 2014-05-14 南开大学 Preparation method of grapheme material with three-dimensional network structure
CN105000886A (en) * 2015-07-13 2015-10-28 郑州大学 Macroscopic three-dimensional ultralight Fe3O4 doped graphene aerogel composite material and preparation method
CN105355866A (en) * 2015-10-16 2016-02-24 上海应用技术学院 Preparation method of cobaltosic oxide composite graphene three-dimensional aerogel
CN105826541A (en) * 2016-06-14 2016-08-03 中科探能(北京)科技有限公司 Graphene-doped stannic-oxide-based lithium nano battery cathode material and preparation method
CN106252607A (en) * 2016-08-11 2016-12-21 郑州大学 Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof
CN106848233A (en) * 2017-02-20 2017-06-13 中国地质大学(北京) A kind of redox graphene mangano-manganic oxide three-dimensional composite material preparation method

Similar Documents

Publication Publication Date Title
Chen et al. Enhanced structural stability of nickel–cobalt hydroxide via intrinsic pillar effect of metaborate for high-power and long-life supercapacitor electrodes
Zhao et al. Recent developments and understanding of novel mixed transition‐metal oxides as anodes in lithium ion batteries
Patel et al. Transition-metal-based layered double hydroxides tailored for energy conversion and storage
Wang et al. One-step accurate synthesis of shell controllable CoFe 2 O 4 hollow microspheres as high-performance electrode materials in supercapacitor
Tang et al. A highly electronic conductive cobalt nickel sulphide dendrite/quasi-spherical nanocomposite for a supercapacitor electrode with ultrahigh areal specific capacitance
Cao et al. Recent progress in conversion reaction metal oxide anodes for Li-ion batteries
Zhang et al. Nanostructured transition metal oxides as advanced anodes for lithium-ion batteries
Liu et al. Ultrasmall TiO2 nanoparticles in situ growth on graphene hybrid as superior anode material for sodium/lithium ion batteries
Yu et al. Decorating nanoporous ZIF-67-derived NiCo 2 O 4 shells on a Co 3 O 4 nanowire array core for battery-type electrodes with enhanced energy storage performance
Guan et al. CoO hollow cube/reduced graphene oxide composites with enhanced lithium storage capability
Tompsett et al. Rutile (β-) MnO2 surfaces and vacancy formation for high electrochemical and catalytic performance
Li et al. Ultra small and highly dispersed Fe3O4 nanoparticles anchored on reduced graphene for supercapacitor application
Zhu et al. Rational design of octahedron and nanowire CeO 2@ MnO 2 core–shell heterostructures with outstanding rate capability for asymmetric supercapacitors
Xing et al. Fabrication and shape evolution of CoS2 octahedrons for application in supercapacitors
Xu et al. Hierarchical mesoporous NiCo 2 O 4@ MnO 2 core–shell nanowire arrays on nickel foam for aqueous asymmetric supercapacitors
Zhang et al. Hierarchical porous MnO2/CeO2 with high performance for supercapacitor electrodes
Cheng et al. Recent development of metal hydroxides as electrode material of electrochemical capacitors
Li et al. Ruthenium based materials as electrode materials for supercapacitors
Xia et al. Solution synthesis of metal oxides for electrochemical energy storage applications
Liu et al. Recent Progress of TiO 2-Based Anodes for Li Ion Batteries.
Lee et al. Cobalt-based compounds and composites as electrode materials for high-performance electrochemical capacitors
Tian et al. Bio-template synthesized NiO/C hollow microspheres with enhanced Li-ion battery electrochemical performance
Yan et al. Research advances of amorphous metal oxides in electrochemical energy storage and conversion
Wang et al. Electrode materials with tailored facets for electrochemical energy storage
Kong et al. The specific capacitance of sol–gel synthesised spinel MnCo2O4 in an alkaline electrolyte

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant