CN104810509B - Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application - Google Patents
Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application Download PDFInfo
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Abstract
The invention discloses ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application.The structure is uniformly to be formed by the ferriferrous oxide particles with multilevel hierarchy after graphene network winding parcel, and the content of graphene is well below similar composite construction in composite construction.Graphene network not only effectively increases the electrical conductivity of ferroso-ferric oxide negative material, effectively volumetric expansion of the ferroso-ferric oxide during charge and discharge cycles is buffered, the submicron particles that ferroso-ferric oxide is self-assembled into size uniformity are additionally aided, the chemical property of negative material is effectively increased.The present invention uses a step solvent-thermal method, based on collaboration self assembly effect, using ethylene glycol water mixed system, assembled while by realizing ferroso-ferric oxide and graphene oxide, the two assembling process influence each other and mutually promoted, and obtain a kind of ferroso-ferric oxide of stabilization/graphene oxide composite aquogel.Method is simple to operate, and process is easily controlled and realized, environment-friendly.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material and its based on collaboration self assembly mechanism preparation method, especially
It is to be related to a kind of method for preparing ferroso-ferric oxide/graphite composite material, belongs to advanced nano composite material fabricating technology
Field and field of lithium ion battery.
Background technology
With the development of current electric automobile, it is desirable to which lithium ion battery of new generation has higher specific capacity and more excellent
High rate performance.Negative material is to constitute one of pith of lithium ion battery, and the negative material of Current commercial is mainly
Natural or electrographite, because of its relatively low specific capacity（372mAhg-1）The energy density of serious restriction lithium ion battery, and
There is also certain potential safety hazard for the relatively low intercalation potential of carbon material.Therefore, new negative material is explored, it is further improved
Capacity, becomes particularly necessary and important.Current transition metal oxide material because its have higher specific capacity, safety and stability with
And be also therefore a research heat of current research work as the more promising negative material of a class the advantages of easily prepare
Point.
Wherein, ferroso-ferric oxide is due to its high theoretical capacity（924mAhg-1）, it is with low cost, environment-friendly and relatively
High electrical conductivity is particularly paid close attention to by people.Ferroso-ferric oxide is to be based on " conversion reaction ", i.e. Fe in charge and discharge process3+Meeting
Fe is reduced into, larger volumetric expansion is caused, causes the efflorescence caved in the electrode destruction of crystal structure, seriously restricts it and follow
The ring life-span.Conventional ameliorative way is mainly two kinds at present, and one is the design of nanostructured, especially multistage or loose structure
Structure, the Volume Changes that cause during lithium ion turnover can be alleviated to a certain extent；Two be the preparation of composite,
It is combined using the preferable class material of electric conductivity, its electric conductivity can also be increased while receiving volume expands, can be with
Its chemical property is substantially improved, conventional composite mainly includes carbon, graphene etc..And the structure of three-dimensional network composite
It is to combine two kinds of method of modifying to build, the characteristics of having the two concurrently, thus increasingly by the pro-gaze of researcher.Particularly four
The synthesis of Fe 3 O/graphene composite material is even more the previous popular research topic of mesh.Such as Sun and its team are reported
A kind of in-situ synthetic method of three-dimensional grapheme/ferroso-ferric oxide, as negative electrode of lithium ion battery in use, with excellent
Storage lithium performance and cyclical stability（Chem. Comm. DOI: 10.1039/c4cc08949a）.Cheng and its team use
Original position calcining or a kind of three-dimensional structure of graphene-supported ferroso-ferric oxide, still keep close after 100 circulations
600mAhg-1Specific capacity（Chem. Mater. 2010, 22, 5306–5313）.But current research is one-sided concentration
In the self assembly of ferroso-ferric oxide or graphene, the rare report of research on the two collaboration self assembly.In addition, four oxidations three
In iron/graphene composite material how ensure its excellent performance on the premise of as far as possible reduce graphene consumption, still no
To good solution.
The content of the invention
In order to overcome the shortcomings of current ferroso-ferric oxide/graphene composite structure negative material and preparation method thereof, this hair
First bright purpose is to provide a kind of three-dimensional composite network structure, wherein the ferriferrous oxide particles with multilevel hierarchy are uniform
By graphene network wind wrap up, while the content of graphene is well below similar composite construction in composite construction.Stone
Black alkene network not only effectively increases the electrical conductivity of ferroso-ferric oxide negative material, has effectively buffered ferroso-ferric oxide in discharge and recharge
Volumetric expansion in cyclic process, additionally aids the submicron particles that ferroso-ferric oxide is self-assembled into size uniformity, effectively improves
The chemical property of negative material.Second object of the present invention is to provide the preparation method of said structure.It is molten using a step
The hot method of agent, based on collaboration self assembly effect during the course of the reaction, three-dimensional can be formed under relatively low graphene oxide concentration
Composite network structure, significantly reduces the consumption of graphene.In addition, the preparation method is with low cost, technique is simple, prepare
Ferroso-ferric oxide/oxidized graphite composite material excellent electrochemical performance.In addition, we additionally provide the lithium using the structure
Ion battery negative pole and lithium ion battery.
A kind of ferroso-ferric oxide/graphene three dimensional composite structure, the main composition of the composite construction is Fe3O4/ graphene；
A diameter of 180 ~ 700nm of wherein spherical ferroso-ferric oxide, and with hierarchy, described hierarchy is by primary particle
Assemble；The three-dimensional network being made up of graphene, winds and coats any one ferriferrous oxide particles, forms stable be combined
Structure, it is 0.6% ~ 6% that graphene, which accounts for composite mass fraction percentage,.
The average diameter of described ferriferrous oxide particles uses 180 ~ 210nm, and graphene accounts for composite mass fraction
Percentage is 3% ~ 4%.
Under freeze-drying state, described composite construction is ferroso-ferric oxide/graphene aerogel.
A kind of preparation method of described composite construction, the collaboration self assembly effect based on ferroso-ferric oxide and graphene oxide
Should, from ferric trichloride, enuatrol, graphene oxide water solution be raw material, during solvent thermal reaction, ferroso-ferric oxide by
Submicron particles of the nano-particles self assemble formation with hierarchy, simultaneous oxidation graphene occurs to reduce and be self-assembly of
The gluey three-dimensional grapheme network structure of water-setting, and the two self assembling processes influence each other and promote, it is final to obtain one
Stable ferroso-ferric oxide/graphene three dimensional composite structure.
Described preparation method, step is as follows：
1）The graphene oxide water solution of different volumes is added in ethylene glycol solution, stirred, yellowish-brown is formed
Ethylene glycol-water mixed system；
2）Ferric trichloride and enuatrol are added in mixed liquor, continues to stir more than 3h, forms stable suspension；
3）Above-mentioned mixed solution is put into reactor, solvent thermal reaction is carried out, heat treatment temperature is 160-240 DEG C, heat
Processing time is 12-24h, is cooled to cleaning after room temperature, and vacuum drying obtains ferroso-ferric oxide/graphene composite structure.
Further carry out step 4）, step 3）Described ferroso-ferric oxide/graphene composite structure by calcination processing,
To remove the organic matter of residual.
Described preparation method, step 1）In the concentration of used graphene oxide water solution be 2mg/mL, ethylene glycol-
0.067 ~ 0.67mg/mL of corresponding concentration in water mixed system；
Step 2）The concentration range of the ferric trichloride of middle addition is 0.05-0.2 mol/L, and the concentration range of enuatrol is
0.02-0.33 mol/L。
Described step 4）In calcination condition be 400-600 DEG C, 5 DEG C/min of heating rate, soaking time is 60-
180min, and be heat-treated under an inert atmosphere.
A kind of negative electrode of lithium ion battery, negative material is used as using described ferroso-ferric oxide/graphene composite structure.
A kind of lithium ion battery, using described negative pole, can be embedded in/the positive pole of deintercalate lithium ions and between described
Electrolyte composition between negative pole and positive pole.
Beneficial effects of the present invention：
1. three-dimensional ferroso-ferric oxide/graphene composite structure that the present invention is provided, the parcel of graphene uniform has multistage
The ferriferrous oxide particles of structure, the structure can effectively solve volumetric expansion and conduction of the composite construction in charge and discharge process
Property difference the problems such as.The structure is obtained by a step solvent-thermal method, and using ethylene glycol-water mixed system, table is used as by the use of enuatrol
Face activating agent and reaction promoter, based on the collaboration self assembly principle in course of reaction, ferroso-ferric oxide and graphene oxide difference
Generation self assembly, and the two self assembling processes interact and promote, and can be obtained under relatively low graphene oxide concentration
Structural integrity, the composite of excellent performance are obtained, the consumption of graphene oxide can be greatly reduced in the industrial production.The party
Method is simple to operate, prepares speed soon, yield is high, process safety is controllable, the potentiality with industrialization large-scale production.
2. three-dimensional network ferroso-ferric oxide/graphene composite material that the present invention is provided is as negative electrode of lithium ion battery material
Material, first discharge specific capacity is up to 1600mAhg-1, by 500 circulations, capacity is positively retained at 1160mAhg-1More than, capacity
Conservation rate is more than 95%（Calculated by second of discharge capacity）.
Brief description of the drawings
Fig. 1 is that the experiment Reaction Mechanisms of the invention provided and the ferroso-ferric oxide formed/graphene three-dimensional are multiple
Close the schematic diagram of structure.
Fig. 2 is the product that is obtained after not be the same as Example and the corresponding experiment condition next step solvent thermal reaction of comparative example
Optical photograph.In order to contrast conveniently, Fig. 2 is divided into a-f parts, wherein, a：The corresponding product of embodiment 2；b：Comparative example 3 is corresponding
Product；c：The corresponding product of embodiment 3；d：The corresponding product of comparative example 4；e：The corresponding product of embodiment 1；f：5 pairs of comparative example
The product answered.
Fig. 3 is corresponding pure ferroso-ferric oxide and ferroso-ferric oxide/graphene composite wood in comparative example 1 and embodiment 2
The microstructural photographs of material, in order to contrast conveniently, Fig. 3 is divided into a-f parts, wherein, a, b：The SEM and TEM of product shine in comparative example 1
Piece；c-f：SEM, TEM and HRTEM photo of product in embodiment 2.
Fig. 4 includes a, b part, is respectively not added with and adds the diameter distribution of ferriferrous oxide particles after graphene oxide
Figure.
Fig. 5 is the correspondingly TEM photos of product, including a-d parts, wherein a under different experimental conditions：Embodiment 3；b：Implement
Example 2；c：Embodiment 4；d：Embodiment 5；
Fig. 6 is embodiment 2（Fe3O4/G）, comparative example 1（bare Fe3O4）With comparative example 2（Fe3O4-G mixed）Middle product
It is used as cycle performance figure during lithium ion battery negative material；
Fig. 7 is embodiment 2（Fe3O4/G）, comparative example 1（bare Fe3O4）With comparative example 2（Fe3O4-G mixed）Middle product
It is used as high rate performance during lithium ion battery negative material and corresponding electrochemical impedance spectrogram.
Embodiment
With reference to embodiment, the present invention is described in further detail.It should be understood that these embodiments are only used for
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
As shown in figure 1, a kind of ferroso-ferric oxide/graphene three dimensional composite structure, the composition of the composite is Fe3O4/ stone
A diameter of 180 ~ the 700nm of black alkene, wherein ferriferrous oxide particles, and with hierarchy, is specifically by primary particle assembling
Into.Graphene network uniformly winds coated ferroferric oxide particle, and the composite construction of formation can be had by freeze-drying
Magnetic ferroso-ferric oxide/graphene aerogel.The mass percent that graphene accounts for composite is 0.6%-6%.
Preferably, described ferriferrous oxide particles size adjustable can select 180 ~ 210nm to one of which.
Preferably, described graphene mass fraction is 3 ~ 4% to one of which.
As shown in figure 1, the preparation of ferroso-ferric oxide/graphene three dimensional composite structure is to use a step solvent-thermal method, it is based on
Cooperate with self assembly principle.Using ethylene glycol-water mixed system, group while by realizing ferroso-ferric oxide and graphene oxide
Dress, the two assembling process influence each other and mutually promoted, and obtain a kind of ferroso-ferric oxide of stabilization/graphene oxide Compound Water
Gel.Self assembly obtains the submicron particles of size uniformity, as shown in Figure 4.Pass through contrast test, it has been found that single oxidation
Graphene solution occurs assembling and requires concentration in more than 0.5mg/mL（Fig. 2）, but if the assembling of ferroso-ferric oxide is introduced, i.e.,
Make that in graphene oxide concentration as little as 0.067mg/mL composite aquogel can also be formed（Fig. 2）, in addition, simple in order to exclude
Fe3+Influence, we have done comparative example 5, find the assembling without ferroso-ferric oxide, can not be formed under very high concentration
Three-dimensional composite aquogel.Contrast test proves correct and its to the critical assembling concentration of graphene the shadow of collaboration self assembly principle
Ring.
The experimentation that the technical program is specifically taken is as follows：
1）The graphene oxide water solution of different volumes is added in ethylene glycol solution, stirred at room temperature, is formed
Filemot ethylene glycol-water mixed system；
2）A certain amount of ferric trichloride and enuatrol are added in mixed liquor, continues to stir more than 3h at ambient temperature,
Form stable suspension；
3）Above-mentioned mixed solution is put into reactor, solvent thermal reaction is carried out, heat treatment temperature is 160-240 DEG C, heat
Processing time is 12-24h, is cooled to after room temperature and uses alcohol washes, in 30-100 DEG C of vacuum drying, obtain ferroso-ferric oxide/
Graphene composite material.
4）The composite is used for before lithium ion battery negative material, calcination processing need to be passed through, it is residual to remove surface
The organic matter stayed.
Embodiment 1
Take 2mL graphene oxide water solutions（2mg/mL）It is added in 28mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring, formed and 0.8g ferric trichlorides are added after stable turbid solution.Stirring more than 3 hours, is formed
The yellowish-brown suspension of stable uniform, is put into 50mL water heating kettles by mixed liquor and is placed into 200 DEG C and be heat-treated.It is incubated 24 small
When after naturally cool to room temperature, product formation hydrogel（Such as Fig. 2 e parts）, after washing separation is dried, obtain the magnetic of black
Powder.
Embodiment 2
Take 6mL graphene oxide water solutions（2mg/mL）It is added in 24mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring, formed and 0.8g ferric trichlorides are added after stable turbid solution.Stirring more than 3 hours, is formed
The yellowish-brown suspension of stable uniform, is put into 50mL water heating kettles by mixed liquor and is placed into 200 DEG C and be heat-treated.It is incubated 24 small
When after naturally cool to room temperature, product formation hydrogel（Such as Fig. 2 a parts）, after washing separation is dried, obtain the magnetic of black
Powder.In order to remove residual organic matter, 500 DEG C need to be carried out to product under an inert atmosphere and be heat-treated 180 minutes, by obtained powder
End is as negative material, and dispensing pasting is assembled into button cell and carries out electrochemical property test.
Embodiment 3
Take 4mL graphene oxide water solutions（2mg/mL）It is added in 26mL ethylene glycol solutions, is stirring evenly and then adding into
0.8g enuatrols proceed stirring, formed and 1.32g ferric trichlorides are added after stable turbid solution.Stirring more than 3 hours, is formed
The yellowish-brown suspension of stable uniform, is put into 50mL water heating kettles by mixed liquor and is placed into 180 DEG C and be heat-treated.It is incubated 18 small
When after naturally cool to room temperature, product formation hydrogel（Such as Fig. 2 b parts）, after washing separation is dried, obtain the magnetic of black
Powder.
Embodiment 4
Take 8mL graphene oxide water solutions（2mg/mL）It is added in 22mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring, formed and 0.8g ferric trichlorides are added after stable turbid solution.Stirring more than 3 hours, is formed
The yellowish-brown suspension of stable uniform, is put into 50mL water heating kettles by mixed liquor and is placed into 200 DEG C and be heat-treated.It is incubated 20 small
When after naturally cool to room temperature, product formation hydrogel after washing separation is dried, obtains the Magnaglo of black.
Embodiment 5
Take 10mL graphene oxide water solutions（2mg/mL）It is added in 20mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring, formed and 0.8g ferric trichlorides are added after stable turbid solution.Stirring more than 3 hours, is formed
The yellowish-brown suspension of stable uniform, is put into 50mL water heating kettles by mixed liquor and is placed into 200 DEG C and be heat-treated.It is incubated 20 small
When after naturally cool to room temperature, product formation hydrogel after washing separation is dried, obtains the Magnaglo of black.
Comparative example 1
1.6g enuatrols are dissolved in 30mL ethylene glycol solutions, 0.8g ferric trichlorides are stirring evenly and then adding into, room temperature is stirred
Mix more than 3 hours, remaining condition is identical with embodiment 2.Obtained powder is made button cell by dispensing pasting and carried out
Electrochemical property test（Its pattern is as shown in Fig. 3 a and b parts, performance of lithium ion battery such as Fig. 6 and Fig. 7）.
Comparative example 2
1.6g enuatrols are dissolved in 30mL ethylene glycol solutions, 0.8g ferric trichlorides are stirring evenly and then adding into, room temperature is stirred
Mix more than 3 hours, by washing separation drying, obtain black powder.The oxygen of the quality such as addition and embodiment 2 in black powder
Graphite alkene, carries out physical grinding, is carried out after being well mixed with implementing the calcining of 2 identicals, dispensing pasting and making button electricity
Pond is handled, and equally tests its chemical property（Performance is as shown in Figure 6 and Figure 7）.
Comparative example 3
Take 6mL graphene oxide water solutions（2mg/mL）It is added in 24mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring.After 3 hours, the brown suspension of stable uniform is formed, mixed liquor is put into 50mL water
Hot kettle is placed into 200 DEG C and is heat-treated.Insulation naturally cools to room temperature, product formation hydrogel after 24 hours（Fig. 2 b
Part）.
Comparative example 4
Take 4mL graphene oxide water solutions（2mg/mL）It is added in 26mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring.After 3 hours, the brown suspension of stable uniform is formed, mixed liquor is put into 50mL water
Hot kettle is placed into 200 DEG C and is heat-treated.Insulation naturally cools to room temperature after 24 hours, and product does not form the water of black
Gel (Fig. 2 d parts).
Comparative example 5
Take 6mL graphene oxide water solutions（2mg/mL）It is added in 24mL ethylene glycol solutions, is stirring evenly and then adding into
1.6g enuatrols proceed stirring, formed and 1.32g ferric trichlorides are added after stable turbid solution（Ensure Fe3+Concentration is with implementing
Example 2 is identical）.Stirring more than 3 hours, forms the yellowish-brown suspension of stable uniform, mixed liquor is put into 50mL water heating kettle juxtapositions
Enter and be heat-treated in 200 DEG C.Insulation naturally cools to room temperature after 24 hours, and product does not form hydrogel (Fig. 2 f portions
Point).
In summary, in conjunction with the embodiments 1,2,4 and comparative example 3,4, it can be deduced that the addition of pure zirconia graphene is 4mL
When cannot form hydrogel, and in the case of ferroso-ferric oxide and graphene oxide are simultaneous, graphene oxide is added
Measure to be even as low as 2mL for 4mL and remain unchanged and can obtain composite construction, it was demonstrated that the presence of collaboration self assembly effect.
In conjunction with the embodiments 2 and comparative example 1 and 2 can obtain, described composite construction compares pure ferriferrous oxide particles
With preferable storage lithium performance, its specific capacity and cycle life are also above equivalent graphene and the sample of ferroso-ferric oxide physical mixed
Product.
Claims (5)
1. a kind of preparation method of ferroso-ferric oxide/graphene three dimensional composite structure, it is characterised in that
The main composition of the composite construction is Fe3O4/ graphene；A diameter of 180 ~ 700nm of wherein spherical ferroso-ferric oxide, and
With hierarchy, described hierarchy is assembled by primary particle；Graphene accounts for composite construction mass fraction percentage
Than for 0.6% ~ 6%；
Collaboration self assembly effect of the described preparation method based on ferroso-ferric oxide and graphene oxide, from ferric trichloride, oil
Sour sodium, graphene oxide water solution are raw material, and during solvent thermal reaction, ferroso-ferric oxide is formed by nano-particles self assemble
Submicron particles with hierarchy, simultaneous oxidation graphene occurs to reduce and be self-assembly of the gluey three-dimensional graphite of water-setting
Alkene network structure, winds and coats any one ferriferrous oxide particles, and the two self assembling processes influence each other and promoted,
Finally obtain a stable ferroso-ferric oxide/graphene three dimensional composite structure；
Step is as follows：
1）The graphene oxide water solution of different volumes is added in ethylene glycol solution, stirred, filemot second is formed
Glycol-water mixed system；
2）Ferric trichloride and enuatrol are added in mixed liquor, continues to stir more than 3h, forms stable suspension；
3）Above-mentioned mixed solution is put into reactor, solvent thermal reaction is carried out, heat treatment temperature is 160-240 DEG C, heat treatment
Time is 12-24h, is cooled to cleaning after room temperature, and vacuum drying obtains ferroso-ferric oxide/graphene composite structure；
Step 1）In the concentration of used graphene oxide water solution be 2mg/mL, correspondence is dense in ethylene glycol-water mixed system
Spend 0.067 ~ 0.67mg/mL；
Step 2）The concentration range of the ferric trichloride of middle addition is 0.05-0.2 mol/L, and the concentration range of enuatrol is 0.02-
0.33 mol/L。
2. preparation method as claimed in claim 1, it is characterised in that further carry out step 4）, step 3）Four described oxygen
Change three-iron/graphene composite structure by calcination processing, to remove the organic matter of residual.
3. preparation method according to claim 2, it is characterised in that：Described step 4）In calcination condition be 400-
600 DEG C, 5 DEG C/min of heating rate, soaking time is 60-180min, and is heat-treated under an inert atmosphere.
4. a kind of negative electrode of lithium ion battery, it is characterised in that：Four oxygen obtained using the preparation method as described in claim 1
Change three-iron/graphene composite structure and be used as negative material.
5. a kind of lithium ion battery, it is characterised in that：Using negative pole as claimed in claim 4, can be embedded in/removal lithium embedded from
The positive pole of son and the electrolyte composition between the negative pole and positive pole.
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