CN104810509A - Ferroferric oxide/graphene three-dimensional composite structure as well as preparation method and application thereof - Google Patents
Ferroferric oxide/graphene three-dimensional composite structure as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ferroferric oxide/graphene three-dimensional composite structure as well as a preparation method and application thereof. The structure is formed in the way that ferroferric oxide particles adopting multilevel structures are uniformly twined and coated by a graphene mesh, and the content of graphene in the composite structure is far lower than that in the congeneric composite structure. The graphene mesh not only effectively improves the conductivity of a ferroferric oxide anode material, and effectively buffers volume expansion of ferroferric oxide in the charge-discharge cyclic process, but also contributes to self-formation of ferroferric oxide into submicron particles with uniform sizes, and effectively improves the electrochemical performance of the anode material. The structure adopts a one-step solvothermal method, is based on a synergetic self-formation effect, adopts an ethanediol-water mixing system, and realizes simultaneous formation of ferroferric oxide and oxidized graphene so as to obtain a stable ferroferric oxide/oxidized graphene compound hydrogel, wherein the two formation processes are in mutual influence and mutual promotion. The method is simple in operation, the process is easy to control and realize, and the environment can be protected.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material and the preparation method based on collaborative self assembly mechanism thereof, particularly relate to a kind of method preparing tri-iron tetroxide/graphite composite material, belong to advanced Nano-composite materials technology field and field of lithium ion battery.
Background technology
Along with the development of current power automobile, require that the lithium ion battery of a new generation has higher specific capacity and more excellent high rate performance.Negative material is one of pith forming lithium ion battery, and the negative material mainly natural or electrographite of Current commercial, because of the specific capacity (372mAhg that it is lower
-1) energy density of serious restriction lithium ion battery, and also there is certain potential safety hazard in the lower intercalation potential of material with carbon element.Therefore, explore novel negative material, improve its capacity further, become particularly necessary and important.Current transition metal oxide material has the advantages such as higher specific capacity, safety and stability and easy preparation because of it, and therefore become the more promising negative material of a class, be also a study hotspot of current research work.
Wherein, tri-iron tetroxide is due to its high theoretical capacity (924mAhg
-1), with low cost, environmental friendliness and relatively high conductivity particularly receive the concern of people.Tri-iron tetroxide is based on " conversion reaction ", i.e. Fe in charge and discharge process
3+can Fe be reduced into, cause larger volumetric expansion, cause caving in of crystal structure to destroy with the efflorescence of electrode, serious its cycle life of restriction.At present conventional ameliorative way mainly two kinds, one is the design of nanostructure, and the structure of especially multistage or loose structure, can alleviate the change in volume caused in lithium ion turnover process to a certain extent; Two is preparations of composite material, and adopt the good class material of conductivity to carry out compound, can also increase its conductivity while receiving volume expands, can greatly improve its chemical property, conventional composite material mainly comprises carbon, Graphene etc.And the structure of three-dimensional network composite material is combined by two kinds of method of modifying, the feature of both, the parent being thus more and more subject to researcher looks at.The particularly research topic of the synthesis of the tri-iron tetroxide/graphene composite material previous hot topic of order especially.Such as Sun and team thereof report a kind of in-situ synthetic method of three-dimensional grapheme/tri-iron tetroxide, when it can be used as lithium ion battery negative to use, there is excellent storage lithium performance and cyclical stability (Chem. Comm. DOI:10.1039/c4cc08949a).Cheng and team thereof adopt the three-dimensional structure of original position calcining or a kind of graphene-supported tri-iron tetroxide, and 100 circulations still keep close to 600mAhg later
-1specific capacity (Chem. Mater. 2010,22,5306 – 5313).But current research just unilaterally concentrates on the self assembly of tri-iron tetroxide or Graphene, the rare report of the research about the two collaborative self assembly.In addition, under the prerequisite ensureing its excellent performance, how to reduce the consumption of Graphene in tri-iron tetroxide/graphene composite material as far as possible, still can not get good solution.
Summary of the invention
In order to overcome the deficiency of current tri-iron tetroxide/graphene composite structure negative material and preparation method thereof, first object of the present invention is to provide a kind of three-dimensional composite network structure, the ferriferrous oxide particles wherein with multilevel hierarchy is wound around parcel by Graphene network uniformly, simultaneously in composite construction the content of Graphene well below similar composite construction.Graphene network not only effectively improves the conductivity of tri-iron tetroxide negative material, effectively cushion the volumetric expansion of tri-iron tetroxide in charge and discharge cycles process, also contribute to the submicron particles that tri-iron tetroxide is self-assembled into size uniformity, effectively improve the chemical property of negative material.Second object of the present invention is to provide the preparation method of said structure.Adopt a step solvent-thermal method, based on the collaborative self assembly effect in course of reaction, three-dimensional composite network structure can be formed under lower graphene oxide concentration, significantly reduce the consumption of Graphene.In addition, this preparation method is with low cost, technique simple, the tri-iron tetroxide/oxidized graphite composite material excellent electrochemical performance of preparation.In addition, we additionally provide the lithium ion battery negative and lithium ion battery that adopt described structure.
A kind of tri-iron tetroxide/Graphene three dimensional composite structure, this composite construction mainly consist of Fe
3o
4/ Graphene; Wherein the diameter of spherical tri-iron tetroxide is 180 ~ 700nm, and has hierarchy, and described hierarchy is assembled by primary particle; The three-dimensional network be made up of Graphene, be wound around and any one ferriferrous oxide particles coated, form stable composite construction, it is 0.6% ~ 6% that Graphene accounts for composite material mass fraction percentage.
The average diameter of described ferriferrous oxide particles adopts 180 ~ 210nm, and it is 3% ~ 4% that Graphene accounts for composite material mass fraction percentage.
Under freeze drying state, described composite construction is tri-iron tetroxide/graphene aerogel.
A kind of preparation method of described composite construction, based on the collaborative self assembly effect of tri-iron tetroxide and graphene oxide, ferric trichloride, enuatrol, graphene oxide water solution is selected to be raw material, in solvent thermal reaction process, tri-iron tetroxide is formed the submicron particles with hierarchy by nano-particles self assemble, there is reduction and the three-dimensional grapheme network configuration of self assembly formation water-setting glue in simultaneous oxidation Graphene, and these two self assembling processes influence each other and promote, tri-iron tetroxide/Graphene three dimensional composite structure that final acquisition one is stable.
Described preparation method, step is as follows:
1) graphene oxide water solution of different volumes is joined in ethylene glycol solution, stir, form filemot ethylene glycol-water mixed system;
2) in mixed liquor, add ferric trichloride and enuatrol, continue to stir more than 3h, form stable suspension-turbid liquid;
3) above-mentioned mixed solution is put into reactor, carry out solvent thermal reaction, heat treatment temperature is 160-240 DEG C, and heat treatment time is 12-24h, and cool to room temperature cleans later, vacuumize, obtains tri-iron tetroxide/graphene composite structure.
Carry out step 4) further, the tri-iron tetroxide/graphene composite structure described in step 3) passes through calcination processing, to remove residual organic substance.
Described preparation method, the concentration of graphene oxide water solution used in step 1) is 2mg/mL, corresponding concentration 0.067 ~ 0.67mg/mL in ethylene glycol-water mixed system;
Step 2) in the concentration range of ferric trichloride that adds be 0.05-0.2 mol/L, the concentration range of enuatrol is 0.02-0.33 mol/L.
Calcination condition in described step 4) is 400-600 DEG C, heating rate 5 DEG C/min, and temperature retention time is 60-180min, and heat treatment under an inert atmosphere.
A kind of lithium ion battery negative, the tri-iron tetroxide/graphene composite structure described in employing is as negative material.
A kind of lithium ion battery, the negative pole described in employing, can the embed/positive pole of deintercalate lithium ions and the electrolyte composition between described negative pole and positive pole.
beneficial effect of the present invention:
1. three-dimensional tri-iron tetroxide/graphene composite structure provided by the invention, the parcel of graphene uniform has the ferriferrous oxide particles of multilevel hierarchy, and this structure effectively can solve the problem such as volumetric expansion and poorly conductive of composite construction in charge and discharge process.This structure is obtained by a step solvent-thermal method, adopt ethylene glycol-water mixed system, utilize enuatrol as surfactant and reaction promoter, based on the collaborative self assembly principle in course of reaction, there is self assembly respectively in tri-iron tetroxide and graphene oxide, and these two self assembling processes interact and promote, can obtain the composite material of structural integrity, excellent performance under lower graphene oxide concentration, can reduce the consumption of graphene oxide in the industrial production greatly.The method is simple to operate, and preparation speed is fast, and productive rate is high, and process safety is controlled, has the potentiality of industrialization large-scale production.
2. three-dimensional network tri-iron tetroxide/graphene composite material provided by the invention is as lithium ion battery negative material, and first discharge specific capacity can reach 1600mAhg
-1, through 500 circulations, capacity can remain on 1160mAhg
-1above, capability retention is more than 95% (calculating by second time discharge capacity).
Accompanying drawing explanation
Fig. 1 is experiment Reaction Mechanisms provided by the invention and the schematic diagram of tri-iron tetroxide/Graphene three dimensional composite structure that formed.
Fig. 2 is the optical photograph of the product obtained after next step solvent thermal reaction of experiment condition corresponding to different embodiment and comparative example.In order to contrast conveniently, Fig. 2 is divided into a-f part, wherein, and a: the product of embodiment 2 correspondence; B: the product of comparative example 3 correspondence; C: the product of embodiment 3 correspondence; D: the product of comparative example 4 correspondence; E: the product of embodiment 1 correspondence; F: the product of comparative example 5 correspondence.
Fig. 3 is pure tri-iron tetroxide corresponding in comparative example 1 and embodiment 2 and the microstructural photographs of tri-iron tetroxide/graphene composite material, and in order to contrast conveniently, Fig. 3 is divided into a-f part, wherein, and a, b: SEM and the TEM photo of product in comparative example 1; C-f: SEM, TEM and HRTEM photo of product in embodiment 2.
Fig. 4 comprises a, b part, is respectively the diameter distribution profile not adding and add ferriferrous oxide particles after graphene oxide.
Fig. 5 is the TEM photo of corresponding product under different experimental conditions, comprises a-d part, wherein a: embodiment 3; B: embodiment 2; C: embodiment 4; D: embodiment 5;
Fig. 6 is embodiment 2(Fe
3o
4/ G), comparative example 1(bare Fe
3o
4) and comparative example 2(Fe
3o
4-G mixed) in product as cycle performance figure during lithium ion battery negative material;
Fig. 7 is embodiment 2(Fe
3o
4/ G), comparative example 1(bare Fe
3o
4) and comparative example 2(Fe
3o
4-G mixed) in product as high rate performance during lithium ion battery negative material and corresponding electrochemical impedance spectrogram.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.But should be understood that these embodiments only for illustration of and be not used in and limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
As shown in Figure 1, a kind of tri-iron tetroxide/Graphene three dimensional composite structure, this composite material consist of Fe
3o
4/ Graphene, wherein ferriferrous oxide particles diameter is 180 ~ 700nm, and has hierarchy, is specifically assembled by primary particle.Graphene network is wound around coated ferroferric oxide particle uniformly, and the composite construction of formation can obtain the magnetic tri-iron tetroxide/graphene aerogel of tool through freeze drying.The mass percent that Graphene accounts for composite material is 0.6%-6%.
Wherein preferably a kind of, described ferriferrous oxide particles size adjustable, can select 180 ~ 210nm.
Wherein preferably a kind of, described Graphene mass fraction is 3 ~ 4%.
As shown in Figure 1, the preparation of tri-iron tetroxide/Graphene three dimensional composite structure is employing one step solvent-thermal method, based on collaborative self assembly principle.Adopt ethylene glycol-water mixed system, assemble while realizing tri-iron tetroxide and graphene oxide, these two assembling process influence each other and mutually promote, and obtain a kind of stable tri-iron tetroxide/graphene oxide composite aquogel.Self assembly obtains the submicron particles of size uniformity, as shown in Figure 4.Pass through contrast test, we find that single graphene oxide solution generation assembling requires that concentration is at more than 0.5mg/mL (Fig. 2), if but introduce the assembling of tri-iron tetroxide, even if composite aquogel (Fig. 2) also can be formed when graphene oxide concentration is low to moderate 0.067mg/mL, in addition, in order to get rid of simple Fe
3+impact, we have done comparative example 5, find not have the assembling of tri-iron tetroxide, even if can not form three-dimensional composite aquogel under very high concentration.Contrast test proves the correct of collaborative self assembly principle and the impact on the critical assembling concentration of Graphene thereof.
The experimentation that the technical program is specifically taked is as follows:
1) join in ethylene glycol solution by the graphene oxide water solution of different volumes, stirred at ambient temperature is even, forms filemot ethylene glycol-water mixed system;
2) in mixed liquor, add a certain amount of ferric trichloride and enuatrol, continue at ambient temperature to stir more than 3h, form stable suspension-turbid liquid;
3) above-mentioned mixed solution is put into reactor, carry out solvent thermal reaction, heat treatment temperature is 160-240 DEG C, heat treatment time is 12-24h, cool to room temperature uses alcohol washes later, 30-100 DEG C of vacuumize, obtains tri-iron tetroxide/graphene composite material.
4) before this composite material is used for lithium ion battery negative material, need through calcination processing, to remove the organic substance of remained on surface.
embodiment 1
Getting 2mL graphene oxide water solution (2mg/mL) joins in 28mL ethylene glycol solution, adds 1.6g enuatrol and proceeds to stir, add 0.8g ferric trichloride after forming stable turbid solution after stirring.Stir more than 3 hours, form the yellowish-brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 24 hours, product forms hydrogel (the e part as Fig. 2), and washing obtains the Magnaglo of black after being separated drying.
embodiment 2
Getting 6mL graphene oxide water solution (2mg/mL) joins in 24mL ethylene glycol solution, adds 1.6g enuatrol and proceeds to stir, add 0.8g ferric trichloride after forming stable turbid solution after stirring.Stir more than 3 hours, form the yellowish-brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 24 hours, product forms hydrogel (a part as Fig. 2), and washing obtains the Magnaglo of black after being separated drying.In order to remove residual organic matter, need carry out 500 DEG C of heat treatments 180 minutes under an inert atmosphere to product, using the powder that obtains as negative material, batching pasting is assembled into button cell and carries out electrochemical property test.
embodiment 3
Getting 4mL graphene oxide water solution (2mg/mL) joins in 26mL ethylene glycol solution, adds 0.8g enuatrol and proceeds to stir, add 1.32g ferric trichloride after forming stable turbid solution after stirring.Stir more than 3 hours, form the yellowish-brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 180 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 18 hours, product forms hydrogel (the b part as Fig. 2), and washing obtains the Magnaglo of black after being separated drying.
embodiment 4
Getting 8mL graphene oxide water solution (2mg/mL) joins in 22mL ethylene glycol solution, adds 1.6g enuatrol and proceeds to stir, add 0.8g ferric trichloride after forming stable turbid solution after stirring.Stir more than 3 hours, form the yellowish-brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 20 hours, product forms hydrogel, and washing obtains the Magnaglo of black after being separated drying.
embodiment 5
Getting 10mL graphene oxide water solution (2mg/mL) joins in 20mL ethylene glycol solution, adds 1.6g enuatrol and proceeds to stir, add 0.8g ferric trichloride after forming stable turbid solution after stirring.Stir more than 3 hours, form the yellowish-brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 20 hours, product forms hydrogel, and washing obtains the Magnaglo of black after being separated drying.
comparative example 1
Be dissolved in by 1.6g enuatrol in 30mL ethylene glycol solution, add 0.8g ferric trichloride after stirring, stirring at room temperature more than 3 hours, all the other conditions are identical with embodiment 2.The powder obtained is made button cell through batching pasting and is carried out electrochemical property test (, as shown in a and the b part of Fig. 3, performance of lithium ion battery is as Fig. 6 and Fig. 7 for its pattern).
comparative example 2
1.6g enuatrol is dissolved in 30mL ethylene glycol solution, after stirring, adds 0.8g ferric trichloride, stirring at room temperature more than 3 hours, be separated through washing dry, obtain black powder.The graphene oxide with quality such as embodiments 2 is added in black powder, carry out physical grinding, carry out the calcining identical with enforcement 2 after mixing, the pasting and make button cell process of preparing burden, same its chemical property of test (performance is as shown in Figure 6 and Figure 7).
comparative example 3
Getting 6mL graphene oxide water solution (2mg/mL) joins in 24mL ethylene glycol solution, adds 1.6g enuatrol and proceed to stir after stirring.After 3 hours, form the brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 24 hours, product forms hydrogel (the b part of Fig. 2).
comparative example 4
Getting 4mL graphene oxide water solution (2mg/mL) joins in 26mL ethylene glycol solution, adds 1.6g enuatrol and proceed to stir after stirring.After 3 hours, form the brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 24 hours, product does not form the hydrogel (the d part of Fig. 2) of black.
comparative example 5
Getting 6mL graphene oxide water solution (2mg/mL) joins in 24mL ethylene glycol solution, adds 1.6g enuatrol and proceeds to stir, add 1.32g ferric trichloride and (ensure Fe after forming stable turbid solution after stirring
3+concentration is identical with embodiment 2).Stir more than 3 hours, form the yellowish-brown suspension-turbid liquid of stable uniform, mixed liquor is put into 50mL water heating kettle and insert 200 DEG C and heat-treat.Be incubated and naturally cool to room temperature after 24 hours, product does not form hydrogel (the f part of Fig. 2).
In sum, in conjunction with the embodiments 1,2,4 and comparative example 3,4, the addition that can draw pure zirconia Graphene just can not form hydrogel when being 4mL, and under tri-iron tetroxide and the simultaneous situation of graphene oxide, graphene oxide addition is that 4mL is even low to moderate 2mL and still can obtains composite construction, proves the existence of collaborative self assembly effect.
In conjunction with the embodiments 2 and comparative example 1 and 2 can obtain, described composite construction is compared pure ferriferrous oxide particles and is had preferably storage lithium performance, and its specific capacity and cycle life are also higher than the sample of equivalent Graphene and tri-iron tetroxide physical mixed.
Claims (10)
1. tri-iron tetroxide/Graphene three dimensional composite structure, is characterized in that, this composite construction mainly consist of Fe
3o
4/ Graphene; Wherein the diameter of spherical tri-iron tetroxide is 180 ~ 700nm, and has hierarchy, and described hierarchy is assembled by primary particle; The three-dimensional network be made up of Graphene, be wound around and any one ferriferrous oxide particles coated, form stable composite construction, it is 0.6% ~ 6% that Graphene accounts for composite material mass fraction percentage.
2. composite construction according to claim 1, is characterized in that, the average diameter of described ferriferrous oxide particles adopts 180 ~ 210nm, and it is 3% ~ 4% that Graphene accounts for composite material mass fraction percentage.
3. composite construction according to claim 1, is characterized in that, under freeze drying state, described composite construction is tri-iron tetroxide/graphene aerogel.
4. the preparation method of a composite construction as claimed in claim 1 or 2, it is characterized in that, based on the collaborative self assembly effect of tri-iron tetroxide and graphene oxide, select ferric trichloride, enuatrol, graphene oxide water solution is raw material, in solvent thermal reaction process, tri-iron tetroxide is formed the submicron particles with hierarchy by nano-particles self assemble, there is reduction and the three-dimensional grapheme network configuration of self assembly formation water-setting glue in simultaneous oxidation Graphene, and these two self assembling processes influence each other and promote, tri-iron tetroxide/Graphene three dimensional composite structure that final acquisition one is stable.
5. preparation method as claimed in claim 4, it is characterized in that, step is as follows:
1) graphene oxide water solution of different volumes is joined in ethylene glycol solution, stir, form filemot ethylene glycol-water mixed system;
2) in mixed liquor, add ferric trichloride and enuatrol, continue to stir more than 3h, form stable suspension-turbid liquid;
3) above-mentioned mixed solution is put into reactor, carry out solvent thermal reaction, heat treatment temperature is 160-240 DEG C, and heat treatment time is 12-24h, and cool to room temperature cleans later, vacuumize, obtains tri-iron tetroxide/graphene composite structure.
6. preparation method as claimed in claim 5, is characterized in that, carry out step 4) further, and the tri-iron tetroxide/graphene composite structure described in step 3) passes through calcination processing, to remove residual organic substance.
7. preparation method according to claim 5, is characterized in that:
The concentration of graphene oxide water solution used in step 1) is 2mg/mL, corresponding concentration 0.067 ~ 0.67mg/mL in ethylene glycol-water mixed system;
Step 2) in the concentration range of ferric trichloride that adds be 0.05-0.2 mol/L, the concentration range of enuatrol is 0.02-0.33 mol/L.
8. preparation method according to claim 6, is characterized in that: the calcination condition in described step 4) is 400-600 DEG C, heating rate 5 DEG C/min, and temperature retention time is 60-180min, and heat treatment under an inert atmosphere.
9. a lithium ion battery negative, is characterized in that: the tri-iron tetroxide/graphene composite structure of employing described in claim 1 or 2 is as negative material.
10. a lithium ion battery, is characterized in that: adopt negative pole according to claim 9, can embed/positive pole of deintercalate lithium ions and the electrolyte composition between described negative pole and positive pole.
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