CN105375061B - A kind of Graphene electrodes - Google Patents
A kind of Graphene electrodes Download PDFInfo
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- CN105375061B CN105375061B CN201510904078.0A CN201510904078A CN105375061B CN 105375061 B CN105375061 B CN 105375061B CN 201510904078 A CN201510904078 A CN 201510904078A CN 105375061 B CN105375061 B CN 105375061B
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of Graphene electrodes, belong to electrode field.A kind of Graphene electrodes of the present invention include weighing a graphite powder, the appropriate concentrated sulfuric acid are added under conditions of ice bath as solvent, controlling reaction temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 are slowly added to sodium nitrate and potassium permanganate into solution, stir 10min；Temperature is risen to 35 DEG C, 3h is stirred to react, according to the concentrated sulfuric acid：Deionized water volume ratio 1:0.2 deionized water is added into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionized water volume ratio 1:0.5 is added deionized water, stops reaction, according to graphite powder：Hydrogen peroxide molar ratio 1:0.2 5% hydrogen peroxide is added into solution, centrifuges while hot, respectively with three steps such as appropriate 5% dilute hydrochloric acid and distillation water washing.A kind of Graphene electrodes of the present invention have to be stablized using process safety, and battery capacity is big, and electrode is not easy to be lost, the excellent feature of discharge performance.
Description
Technical field
The present invention relates to a kind of electrode, especially a kind of Graphene electrodes.
Background technology
After Pu Lai get in 1859 trial-produces chemical conversion formula lead-acid accumulator successfully, electrochmical power source enters budding state.
In evolution in more than 100 years, the electrochmical power source of new range continuously emerges, and the performance of electrochmical power source is constantly improved.Especially
It is after World War II, the development of electrochmical power source is rapider.Cd-Ni batteries, production the 1980s are produced later
MH-Ni batteries have been given birth to, by nearly exploration in 20 years, have developed lithium ion battery and lighium polymer in early 1990s finally
Battery, the stage that will be commercialized also has been arrived in their development, currently, lithium ion battery is with its high specific energy density and service life
It grows and is taken seriously, quickly grow, lithium polymer battery is also given priority in the countries and regions such as the U.S., Japan and Taiwan.Lithium is poly-
It is swift and violent to close the development of object battery, gradually replaces cadmium nickel and Ni-H cell, grinding for electrode and electrolyte is made using polymer
It is particularly noticeable to study carefully exploitation.But the ionic conductivity and mechanical strength of current lithium polymer battery are poor, manufacturing process
Complexity, battery volume is larger, and battery capacity is inadequate, since positive active material and negative electrode active material are easy to fall off, for a long time
Poor using rear ionic conductivity and electrochemical stability, film strength and stability is isolated can also become with the use of battery
Change, it is easy to lithium polymer battery aging after prolonged use, the service life of charge and discharge be caused to be very restricted.
Invention content
The goal of the invention of the present invention is：In view of the above problems, provide it is a kind of stablized using process safety, battery
Capacity is big, and electrode is not easy to be lost, the excellent Graphene electrodes of discharge performance.
The technical solution adopted by the present invention is as follows：
A kind of Graphene electrodes of the present invention, are prepared by following steps：
Step 1：A graphite powder is weighed, the appropriate concentrated sulfuric acid is added under conditions of ice bath as solvent, stirs, control
Reaction temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 is slow into solution
Sodium nitrate and potassium permanganate is added, stirs 10min；Temperature is risen to 35 DEG C, 3h is stirred to react, according to the concentrated sulfuric acid：Deionized water
Volume ratio 1:0.2 deionized water is added into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionization water body
Product ratio 1:0.5 is added deionized water, stops reaction, according to graphite powder：Hydrogen peroxide molar ratio 1:0.2 5% pair is added into solution
Oxygen water, centrifuges while hot, and respectively with appropriate 5% dilute hydrochloric acid and distillation water washing, graphene oxide is made；
Step 2：Weigh a Rh（Ac）3, take proper amount of methanol as solvent, stirring at normal temperature dissolves, under condition of ice bath,
According to rhodium acetate：Lithium hydroxide molar ratio 1:1.2 LiOHH is added into solution2The methanol solution of O, 0 DEG C of controlling reaction temperature
8h is stirred, into solution according to rhodium acetate：N-hexane molar ratio 1:20 n-hexane is added into solution, continues to stir 1h, filter,
Precipitation is washed 3 times with distilled water and absolute methanol respectively, and product is scattered in ethyl alcohol, is configured to a concentration of 13.7mg/mL's
Rh（OH）3Alcohol dispersion liquid；
Step 3：It weighs a graphene oxide to be scattered in suitable absolute ethyl alcohol with ultrasonic wave, according to graphite oxide
Alkene：Rhodium hydroxide：Urea mol ratio 1:1:0.5 the alcohol dispersion liquid of a concentration of 13.7mg/mL rhodium hydroxides is added into solution
With urea-ethanol solution of 5mol/L, after 30min is stirred at room temperature, solution is transferred in reaction kettle, is passed through argon gas as protection
Hermetic seal, at 160 DEG C, reaction for 24 hours, stops reaction, after product is filtered, is washed with distilled water, then the item for being 0.98 in vacuum degree
It is lyophilized under part, then product is put into reaction kettle, be passed through after argon gas is used as protection hermetic seal and heated under conditions of 300 DEG C
5.5h obtains a nanometer Rh- graphene combination electrodes.
As the above scheme is adopted, from microstructure, Rh is attached to graphene in porous side's laminated structure and receives
Rice on piece is conducive to increase the contact area of rhodium and electrolyte, improves the utilization rate of active material, while graphene also contributes to
Improve the electric conductivity of material.
A kind of Graphene electrodes of the present invention, the specific capacitance of discharging when electric current is 1A/g is 576.3F/g.
By adopting the above-described technical solution, the electric discharge specific capacitance of the electrode is higher than the prior art.
A kind of Graphene electrodes of the present invention, application of the electrode in lithium polymer battery.
By adopting the above-described technical solution, can as the positive electrode of battery using nanometer Rh- graphene combination electrodes
The battery performance for improving positive plate, to improve the working efficiency of battery.
The present invention a kind of Graphene electrodes, the lithium polymer battery include be set to battery case inside positive plate and
Negative plate is equipped with isolation film between the positive plate and negative plate；It is covered successively equipped with anode between the positive plate and isolation film
Film and anode catalytic net, the anode overlay film are overlying on the surface of positive plate, and the anode catalytic net is overlying on the surface of isolation film；Institute
It states and is equipped with cathode catalysis net and cathode overlay film between isolation film and negative plate successively, the cathode catalysis net is overlying on the table of isolation film
Face, the cathode overlay film are overlying on the surface of negative plate；The positive plate is nanometer Rh- graphene combination electrodes, the positive plate
Thickness be 40 μm；The negative plate is nano Co2SnO4The thickness of polysulfonate acid naphthalene electrode, the negative plate is 50 μm, described negative
Pole piece specific capacitance of discharging when electric current is 1A/g is 817.6F/g.
By adopting the above-described technical solution, lithium battery during charge and discharge, can be passivated due to overload in electricity
Oxide is formed on extremely, so as to cause the decline of battery capacity, the efficiency for charge-discharge of electrode reduces, in positive plate and negative plate table
Face overlay film, the affinity that can be effectively improved between electrode and diaphragm increase ionic conducting property, reduce the generation of oxide,
To the service life of extended battery.Negative plate material is from microstructure, Co2SnO4It is mutually inlayed with polysulfonate acid naphthalene,
Three dimensions stereochemical structure is formed, Co is improved2SnO4The reunion of particle forms a good space conductive network, improves
The battery performance of negative plate, to improving the working efficiency of battery.
The thickness of a kind of Graphene electrodes of the present invention, the anode catalytic net is 10 μm, the anode catalytic net load
It is Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymers, the anode to have anode catalyst, the anode catalyst
The bearing capacity of anode catalyst is 0.38mg/cm on catalysis net2；The thickness of the cathode catalysis net is 10 μm, and the cathode is urged
It is oligomeric cagelike silsesquioxane-graphene, the cathode catalysis net to change net load to have cathode catalyst, the cathode catalyst
The bearing capacity of upper cathode catalyst is 0.71mg/cm2。
By adopting the above-described technical solution, suitable catalyst is added on anode and cathode, it can be in wider temperature
The capacity of battery and workbench is set to be improved in degree range, especially in low temperature and heavy-current discharge, to effectively
It avoids Li ions from forming oxide in electrode passivation, extends the service life of battery, the catalyst that the present invention uses can ensure
Battery can work normally in the range of -50 ~ 60 DEG C.
A kind of Graphene electrodes of the present invention, the isolation film are polymer-LiClO4-Li4Ti5O12Composite electrolyte, institute
It is polystyrene-ethylene pyrrolidones-styrene triblock copolymer to state polymer, and the thickness of the isolation film is 40 μm；Institute
It states isolation film surface and is covered with coat, the coat is Kynoar-hexafluoropropene, and the thickness of the coat is
100nm。
By adopting the above-described technical solution, polystyrene-ethylene pyrrolidones-styrene triblock copolymer is as base
Matter has stronger polarity, and containing the group for easily forming hydrogen bond, can improve the conduction of lithium ion in conjunction with some small molecules
Efficiency, ion conductor Li4Ti5O12The addition of nano-particle reduces the crystallinity of polymer, improves polymer dielectric
Conductivity increases carrier number in polymer, to improve the working efficiency of battery；Polystyrene-ethylene pyrrole simultaneously
Pyrrolidone-styrene triblock copolymer has good elasticity, and lighter weight, from microcosmic, molecular structure presents steady
Fixed reticular structure, apparent activation energy are larger.After coating, the tensile strength of diaphragm enhances, and increases the adsorption capacity of electronics, receives
Shrinkage reduces, and venting capability slightly reduces, and internal resistance is greatly lowered, and generates, increases the phenomenon that inside battery fever to reduce
The safety and stability performance of battery is added.
A kind of Graphene electrodes of the present invention, the anode overlay film are cell nafion proton membrane, and the cathode overlay film is two
The thickness of silica, the anode overlay film is 300nm, the thickness 300nm of the cathode overlay film.
By adopting the above-described technical solution, in the overlay film of positive plate and negative plate surface, can be effectively improved electrode with
Affinity between diaphragm increases ionic conducting property, reduces the generation of oxide, to the service life of extended battery.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1, the contact area for increasing metal and electrolyte, improves the utilization rate of active material, electric conductivity is improved.
2, the capacity of battery and workbench can be made to be improved within the scope of wider temperature, especially in low temperature and
When heavy-current discharge, oxide is formed in electrode passivation to be effectively prevented from Li ions.
3, internal resistance is greatly lowered, and generates the phenomenon that inside battery fever to reduce, goes wrong in inside battery
When, it timely embodies, shows as bulging without exploding, increase the safety and stability performance of battery.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of lithium polymer battery；
Fig. 2 is the SEM figures of positive plate；
Fig. 3 is the SEM figures of negative plate；
Fig. 4 is the SEM figures of polystyrene-ethylene pyrrolidones-styrene triblock copolymer.
It is marked in figure：1 is positive plate, and 2 be negative plate, and 3 be anode catalytic net, and 4 be cathode catalysis net, and 5 be isolation film, 6
It is positive overlay film for battery case, 7,8 be cathode overlay film.
Specific implementation mode
Below in conjunction with the accompanying drawings, the present invention is described in detail.
In order to make the object, technical solution and advantage of invention be more clearly understood, with reference to the accompanying drawings and embodiments, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1
As shown in Fig. 2, a kind of Graphene electrodes, nanometer Rh- graphene combination electrodes are prepared by following steps,
Step 1：A graphite powder is weighed, the appropriate concentrated sulfuric acid is added under conditions of ice bath as solvent, stirs, control
Reaction temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 is slow into solution
Sodium nitrate and potassium permanganate is added, stirs 10min；Temperature is risen to 35 DEG C, 3h is stirred to react, according to the concentrated sulfuric acid：Deionized water
Volume ratio 1:0.2 deionized water is added into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionization water body
Product ratio 1:0.5 is added deionized water, stops reaction, according to graphite powder：Hydrogen peroxide molar ratio 1:0.2 5% pair is added into solution
Oxygen water, centrifuges while hot, and respectively with appropriate 5% dilute hydrochloric acid and distillation water washing, graphene oxide is made；
Step 2：Weigh a Rh（Ac）3, take proper amount of methanol as solvent, stirring at normal temperature dissolves, under condition of ice bath,
According to rhodium acetate：Lithium hydroxide molar ratio 1:1.2 LiOHH is added into solution2The methanol solution of O, 0 DEG C of controlling reaction temperature
8h is stirred, into solution according to rhodium acetate：N-hexane molar ratio 1:20 n-hexane is added into solution, continues to stir 1h, filter,
Precipitation is washed 3 times with distilled water and absolute methanol respectively, and product is scattered in ethyl alcohol, is configured to a concentration of 13.7mg/mL's
Rh（OH）3Alcohol dispersion liquid；
Step 3：It weighs a graphene oxide to be scattered in suitable absolute ethyl alcohol with ultrasonic wave, according to graphite oxide
Alkene：Rhodium hydroxide：Urea mol ratio 1:1:0.5 the alcohol dispersion liquid of a concentration of 13.7mg/mL rhodium hydroxides is added into solution
With urea-ethanol solution of 5mol/L, after 30min is stirred at room temperature, solution is transferred in reaction kettle, is passed through argon gas as protection
Hermetic seal, at 160 DEG C, reaction for 24 hours, stops reaction, after product is filtered, is washed with distilled water, then the item for being 0.98 in vacuum degree
It is lyophilized under part, then product is put into reaction kettle, be passed through after argon gas is used as protection hermetic seal and heated under conditions of 300 DEG C
5.5h obtains a nanometer Rh- graphene combination electrodes.
Nanometer Rh- graphene combination electrodes obtained specific capacitance of discharging when electric current is 1A/g is 576.3F/g.
Embodiment 2
As shown in Figure 1, a kind of lithium polymer battery, includes the positive plate 1 and negative plate 2 inside battery case 6, just
Isolation film 5 is equipped between pole piece 1 and negative plate 2；Positive overlay film 7 and anode catalytic are equipped between positive plate 1 and isolation film 5 successively
Net 3, positive overlay film 7 are overlying on the surface of positive plate 1, and anode catalytic net 3 is overlying on the surface of isolation film 5；Isolation film 5 and negative plate 2
Between be equipped with cathode catalysis net 4 and cathode overlay film 8 successively, cathode catalysis net 4 is overlying on the surface of isolation film 5, and cathode overlay film 8 is overlying on
The surface of negative plate 2, positive overlay film 7 connect with anode catalytic net 3, and cathode overlay film 8 connects with cathode catalysis net 4.
Positive plate 1 is nanometer Rh- graphene combination electrodes, and the thickness of positive plate 1 is 40 μm；Negative plate 2 is nanometer
Co2SnO4The thickness of polysulfonate acid naphthalene electrode, negative plate 2 is 50 μm；The specific capacitance of discharging when electric current is 1A/g of positive plate 1 is
576.3F/g, the specific capacitance of discharging when electric current is 1A/g of negative plate 2 is 817.6F/g.
The thickness of anode catalytic net 3 is 10 μm, and it is Cr- bis- that the load of anode catalytic net 3, which has anode catalyst, anode catalyst,
Thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer, the bearing capacity of anode catalyst is 0.38mg/ on anode catalytic net 3
cm2；The thickness of cathode catalysis net 4 is 10 μm, and it is oligomeric cage type that the load of cathode catalysis net 4, which has cathode catalyst, cathode catalyst,
Silsesquioxane-graphene, the bearing capacity of cathode catalyst is 0.71mg/cm on cathode catalysis net 42。
Isolation film 5 is polymer-LiClO4-Li4Ti5O12Composite electrolyte, polymer are polystyrene-ethylene pyrrolidines
The thickness of ketone-styrene triblock copolymer, isolation film 5 is 40 μm.5 surface of isolation film is covered with coat, and coat is poly- inclined
The thickness of vinyl fluoride-hexafluoropropene, coat is 100nm.
Positive overlay film 6 is cell nafion proton membrane, and cathode overlay film 7 is silica, and the thickness of positive overlay film 6 is 300nm,
The thickness 300nm of cathode overlay film 7.
Battery case 6 is made of soft plastic, and soft plastic includes dimethicone 18.5%, talcum powder 7.8%,
TPR33%, zinc stearate 2.2%, white carbon 10.2%, boric acid 1.2%, deca-BDE 9.5%, antioxidant 168 are 0.25%, mustard
Sour amide 3.3%, organic siliconresin 14.05%.
Embodiment 3
As shown in figure 3, nano Co2SnO4Polysulfonate acid naphthalene electrode is prepared by following steps,
Step 1：Weigh a SnCl4, take appropriate amount of deionized water as solvent, stirring and dissolving, according to stannic chloride：Chlorination
Cobalt molar ratio 1:2 CoCl is added into solution2, according to stannic chloride：Sodium hydroxide molar ratio 1:10 are added NaOH's into solution
Aqueous solution, stirring at normal temperature 10min, solution is placed in reaction kettle, is passed through nitrogen：Oxygen 15:1 is passed through the mixing of nitrogen and oxygen
Gas, sealing, reacts 30h under conditions of 240 DEG C, and cooled to room temperature is washed with deionized water and absolute ethyl alcohol respectively,
It is lyophilized under conditions of vacuum degree is 0.98, obtains Co2SnO4Powder；
Step 2：Weigh a Co2SnO4Powder, by cobaltous stannate：Hydrochloric acid molar ratio 1:15 are added the hydrochloric acid solution of 2mol/L
As solvent, stirring and dissolving, according to cobaltous stannate：Sulfonic acid naphthalene：Potassium peroxydisulfate molar ratio 1:20：5 into solution be added sulfonic acid naphthalene and
Potassium peroxydisulfate reacts 5min after ultrasonic wave disperses 30min under power 2000W microwave conditions, filters, and takes filter residue respectively with steaming
Distilled water and absolute ethyl alcohol washing filtrate are in neutrality, and under conditions of vacuum degree is 0.98, air drying for 24 hours, obtains nanometer
Co2SnO4Polysulfonate acid naphthalene.
Embodiment 4
Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymers are prepared by following steps,
Step 1：Weigh a 1,2- dicyanos -1,2- two（2 ', 4 ', 5 '-trimethyls -3 '-thiophene）Ethylene takes appropriate
N-amyl alcohol is dissolved as stirring solvent, according to 1,2- dicyanos -1,2- bis-（2 ', 4 ', 5 '-trimethyls -3 '-thiophene）Ethylene：Vinegar
Sour chromium molar ratio 1:2 six water and chromic acetate are added into solution, and appropriate DBU catalyst is added, and heating reflux reaction 20h is natural
It is cooled to room temperature, is steamed solvent by Rotary Evaporators, obtain Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin polymer；
Step 2：A Cr- di-thiofuran ethylenes base tetraazatetradecane porphyrin polymer is weighed, q. s. methylene chloride is taken to make solvent,
Ultrasonic wave dispersion 30min is put into reaction kettle under the pressure of 5 atmospheric pressure and heats 5h under conditions of 150 DEG C, naturally cold
But to room temperature, filtering is washed with deionized, and under conditions of vacuum degree is 0.98, air drying for 24 hours, obtains Cr- Dithiophenes
Vinyl tetraazatetradecane porphyrin two dimension conjugated polymer.
Embodiment 5
Oligomeric cagelike silsesquioxane-graphene is prepared by following steps,
Step 1：A gamma-aminopropyl-triethoxy-silane is weighed, takes appropriate absolute ethyl alcohol as solvent, stirs evenly,
According to gamma-aminopropyl-triethoxy-silane：Phenyl triethoxysilane molar ratio 1:1 phenyltriethoxy silane is added into solution
Alkane, after stirring evenly, according to gamma-aminopropyl-triethoxy-silane：Tetraethyl ammonium hydroxide molar ratio 1:1.2 are added into solution
Tetraethyl ammonium hydroxide, heating reflux reaction 48h, naturally cools to room temperature, steams solvent by Rotary Evaporators, obtains stone
Grey milky product, with the mixed solution washed product of tetrahydrofuran and methanol, under vacuum condition freeze-drying obtain diamine POSS；
Step 2：A graphite powder is weighed, the appropriate concentrated sulfuric acid is added under conditions of ice bath as solvent, stirs, control
Reaction temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 is slow into solution
Sodium nitrate and potassium permanganate is added, stirs 10min；Temperature is risen to 35 DEG C, 3h is stirred to react, according to the concentrated sulfuric acid：Deionized water
Volume ratio 1:0.2 deionized water is added into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionization water body
Product ratio 1:0.5 is added deionized water, stops reaction, according to graphite powder：Hydrogen peroxide molar ratio 1:0.2 5% pair is added into solution
Oxygen water, centrifuges while hot, and respectively with appropriate 5% dilute hydrochloric acid and distillation water washing, graphene oxide is made；
Step 3：It weighs a graphene oxide to be scattered in suitable absolute ethyl alcohol with ultrasonic wave, after stirring evenly, press
According to graphene oxide：Diamine POSS molar ratios 1:12 diamine POSS is added into solution, according to graphene oxide：Dichloro two
Luxuriant titanium molar ratio 1:0.5 cyclopentadienyl titanium dichloride is added into solution, and after 30min is stirred at room temperature, solution is transferred in reaction kettle, leads to
Enter argon gas as protection hermetic seal, 36h is reacted at 210 DEG C, stops reaction, after product is filtered, is washed with distilled water, then true
Reciprocal of duty cycle is lyophilized under conditions of being 0.98, obtains oligomeric cagelike silsesquioxane-graphene.
Embodiment 6
As shown in figure 4, polymer-LiClO4-Li4Ti5O12Composite electrolyte is prepared by following steps,
Step 1：A styrene is weighed, takes appropriate hexamethylene as solvent, stirring and dissolving, according to styrene：Tertiary butyl
Lithium molar ratio 1:1.2 tert-butyl lithium is added into solution, after stirring evenly, is put into reaction kettle, is heated to 80 DEG C, reacts 1h,
Postcooling is reacted to 20 DEG C, according to styrene：Vinylpyrrolidone molar ratio 1:1 vinylpyrrolidone is added into solution, stirs
It mixes and is passed through nitrogen in uniformly backward reaction kettle as gas is protected, after being warming up to 240 DEG C of reaction 3h, 20 DEG C are cooled to, according still further to second
Alkene pyrrolidone：Styrene molar ratio 1:1 styrene is added into solution, is passed through nitrogen conduct after stirring evenly into reaction kettle
Gas is protected, 240 DEG C of reaction 3h is warming up to, absolute methanol is added and terminates reaction, solution is poured into absolute ethyl alcohol and is precipitated, filters
Afterwards, dry under vacuum condition, polystyrene-ethylene pyrrolidones-styrene triblock copolymer is made；
Step 2：A LiOH is weighed, according to lithium hydroxide：Titanium dioxide molar ratio 1:1 by lithium hydroxide solid and two
Titanium oxide solid is uniformly mixed, and is placed in Muffle furnace and is warming up to 800 DEG C of progress high temperature solid state reactions, naturally cold completely after reaction
But it takes out, ball milling sub-sieve obtains Li4Ti5O12Nano-particle；
Step 3：A polystyrene-ethylene pyrrolidones-styrene triblock copolymer is weighed, appropriate acetonitrile is taken to make
For solvent, according to polystyrene-ethylene pyrrolidones-styrene triblock copolymer after stirring evenly：LiClO4Molar ratio 20:
1 LiClO is added into solution4, according to LiClO after stirring evenly4：Li4Ti5O12Molar ratio 1:1 Li is added into solution4Ti5O12
Nano-particle stirs to get white viscous liquid, and mucus is poured into Teflon mould, is lyophilized, obtains under vacuum condition
Polymer-LiClO4-Li4Ti5O12Composite electrolyte.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (2)
1. a kind of preparation method of Graphene electrodes, which is characterized in that it includes the following steps：
Step 1：A graphite powder is weighed, the appropriate concentrated sulfuric acid is added under conditions of ice bath as solvent, stirring, control reaction
Temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 are slowly added into solution
Sodium nitrate and potassium permanganate stir 10min；Temperature is risen to 35 DEG C, 3h is stirred to react, according to the concentrated sulfuric acid：Deionized water volume
Than 1:0.2 deionized water is added into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionized water volume ratio
1:0.5 is added deionized water, stops reaction, according to graphite powder：Hydrogen peroxide molar ratio 1:0.2 5% dioxygen is added into solution
Water centrifuges while hot, and respectively with appropriate 5% dilute hydrochloric acid and distillation water washing, graphene oxide is made；
Step 2：Weigh a Rh（Ac）3, take proper amount of methanol as solvent, stirring at normal temperature dissolving, under condition of ice bath, according to second
Sour rhodium：Lithium hydroxide molar ratio 1:1.2 LiOHH is added into solution2The methanol solution of O, 0 DEG C of stirring of controlling reaction temperature
8h, into solution according to rhodium acetate：N-hexane molar ratio 1:20 n-hexane is added into solution, continues to stir 1h, filter, precipitation
It is washed 3 times with distilled water and absolute methanol respectively, product is scattered in ethyl alcohol, be configured to the Rh of a concentration of 13.7mg/mL
（OH）3Alcohol dispersion liquid；
Step 3：It weighs a graphene oxide to be scattered in suitable absolute ethyl alcohol with ultrasonic wave, according to graphene oxide：Hydrogen
Rhodium oxide：Urea mol ratio 1:1:0.5 be added into solution a concentration of 13.7mg/mL rhodium hydroxides alcohol dispersion liquid and
Urea-ethanol solution of 5mol/L, after 30min is stirred at room temperature, solution is transferred in reaction kettle, is passed through argon gas as protection gas
Sealing, at 160 DEG C, reaction for 24 hours, stops reaction, after product is filtered, is washed with distilled water, then the condition for being 0.98 in vacuum degree
Lower freeze-drying, then product is put into reaction kettle, it is passed through after argon gas is used as protection hermetic seal and heats 5.5h under conditions of 300 DEG C,
Obtain a nanometer Rh- graphene combination electrodes.
2. a kind of Graphene electrodes, which is characterized in that it is prepared by preparation method described in claim 1.
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| CN104148666A (en) * | 2014-07-26 | 2014-11-19 | 哈尔滨工业大学 | Method for modifying graphene through nano-sliver |
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| CN104148666A (en) * | 2014-07-26 | 2014-11-19 | 哈尔滨工业大学 | Method for modifying graphene through nano-sliver |
| CN104211055A (en) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene metal nanoparticle composite membrane |
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Effective date of registration: 20190510 Address after: 158100 Alkali Field Commission of Lishu District, Jixi City, Heilongjiang Province Patentee after: Jixi care-well carbon products Co. Ltd. Address before: 610041 6, 2 Building 3, unit 2, Gaosheng North Street, Wuhou District, Chengdu, Sichuan, 3 Patentee before: Song Hongting |