CN106935805A - A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode - Google Patents
A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode Download PDFInfo
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- CN106935805A CN106935805A CN201710226990.4A CN201710226990A CN106935805A CN 106935805 A CN106935805 A CN 106935805A CN 201710226990 A CN201710226990 A CN 201710226990A CN 106935805 A CN106935805 A CN 106935805A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode, it is related to a kind of preparation method of self-supporting electrode.Present invention aim to address existing method prepare lithium ion battery self-supporting negative material present in yield poorly, specific capacity is low, circulation volume retention difference and high rate performance difference the problems such as.Method：First, solution is configured；2nd, mixed solution is prepared；3rd, product I is prepared；4th, the suspension for adding binding agent is prepared；5th, self-supporting material is prepared；6th, high-temperature calcination.The half-cell of the di-iron trioxide/Graphene self-supporting electrode assembling prepared using the present invention first takes 100mA/g to circulate 3 times, charge specific capacity is more than 600mAh/g after circulating 500 times using 1000mA/g again, for compared with initial charge specific capacity, capability retention is up to 89.79%.The present invention can obtain a kind of preparation method of di-iron trioxide/Graphene self-supporting electrode.
Description
Technical field
The present invention relates to a kind of preparation method of self-supporting electrode.
Background technology
With the development of science and technology, electrochemical energy storage device plays more and more important effect in clean energy resource of new generation.
Compared to the traditional chemical power supply such as plumbic acid, ickel-cadmium cell, lithium rechargeable battery is due to close with higher discharge voltage and energy
Degree, environmental protection and be widely used in portable electric appts, electric motor car and hybrid electric vehicle field.Lithium is commercialized at present
Ion battery cathode material is mainly graphite-like carbon material, but the relatively low theoretical specific capacity of graphite cathode (372mAh/g) is not
Can meet now to the demand of lithium ion battery with high energy density, it is easily produced because charging/discharging voltage platform is low in charging process
Give birth to Li dendrite and cause barrier film to puncture and battery short circuit, so as to trigger security incident.
Iron oxide is due to theoretical specific capacity (1007mAh/g) high, charging/discharging voltage platform higher and wide material sources, honest and clean
Valency, nontoxic, advantages of environment protection become the focus of research.
Graphene is due to conductive good, and specific surface area is high, the advantages of satisfactory mechanical property, is widely used in recent years
In the research of composite.Because iron oxide is non-conductive, and during as lithium ion battery electrode material, the meeting in charge and discharge process
More serious bulk effect is produced, therefore causes the rapid decay of capacity.Iron oxide is combined with both Graphenes, on the one hand
The nonconducting shortcoming of iron oxide is made up using Graphene satisfactory electrical conductivity, on the other hand generally alleviates oxygen using Graphene as skeleton
Change the bulk effect of iron so that material morphology structure has preferably holding, is conducive to the holding of capacity.
Self-supporting electrode refer to electrode active material in the case of not against collector, can independently as electrode assembling
Battery is used.The appearance of self-supporting electrode saves the use of collector, simplifies the preparation technology of electrode, shortens electrode
Preparation time, with actual application value.
Because hydro-thermal method is easily-synthesized morphology controllable, well-crystallized, purity material high, oxygen is synthesized using hydro-thermal method in recent years
Changing iron/Graphene self-supporting electrode material turns into the focus of research.
But the hydro-thermal method for using now prepares iron oxide/Graphene self-supporting electrode material and has the disadvantages that：(1) hydro-thermal
The molysite of mixed liquor and Graphene concentration are low in kettle so that yield poorly, far from the demand commercially produced is reached, to high concentration
Lower preparation technology lacks research；(2) Graphene generally prepares graphene oxide and the system of reducing using Hummers methods or its improved method
, Graphene yield prepared by the method is small, and the electric conductivity of reduced graphene is undesirable, have impact on the performance of material；(3) will
Obtained self-supporting electrode assembling is paid no attention into lithium ion battery, specific capacity, capacity retention, cycle performance and high rate performance
Think.
The content of the invention
Yield present in the lithium ion battery self-supporting negative material prepared present invention aim to address existing method
Low, specific capacity is low, circulation volume retention difference and high rate performance difference the problems such as, and propose a kind of di-iron trioxide/Graphene
The preparation method of self-supporting electrode.
A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode, is specifically realized by the following steps：
First, solution is configured：
1., molysite is dissolved in deionized water, iron salt solutions are obtained；
Step one 1. described in the volume ratio of quality and deionized water of molysite be (2g~5g):(5mL~40mL)；
2., urea is dissolved in deionized water, urea liquid is obtained；
Step one 2. described in the volume ratio of quality and deionized water of urea be (0.66g~2g):(5mL~
10mL)；
3., the graphene conductive liquid that Graphene mass fraction is 3% is added in deionized water, graphene dispersion is obtained
Liquid；
Step one 3. described in Graphene mass fraction be 3% graphene conductive liquid quality and deionized water body
Product is than being (4.93g~23.66g):(10mL~25mL)；
2nd, under low whipping speed is 150r/min~400r/min, iron salt solutions are dropwise added drop-wise to graphene dispersing solution
In, then low whipping speed is continuation stirring 20min~40min under 150r/min~400r/min, then urea liquid is dropwise instilled,
Low whipping speed is continuation stirring 20min~40min under 150r/min~400r/min again；Obtain mixed solution；
Iron salt solutions and the volume ratio of graphene dispersing solution described in step 2 are (5~40):(10~25)；
Iron salt solutions and the volume ratio of urea liquid described in step 2 are (5~40):(5~10)；
3rd, mixed solution is transferred in the water heating kettle containing polytetrafluoroethyllining lining, then will be containing in polytetrafluoroethylene (PTFE)
The water heating kettle of lining is reacted in oil bath, obtains product I；
Contain poly- four when the water heating kettle containing polytetrafluoroethyllining lining is reacted in oil bath described in step 3
Mixing speed in the water heating kettle of PVF liner is 100r/min~400r/min, and oil bath temperature is 110 DEG C~220 DEG C, oil
The bath reaction time is 4h~20h；
4th, the low whipping speed of product I that will be obtained in step 3 is magnetic agitation under 150r/min~400r/min
5min~10min, obtains finely dispersed suspension；To deionized water is added in finely dispersed suspension, bonding is added
Agent solution, then ultrasonic disperse 10min~30min, obtain adding the suspension of binding agent；
Finely dispersed suspension and the volume ratio of deionized water described in step 4 are 0.7:10；
The quality of the binder solution described in step 4 is 0.2g with the volume ratio of finely dispersed suspension:(0.5mL
~3mL)；
The suspension of the addition binding agent that the 5th, will be obtained in step 4 carries out vacuum filtration, obtains product II；Again by product
II and filter membrane be dried, finally remove filter membrane, obtain self-supporting material；
6th, self-supporting material is put into tube furnace, then by tube furnace with heating rate be 2 DEG C/min~5 DEG C/min's
Heating rate is warming up to 300 DEG C~800 DEG C, then calcines 0.5h~10h in the case where temperature is for 300 DEG C~800 DEG C, obtains three oxidations two
Iron/Graphene self-supporting electrode material.
Principle of the invention and advantage：
First, the present invention is with commercialization graphene conductive liquid (i.e. Graphene mass fraction is 3% graphene conductive liquid) generation
Graphene is prepared for traditional Hummers and its modified method, the graphene conductive for solving conventional method preparation is poor, it is impossible to big
The shortcoming that sizable application is produced in composite；
2nd, the present invention increases the concentration of molysite on the basis of conventional hydrothermal method, is conducive to further increasing yield；In water
One-step method fabricated in situ composite is used in hot kettle, and directly suction filtration, into self-supporting material, self-supporting material through and calcining
Treatment obtains di-iron trioxide/Graphene self-supporting electrode material, beneficial to Fe2O3Being uniformly distributed in Graphene；
3rd, iron salt solutions, urea liquid and graphene dispersing solution are mixed, the mixed liquor for obtaining, only 40mL mixed liquors
The yield of obtained di-iron trioxide/Graphene self-supporting electrode is just up to more than 2g；Electrochemical results show, of the invention
The discharge capacity first of the di-iron trioxide of preparation/Graphene self-supporting electrode has reached 937mAh/g, and initial charge capacity is
674mAh/g, coulombic efficiency is 72%；First take half-cell 100mA/g to circulate 3 times, then circulated 500 times using 1000mA/g,
Capacity gradually recovers in cyclic process, the charge specific capacity after circulation 500 times more than 600mAh/g, 100mA/ first
For g charge specific capacities, capability retention is up to 89.79%, and di-iron trioxide/Graphene self-supporting electricity prepared by the present invention
The high rate performance of pole is good, and specific capacity reaches 262mAh/g under 2000mA/g current densities, under 5000mA/g current densities
Specific capacity has reached 130mAh/g；And find that the di-iron trioxide/Graphene self-supporting electrode of present invention preparation has well
Invertibity, after circulating 10 times under 5000mA/g, when current density is recovered to 100mA/g, specific capacity remains to reach 570mAh/g.
The present invention can obtain a kind of preparation method of di-iron trioxide/Graphene self-supporting electrode.
Brief description of the drawings
Fig. 1 is the digital photograph figure of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one；
Fig. 2 is that di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one is activated under 100mA/g current densities
After 3 circulations, the cycle performance figure under 1000mAh/g current densities；
Fig. 3 be embodiment one prepare di-iron trioxide/Graphene self-supporting electrode 100 milliamperes/gram, 200 milliamperes/
Gram, 500 milliamperes/gram, 1000 milliamperes/gram, 2000 milliamperes/gram, 5000 milliamperes/gram, respectively circulate under 100 milliampere/gram current densities
The performance map of 10 times；
Fig. 4 is first three cyclic voltammetry curve of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one, 1
It is first time cyclic voltammetry curve, 2 is second cyclic voltammetry curve, and 3 is third time cyclic voltammetry curve；
Fig. 5 is the first charge-discharge curve of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one, and 1 is to fill
Electric curve, 2 is discharge curve；
Fig. 6 is the SEM figures of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of preparation method of di-iron trioxide/Graphene self-supporting electrode,
It is specifically realized by the following steps：
First, solution is configured：
1., molysite is dissolved in deionized water, iron salt solutions are obtained；
Step one 1. described in the volume ratio of quality and deionized water of molysite be (2g~5g):(5mL~40mL)；
2., urea is dissolved in deionized water, urea liquid is obtained；
Step one 2. described in the volume ratio of quality and deionized water of urea be (0.66g~2g):(5mL~
10mL)；
3., the graphene conductive liquid that Graphene mass fraction is 3% is added in deionized water, graphene dispersion is obtained
Liquid；
Step one 3. described in Graphene mass fraction be 3% graphene conductive liquid quality and deionized water body
Product is than being (4.93g~23.66g):(10mL~25mL)；
2nd, under low whipping speed is 150r/min~400r/min, iron salt solutions are dropwise added drop-wise to graphene dispersing solution
In, then low whipping speed is continuation stirring 20min~40min under 150r/min~400r/min, then urea liquid is dropwise instilled,
Low whipping speed is continuation stirring 20min~40min under 150r/min~400r/min again；Obtain mixed solution；
Iron salt solutions and the volume ratio of graphene dispersing solution described in step 2 are (5~40):(10~25)；
Iron salt solutions and the volume ratio of urea liquid described in step 2 are (5~40):(5~10)；
3rd, mixed solution is transferred in the water heating kettle containing polytetrafluoroethyllining lining, then will be containing in polytetrafluoroethylene (PTFE)
The water heating kettle of lining is reacted in oil bath, obtains product I；
Contain poly- four when the water heating kettle containing polytetrafluoroethyllining lining is reacted in oil bath described in step 3
Mixing speed in the water heating kettle of PVF liner is 100r/min~400r/min, and oil bath temperature is 110 DEG C~220 DEG C, oil
The bath reaction time is 4h~20h；
4th, the low whipping speed of product I that will be obtained in step 3 is magnetic agitation under 150r/min~400r/min
5min~10min, obtains finely dispersed suspension；To deionized water is added in finely dispersed suspension, bonding is added
Agent solution, then ultrasonic disperse 10min~30min, obtain adding the suspension of binding agent；
Finely dispersed suspension and the volume ratio of deionized water described in step 4 are 0.7:10；
The quality of the binder solution described in step 4 is 0.2g with the volume ratio of finely dispersed suspension:(0.5mL
~3mL)；
The suspension of the addition binding agent that the 5th, will be obtained in step 4 carries out vacuum filtration, obtains product II；Again by product
II and filter membrane be dried, finally remove filter membrane, obtain self-supporting material；
6th, self-supporting material is put into tube furnace, then by tube furnace with heating rate be 2 DEG C/min~5 DEG C/min's
Heating rate is warming up to 300 DEG C~800 DEG C, then calcines 0.5h~10h in the case where temperature is for 300 DEG C~800 DEG C, obtains three oxidations two
Iron/Graphene self-supporting electrode material.
Present embodiment step one 3. described in Graphene mass fraction be 3% the purchase of graphene conductive liquid from Shenzhen
Bei Terui nanosecond science and technology Co., Ltd of city.
The principle and advantage of present embodiment：
First, with commercialization graphene conductive liquid, (i.e. Graphene mass fraction is 3% graphene conductive to present embodiment
Liquid) Graphene is prepared instead of traditional Hummers and its modified method, the graphene conductive for solving conventional method preparation is poor,
It is unable to the shortcoming that large-scale application is produced in composite；
2nd, present embodiment increased the concentration of molysite on the basis of conventional hydrothermal method, is conducive to further increasing and produces
Amount；One-step method fabricated in situ composite is used in water heating kettle, and directly suction filtration, into self-supporting material, self-supporting material is passed through
Cross calcination processing and obtain di-iron trioxide/Graphene self-supporting electrode, beneficial to Fe2O3Being uniformly distributed in Graphene；
3rd, iron salt solutions, urea liquid and graphene dispersing solution are mixed, the mixed liquor for obtaining, only 40mL mixed liquors
The yield of obtained di-iron trioxide/Graphene self-supporting electrode is just up to more than 2g；Electrochemical results show, this implementation
The discharge capacity first of di-iron trioxide prepared by mode/Graphene self-supporting electrode has reached 937mAh/g, and initial charge holds
It is 674mAh/g to measure, and coulombic efficiency is 72%；100mA/g is first taken half-cell to circulate 3 times, then using 1000mA/g circulations
500 times, capacity gradually recovers in cyclic process, the charge specific capacity after circulation 500 times more than 600mAh/g, first
For 100mA/g charge specific capacities, capability retention is up to 89.79%, and di-iron trioxide/graphite prepared by present embodiment
The high rate performance of alkene self-supporting electrode is good, and specific capacity reaches 262mAh/g under 2000mA/g current densities, in 5000mA/g
Specific capacity has reached 130mAh/g under current density；And find di-iron trioxide/Graphene self-supporting prepared by present embodiment
Electrode has good invertibity, and after circulating 10 times under 5000mA/g, when current density is recovered to 100mA/g, specific capacity is still
570mAh/g can be reached.
Present embodiment can obtain a kind of preparation method of di-iron trioxide/Graphene self-supporting electrode.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Step one 1. described in iron
Salt is FeCl3·6H2One kind or wherein several mixtures in O, ferric nitrate and iron chloride.Other steps and specific embodiment party
Formula one is identical.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference is：Institute in step 4
The power of the ultrasonic disperse stated is 100W.Other steps are identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Institute in step 4
The concentration of the binder solution stated is 1%~5%；Described binder solution is carboxymethylcellulose sodium solution or sodium alginate
Solution.Other steps are identical with specific embodiment one to three.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Step one 1. in
The quality of described molysite is 4g with the volume ratio of deionized water:(5mL~20mL).Other steps and specific embodiment one to
Four is identical.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Step one 2. in
The quality of described urea is (1.33g~2g) with the volume ratio of deionized water:(5mL~10mL).Other steps and specific reality
Apply mode one to five identical.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Institute in step 4
The quality of the binding agent stated is 0.2g with the volume ratio of finely dispersed suspension:(0.5mL~0.7mL).Other steps and tool
Body implementation method one to six is identical.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Will in step 6
Self-supporting material calcines 0.5h~3h at being 300 DEG C~450 DEG C in temperature, obtains di-iron trioxide/Graphene self-supporting electrode.
Other steps are identical with specific embodiment one to seven.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Will in step 5
The suspension of the addition binding agent obtained in step 4 carries out vacuum filtration, obtains product II；Product II and filter membrane are carried out again
Dry, finally remove filter membrane, obtain self-supporting material, specifically carry out according to the following steps：By 0.01g Graphene mass fractions
Graphene conductive liquid for 3% is scattered in 40mL deionized waters, then the ultrasonic disperse 5min in the case where ultrasonic power is 100W, is obtained
The graphene dispersing solution of suction filtration；Take 3mL suction filtrations with graphene dispersing solution be poured over suction filtration carried out on filter membrane, obtain Graphene
Substrate；The suspension of binding agent will be added to be poured on graphene-based bottom again, then carry out vacuum filtration, obtain product II；
5min~30min is dried at being 60 DEG C in temperature by product II and filter membrane, the product II of partial desiccation state is obtained, then will be half-dried
The product II of dry state is taken off from filter membrane, obtains self-supporting material.Other steps are identical with specific embodiment one to eight.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：Will in step 5
Product II and filter membrane are dried, and finally remove filter membrane, and obtain self-supporting material is carried out according to the following steps：By product
II and filter membrane be 60 DEG C in temperature at dry, after product II and filter membrane are completely dried, filter membrane is burnt, obtain self-supporting material
Material.Other steps are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode, is specifically realized by the following steps：
First, solution is configured：
1., molysite is dissolved in deionized water, iron salt solutions are obtained；
Step one 1. described in the volume ratio of quality and deionized water of molysite be 4g:20mL；
Step one 1. described in molysite be FeCl3·6H2O；
2., urea is dissolved in deionized water, urea liquid is obtained；
Step one 2. described in the volume ratio of quality and deionized water of urea be 1.33g:8mL；
3., the graphene conductive liquid that Graphene mass fraction is 3% is added in deionized water, graphene dispersion is obtained
Liquid；
Step one 3. described in Graphene mass fraction be 3% graphene conductive liquid quality and deionized water body
Product is than being 11.25g:12mL；
2nd, under low whipping speed is 240r/min, 20mL iron salt solutions are dropwise added drop-wise in 12mL graphene dispersing solutions,
Low whipping speed is continuation stirring 30min under 240r/min again, then dropwise instills 8mL urea liquids, then low whipping speed is
Continue to stir 30min under 240r/min；Obtain mixed solution；
3rd, mixed solution is transferred in the water heating kettle containing polytetrafluoroethyllining lining, then will be containing in polytetrafluoroethylene (PTFE)
The water heating kettle of lining is reacted in oil bath, obtains product I；
Contain poly- four when the water heating kettle containing polytetrafluoroethyllining lining is reacted in oil bath described in step 3
Mixing speed in the water heating kettle of PVF liner is 100r/min, and oil bath temperature is 160 DEG C, and the oil bath reaction time is 8h；
4th, the low whipping speed of product I that will be obtained in step 3 is magnetic agitation 10min under 240r/min, is obtained
Finely dispersed suspension；To deionized water is added in finely dispersed suspension, binder solution, then ultrasonic disperse are added
10min, obtains adding the suspension of binding agent；
The concentration of the binder solution described in step 4 is 3%；Described binder solution is sodium carboxymethylcellulose
Solution；
Finely dispersed suspension and the volume ratio of deionized water described in step 4 are 0.7:10；
The quality of the binder solution described in step 4 is 0.2g with the volume ratio of finely dispersed suspension:0.7mL；
The power of the ultrasonic disperse described in step 4 is 100W；
The suspension of the addition binding agent that the 5th, will be obtained in step 4 carries out vacuum filtration, obtains product II；Again by product
II and filter membrane be dried, finally remove filter membrane, obtain self-supporting material；
6th, self-supporting material is put into tube furnace, then the heating rate liter by tube furnace with heating rate as 3 DEG C/min
Temperature calcines 3h to 450 DEG C, then in the case where temperature is for 450 DEG C, obtains di-iron trioxide/Graphene self-supporting electrode.
The suspension of the addition binding agent that will be obtained in step 4 in the step 5 of embodiment one carries out vacuum filtration, is produced
Thing II；Product II and filter membrane are dried again, finally remove filter membrane, obtain self-supporting material, specifically entered according to the following steps
Capable：The graphene conductive liquid that 0.01g Graphene mass fractions are 3% is scattered in 40mL deionized waters, then in ultrasonic work(
Rate is ultrasonic disperse 5min under 100W, obtains the graphene dispersing solution of suction filtration；The graphene dispersing solution for taking 3mL suction filtrations is toppled over
Suction filtration is carried out on filter membrane, graphene-based bottom is obtained；The suspension of binding agent will be added to be poured on graphene-based bottom again, then entered
Row vacuum filtration, obtains product II；5min~30min is dried at being 60 DEG C in temperature by product II and filter membrane, partial desiccation is obtained
The product II of state, then the product II of partial desiccation state is taken off from filter membrane, obtain self-supporting material.
Di-iron trioxide prepared by the embodiment one after cutting/Graphene self-supporting electrode is placed in anode cover, is added
One layer of lithium ion battery separator, is added dropwise 5 and drips lithium ion battery lithium based electrolyte, adds second layer lithium ion battery separator, according to
It is secondary to be put into lithium piece, nickel foam, negative electrode casing is covered, to battery seal on battery sealing machine after compression, pressure is 500psi, static
24h, is utilized the di-iron trioxide/Graphene self-supporting electrode assembling of the preparation of embodiment one into lithium ion half-cell；By profit
Di-iron trioxide/Graphene self-supporting the electrode assembling prepared with embodiment one carries out chemical property survey into lithium ion half-cell
Examination.
Fig. 1 is the digital photograph figure of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one；
Fig. 2 is that di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one is activated under 100mA/g current densities
After 3 circulations, the cycle performance figure under 1000mAh/g current densities；
As can be seen from Figure 2, embodiment one prepare di-iron trioxide/Graphene self-supporting electrode cycle during capacity gradually
Recover, initial charge specific capacity is 673.8mAh/g, the charge specific capacity after circulating 500 times is 605mAh/g, capacity
Conservation rate is up to 89.79%.
Fig. 3 be embodiment one prepare di-iron trioxide/Graphene self-supporting electrode 100 milliamperes/gram, 200 milliamperes/
Gram, 500 milliamperes/gram, 1000 milliamperes/gram, 2000 milliamperes/gram, 5000 milliamperes/gram, respectively circulate under 100 milliampere/gram current densities
The performance map of 10 times；
As can be seen from Figure 3, the high rate performance of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one is good,
Specific capacity reaches 262mAh/g under 2000mA/g current densities, and specific capacity has reached 130mAh/ under 5000mA/g current densities
g.And find that this electrode has good invertibity, under the 5000mA/g after circulation 10 times, when current density recover to
100mA/g, specific capacity remains to reach 570mAh/g.
Fig. 4 is first three cyclic voltammetry curve of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one, 1
It is first time cyclic voltammetry curve, 2 is second cyclic voltammetry curve, and 3 is third time cyclic voltammetry curve；
As can be seen from Figure 4, the embedding lithium peak main first of di-iron trioxide/Graphene self-supporting electrode that prepared by embodiment one is
0.3V, it is 1.75V to take off lithium peak, and the embedding de- lithium peak position of second and third circulation occurs to shuffle to a certain degree.Second and third cyclic curve
Almost overlap, illustrate the stable performance of material, capacity keeps effect fine.
Fig. 5 is the first charge-discharge curve of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one, and 1 is to fill
Electric curve, 2 is discharge curve；
As can be known from Fig. 5, discharge capacity reaches di-iron trioxide/Graphene self-supporting electrode that prepared by embodiment one first
937mAh/g, initial charge capacity is 674mAh/g, and coulombic efficiency is 72%.
Fig. 6 is the SEM figures of di-iron trioxide/Graphene self-supporting electrode prepared by embodiment one.
As can be seen from Figure 6, ferric oxide particle is evenly distributed between graphene layer, and dispersion effect is good.
Claims (10)
1. the preparation method of a kind of di-iron trioxide/Graphene self-supporting electrode, it is characterised in that the method is specifically by following
What step was completed：
First, solution is configured：
1., molysite is dissolved in deionized water, iron salt solutions are obtained；
Step one 1. described in the volume ratio of quality and deionized water of molysite be (2g~5g):(5mL~40mL)；
2., urea is dissolved in deionized water, urea liquid is obtained；
Step one 2. described in the volume ratio of quality and deionized water of urea be (0.66g~2g):(5mL~10mL)；
3., the graphene conductive liquid that Graphene mass fraction is 3% is added in deionized water, graphene dispersing solution is obtained；
Step one 3. described in Graphene mass fraction be 3% graphene conductive liquid quality and deionized water volume ratio
It is (4.93g~23.66g):(10mL~25mL)；
2nd, under low whipping speed is 150r/min~400r/min, iron salt solutions are dropwise added drop-wise in graphene dispersing solution, then
Low whipping speed is continuation stirring 20min~40min under 150r/min~400r/min, then dropwise instills urea liquid, then
Mixing speed is continuation stirring 20min~40min under 150r/min~400r/min；Obtain mixed solution；
Iron salt solutions and the volume ratio of graphene dispersing solution described in step 2 are (5~40):(10~25)；
Iron salt solutions and the volume ratio of urea liquid described in step 2 are (5~40):(5~10)；
3rd, mixed solution is transferred in the water heating kettle containing polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining will be contained
Water heating kettle is reacted in oil bath, obtains product I；
Contain polytetrafluoroethyl-ne when the water heating kettle containing polytetrafluoroethyllining lining is reacted in oil bath described in step 3
Mixing speed in the water heating kettle of alkene liner is 100r/min~400r/min, and oil bath temperature is 110 DEG C~220 DEG C, and oil bath is anti-
It is 4h~20h between seasonable；
4th, the low whipping speed of product I that will be obtained in step 3 is magnetic agitation 5min under 150r/min~400r/min
~10min, obtains finely dispersed suspension；To deionized water is added in finely dispersed suspension, binding agent is added molten
Liquid, then ultrasonic disperse 10min~30min, obtain adding the suspension of binding agent；
Finely dispersed suspension and the volume ratio of deionized water described in step 4 are 0.7:10；
The quality of the binder solution described in step 4 is 0.2g with the volume ratio of finely dispersed suspension:(0.5mL~
3mL)；
The suspension of the addition binding agent that the 5th, will be obtained in step 4 carries out vacuum filtration, obtains product II；Again by the He of product II
Filter membrane is dried, and finally removes filter membrane, obtains self-supporting material；
6th, self-supporting material is put into tube furnace, then the intensification by tube furnace with heating rate as 2 DEG C/min~5 DEG C/min
Speed is warming up to 300 DEG C~800 DEG C, then calcines 0.5h~10h at being 300 DEG C~800 DEG C in temperature, obtain di-iron trioxide/
Graphene self-supporting electrode material.
2. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
Step one 1. described in molysite be FeCl3·6H2One kind or wherein several mixtures in O, ferric nitrate and iron chloride.
3. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
The power of the ultrasonic disperse described in step 4 is 100W.
4. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
The concentration of the binder solution described in step 4 is 1%~5%；Described binder solution is carboxymethylcellulose sodium solution
Or sodium alginate soln.
5. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
Step one 1. described in the volume ratio of quality and deionized water of molysite be 4g:(5mL~20mL).
6. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
Step one 2. described in the volume ratio of quality and deionized water of urea be (1.33g~2g):(5mL~10mL).
7. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
The quality of the binding agent described in step 4 is 0.2g with the volume ratio of finely dispersed suspension:(0.5mL~0.7mL).
8. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
Self-supporting material is calcined into 0.5h~3h in the case where temperature is for 300 DEG C~450 DEG C in step 6, di-iron trioxide/Graphene is obtained
Self-supporting electrode material.
9. the preparation method of a kind of di-iron trioxide according to claim 1/Graphene self-supporting electrode, it is characterised in that
The suspension of the addition binding agent that will be obtained in step 4 in step 5 carries out vacuum filtration, obtains product II；Again by product II
It is dried with filter membrane, finally removes filter membrane, obtain self-supporting material, is specifically carried out according to the following steps：By 0.01g graphite
Alkene mass fraction is that 3% graphene conductive liquid is scattered in 40mL deionized waters, then the ultrasound point in the case where ultrasonic power is 100W
5min is dissipated, the graphene dispersing solution of suction filtration is obtained；Take 3mL suction filtrations with graphene dispersing solution be poured on filter membrane and taken out
Filter, obtains graphene-based bottom；The suspension of binding agent will be added to be poured on graphene-based bottom again, then carry out vacuum filtration, obtained
To product II；5min~30min is dried at being 60 DEG C in temperature by product II and filter membrane, the product II of partial desiccation state is obtained, then
The product II of partial desiccation state is taken off from filter membrane, self-supporting material is obtained.
10. a kind of preparation method of di-iron trioxide according to claim 1/Graphene self-supporting electrode, its feature exists
Product II and filter membrane are dried in step 5, finally remove filter membrane, it is to carry out according to the following steps to obtain self-supporting material
's：After drying at being 60 DEG C in temperature by product II and filter membrane, product II and filter membrane are completely dried, filter membrane is burnt, obtain certainly
Backing material.
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