CN103915613B - Hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material - Google Patents

Hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material Download PDF

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CN103915613B
CN103915613B CN201410142978.1A CN201410142978A CN103915613B CN 103915613 B CN103915613 B CN 103915613B CN 201410142978 A CN201410142978 A CN 201410142978A CN 103915613 B CN103915613 B CN 103915613B
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mno
graphene
spray pyrolysis
manganese
preparation
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CN103915613A (en
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蒲薇华
王珊珊
李青海
陈敏
叶霞
唐廎
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Shandong Realdevelop Power Supply Technology Co Ltd
Tsinghua University
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Shandong Realdevelop Power Supply Technology Co Ltd
Tsinghua University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of hydrothermal reaction coupling spray pyrolysis MnO for belonging to energy-storage system electrode material technical field2The preparation method of/Graphene electrodes material.The graphene oxide first prepared by Hummer methods(GO)It is well mixed with the aqueous solution of manganous salt and doped metal ion compound, adds dispersant, oxidant and surfactant, ultrasonic disperse certain time;Mixed solution is placed in water heating kettle, temperature, certain time is adjusted;Reaction product is filtered, washed, presoma is obtained;Then, the presoma is added into dispersant and surfactant, be uniformly mixed, regulation solid-to-liquid ratio, inlet temperature and outlet temperature carry out spray pyrolysis, obtain the MnO of metal ion mixing2/ graphene nano combination electrode material.Nanometer combined electrode material composition prepared by the present invention is uniform, and batch stability is good.

Description

Hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material
Technical field
The invention belongs to energy-storage system nano-electrode material technical field, more particularly to a kind of hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material.
Background technology
The energy and environmental problem are two hang-ups of current facing mankind, force people to constantly look for the new energy more cleaned Source.Solar energy, wind energy, nuclear energy, ocean energy etc. are the clean energy resourcies largely existed on the earth, but these energy use by one The limitation of fixed condition, it is necessary to just can efficiently be utilized by special energy storage device.Energy storage and the energy are only solved well Efficient Conversion problem, could really realize the efficient utilization of new energy.Therefore, exploitation excellent combination property lithium ion battery, Lithium secondary battery and ultracapacitor critical material, just turn into the emphasis of high-performance energy storage device developmental research, are also final Solve the problems, such as the key point of new energy resources system energy storage.
Transition-metal oxide, such as manganese dioxide(MnO2, theoretical specific capacity is 1232mAh/g)With very high theoretical storage Electric specific capacity, and Li dendrite is not generated during storage lithium ion formation electric current, safety in utilization is good, preparation method letter It is single, environment-friendly, it is abundance, with low cost.But MnO2Fatal shortcoming is poorly conductive, in storage lithium and storage electric charge process In easily occur volumetric expansion, cause material discharging performance and cycle life not good, except MnO2Material is in lithium primary battery Using outer, at present, transition metal oxide material can not also be actual in lithium secondary battery, lithium ion battery and ultracapacitor Use.Therefore, it is necessary to find influence MnO2The root of electric conductivity and structural stability simultaneously proposes specific solution, i.e., from material Expect to solve the bottleneck problem that material is present in terms of synthesis technique.Graphene(RGO)It is a kind of tool just grown up in recent years There are high conductivity, pliability, light-high-strength, the two-dimensional nano lamella new material of the high-ratio surface of thermal conductive resin.It is high Electric conductivity and pliability have very strong attraction in terms of energy storage combination electrode material research and are widely applied prospect.
Based on this, present invention exploitation hydrothermal reaction coupling spray pyrolysis process prepares MnO2Used with the nano composite material of graphene The lithium ion battery and ultracapacitor being related in energy-storage system.
2000, P. Poizot et al. published an article in Nuture periodicals, first using nano transition metal oxides as Lithium ion battery negative material is studied, it is found that the initial discharge capacity of transition metal oxide material is very high, but multiple Capacity declines rapidly after discharge and recharge, and main cause is the volumetric expansion and contraction of transition metal oxide material in charge and discharge process It is larger, cause electrode structure to destroy, cycle performance is poor.Then, Patents and document report some improve transition metal Oxide conducting and circulative method, these methods cut both ways:High temperature solid-state method mixing is uneven, synthesis product grain It is micron order that degree is most of, and wider distribution, and sintering particle aggregation is serious, often contains impurity, pattern is irregular, different batches The chemical property of material differs greatly, and it is larger to consume energy;Sol-gal process is difficult industrialization;Electrodeposition process technique is difficult to control And it is difficult to scale;Hydro-thermal method is to prepare the more commonly used technique of nano material;Spray pyrolysis process comparative maturity, can fast rapid-curing cutback Dry nano material, prevents material from reuniting and growing up, and be easy to scale.Therefore, hydro-thermal method and spray pyrolysis process are subjected to coupling Conjunction applies to prepare MnO2The method of/graphene nano material has the feasibility of innovative and practical application, can not only be accurate Control Mn2+And Doped ions content, control crystallization shape, granule size, improve combination electrode material electric conductivity and Stability Analysis of Structures Property, it can also improve the stability of bulk article performance.
The content of the invention
In order to overcome the various drawbacks of conventional art, it is an object of the invention to provide a kind of hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, it is characterised in that this method is carried out according to the following steps:
(1)The graphene oxide first prepared by Hummer methods and the bivalent manganese that manganese ion concentration is 0.1~1.5mol/l The aqueous solution mixing of salt and the metal ion compound to be adulterated, graphene oxide is 1 with the mass ratio that manganese salt is combined:200~1: 5, oxidant, dispersant and surfactant are added, ultrasonic disperse 30 ~ 120 minutes forms uniform mixed solution;
(2)Step(1)Obtained mixed solution is placed in water heating kettle, and regulation hydrothermal reaction process temperature is 100~250 DEG C, it is 2~24hr to continue the hydro-thermal reaction time, and reaction product is filtered, washed, presoma is obtained;
(3)By step(2)Obtained presoma adds the addition of dispersant and surfactant, wherein surfactant For the 0.01~0.5% of forerunner's weight, it is uniformly mixed, obtains the mixed slurry of solid content 5 ~ 25%, regulation import is temperature 150~240 DEG C of degree, outlet temperature is 80~130 DEG C, carries out spray pyrolysis, obtains the MnO of ion doping2/ Graphene electrodes material Material.
According to described hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, the manganese salt chemical combination Thing is one kind in manganese chloride, manganese sulfate, manganese nitrate, manganese acetate and manganese oxalate.
According to described hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, step(1)Described in Doped metal ion is Li+、Mg2+、Al3+、Cr3+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、V2+、Sn4+、Ti4+One in metal ion Plant or two kinds, doping is the 1~10% of manganese ion molar concentration.
According to described hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, described step(1) In oxidant be KMnO4, H2O2、KClO3In one kind, addition in molar ratio be Mn2+The 2/3 ~ 2 of content.
According to described hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, step(1)And step (3)In, the dispersant is one kind or two in water, ethanol, n-butanol, isopropanol, pentaerythrite, polyethylene glycol and polyethers Kind, step(1)The addition of middle dispersant be ensure the step formation mixed solution concentration between 0.01 ~ 1mol/l, step Suddenly(3)The addition of middle dispersant is the solid content for ensuring the mixed slurry that the step is obtained between 5 ~ 25%.
According to described hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, step(1)And step (3)In, the surfactant is lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, poly- second two Alcohol, dioctyl succinate disulfonate acid, fatty acid sorbitan, polysorbate, polyoxyethylene, polyvinyl alcohol, methyl anyl alcohol, polypropylene Any one in acid amides, fatty acid polyethylene glycol ester or two kinds, the total amount of adding of surfactant is respectively step(1)Manganese salt matter Amount and step(3)The 0.01~0.5% of forerunner's weight.
According to described hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, described is obtained MnO2Graphene content in/graphene nano combination electrode material is 1.0~25%, and particle mean size is between 10~80nm, system The MnO obtained2/ graphene nano combination electrode material first discharge specific capacity is more than 1300mAh/g, and specific capacitance is more than 360F/g.
The invention provides a kind of hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, first will Graphene oxide prepared by Hummer methods(GO)It is well mixed with the aqueous solution of manganous salt and doped metal ion compound, then Add dispersant, oxidant and surfactant, ultrasonic disperse certain time;Mixed solution is placed in water heating kettle, regulation temperature Reaction product is filtered, washed, obtains presoma by degree, certain time;Then, the presoma is added into dispersant and table Face activating agent, is uniformly mixed, and regulation solid-to-liquid ratio, charging rate and inlet temperature carry out spray pyrolysis, obtain metal ion The MnO of doping2/ Graphene electrodes material.Prepared nano composite material can not only be used for the electrode material of super capacitor, can also It is used as the negative material of lithium ion battery.
Beneficial effects of the present invention are:
(1)MnO2 is transition metal oxide, and raw material sources are extensive, cheap, is carried with the compound rear electric conductivity of graphene Height, in addition, doped metal ion, can stablize MnO2 structures, suppresses the Volume Changes in charge and discharge process, improves the circulation longevity Life.Therefore, the electrode material that prepared by the complex method is applied in energy-storage system has good practical value and market prospects.
(2)Dispersant and surfactant hybrid reaction material are added, not only mixing efficiency is high, and in hydro-thermal-spraying heat The regulation and control of nano particle pattern, crystal formation and granularity are helped in solution technical process.
(3)Hydro-thermal method technique is simple, it is easy to control, and also easily realizes metal ion Uniform Doped, product quality uniformity Height, performance is stable, prepares cost low.
(4)Using spray pyrolysis process, wink-dry slurry, it is to avoid segregation in composition drying process, it is to avoid nano particle Reunion is grown up, and products obtained therefrom composition is uniform, and batch stability is good, is adapted to large batch of industrialized production;
(5)The MnO prepared using the technique2/ graphene nano combination electrode material is used as electrode material for super capacitor Good chemical property is shown with lithium ion battery negative material.In aqueous systems electrolyte, 100mA/g current densities Lower electric capacity is more than 1300mAh/g in more than 360F/g, at room temperature 0.1C multiplying power dischargings specific capacity, and cycle performance is good.
Brief description of the drawings
Fig. 1 is the MnO prepared by embodiment one2The TEM of/Graphene electrodes material.
Fig. 2 is the MnO prepared by embodiment one2The XRD of/Graphene electrodes material.
Fig. 3 is the MnO prepared by embodiment one2The discharge curve first of/Graphene electrodes material.
Fig. 4 is the MnO prepared by embodiment one2The CV curves of/Graphene electrodes material.
Embodiment
Technical scheme is described further with reference to embodiment, following examples are not to present invention generation Limitation.
Embodiment one:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1)With graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, improved Hummers is utilized Method prepares graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2)Take 0.005g steps(1)The GO of preparation, adds ultrasound 0.5hr under 20mL deionized waters, 200w power, obtains Even GO deionized waters dispersion liquid;
(3)Using potassium permanganate and manganese acetate as raw material, weigh 0.3g potassium permanganate and 0.7g manganese acetates, add 30mL go from Sub- water, adds 20mL steps(2)The GO deionized water dispersion liquids of preparation, 20mL 0.001M Ni (NO3)2Solution, 0.1g ten Sodium dialkyl sulfate, ultrasonic 0.5hr forms uniform mixed solution, inserts water heating kettle, and controlling reaction temperature is 250 DEG C, is continued Reaction time is 2hr, and question response product is cooled to after room temperature, removes separation, washing and obtains compound precursor.
(4)In step(3)Obtained MnO2/ graphene complex presoma adds deionized water and 0.25mg dodecyls Sodium sulphate is made into the slurry that solid content is 10%, using cocurrent drying mode, and atomising device uses double-current method nozzle, controls nozzle Gas flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 150 DEG C, outlet temperature is 80 DEG C, outlet Air is separated through one-level whirlpool and is vented, and obtains well mixed Ni doping MnO2/ graphene complex.
(5)Testing procedure(4)Obtained Ni doping MnO2Graphene content in/graphene nanocomposite material is 1.0%。
(6)Testing procedure(4)Obtained Ni doping MnO2/ graphene nanocomposite material granularity is 15nm.
(7)By Ni dopen Nanos MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF(It is dissolved in NMP In)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, is then scratched the nickel foam in 1 millimeters thick On, electrode plates are obtained after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, being filled in the glove box full of argon gas to test Battery, charge-discharge test is carried out with constant current, and charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is measured discharges first under 0.1C multiplying powers Specific capacity is more than 1650mAh/g.
(8)Using three-electrode system in 1M Na2SO4Prepared Ni doping MnO is tested in the aqueous solution2/ graphene nano is multiple The specific capacitance of condensation material is 465F/g.
Embodiment two:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1)With graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, using improved Hummers methods prepare graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2)Take 0.05g steps(1)The GO of preparation, adds ultrasound 1hr under 20mL ethanol, 200w power, obtains uniform GO and disperses Liquid;
(3)Using potassium permanganate and manganese acetate as raw material, weigh 1.6g potassium permanganate and 3.7g manganese acetates, add 30mL go from Sub- water, 0.3g lauryl sodium sulfate adds 20mL steps(2)The GO dispersion liquids of preparation, 20mL 0.025M Ni (NO3)2 Solution, ultrasonic 1hr forms uniform mixed solution, inserts water heating kettle, and controlling reaction temperature is 160 DEG C, and the sustained response time is 12hr, question response product is cooled to after room temperature, is removed separation, washing and is obtained compound precursor.
(4)In step(3)Ni dopen Nanos MnO is made2/ graphene complex presoma adds ethanol and 0.25mg ten Sodium dialkyl sulfate is made into the slurry that solid content is 10%, using cocurrent drying mode, and atomising device uses double-current method nozzle, control Orifice gas flow and pressure processed and with peristaltic pump charging rate, inlet temperature is maintained at 200 DEG C, outlet temperature is 100 DEG C, outlet air is separated through one-level whirlpool and is vented, and obtains well mixed Ni doping MnO2/ graphene complex.
(5)Testing procedure(4)Obtained Ni doping MnO2Graphene content in/graphene nanocomposite material is 3%.
(6)Testing procedure(4)Obtained Ni doping MnO2/ graphene nanocomposite material particle mean size is 12nm.
(7)Ni nanoparticle is adulterated MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF(It is dissolved in NMP In)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, is then scratched the nickel foam in 1 millimeters thick On, electrode plates are obtained after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, being filled in the glove box full of argon gas to test Battery, charge-discharge test is carried out with constant current, and charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is measured discharges first under 0.1C multiplying powers Specific capacity is more than 1520mAh/g.
(8)Using three-electrode system in 1M Na2SO4Prepared Ni dopen Nanos MnO is tested in the aqueous solution2/ graphene is received The specific capacitance of nano composite material is 407F/g.
Embodiment three:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1) with graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, improved Hummers is utilized Method prepares graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2) 0.2g steps are taken(1)The GO of preparation, adds ultrasound 2hr under 20mL deionized waters, 200w power, obtains uniform GO Deionized water dispersion liquid;
(3) 3.2g potassium permanganate and 7.5g manganese acetates are weighed using potassium permanganate and manganese acetate as raw material, add 30mL go from Sub- water, 0.5g polyvinyl alcohol adds 20mL steps(2)The GO deionized water dispersion liquids of preparation, 20mL 0.08mol/L Ni (NO3)2Solution, ultrasonic 2hr forms uniform mixed solution, inserts water heating kettle, and controlling reaction temperature is 180 DEG C, sustained response Time is 8hr, and question response product is cooled to after room temperature, removes separation, washing and obtains compound precursor.
(4) in step(3)Obtained MnO2/ graphene complex presoma adds deionized water and 0.25mg polyvinyl alcohol The slurry that solid content is 20% is made into, is dried with pneumatic spray drying device, using cocurrent drying mode, atomising device is using double Stream nozzle, control orifice gas flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 200 DEG C, go out Mouth temperature is 120 DEG C, and outlet air is separated through one-level whirlpool and is vented, and obtains well mixed Ni doping MnO2/ graphene is combined Thing.
(5) testing procedure(4)Obtained Ni doping MnO2Graphene content in/graphene nanocomposite material is 5%.
(6) Ni doping MnO is measured2/ graphene nanocomposite material particle mean size is 10nm.
(7) by Ni dopen Nanos MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF(It is dissolved in NMP In)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, is then scratched the nickel foam in 1 millimeters thick On, electrode plates are obtained after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, being filled in the glove box full of argon gas to test Battery, charge-discharge test is carried out with constant current, and charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is measured discharges first under 0.1C multiplying powers Specific capacity is more than 1380mAh/g.
(8) using three-electrode system in 1M Na2SO4Prepared Ni doping MnO is tested in the aqueous solution2/ graphene nano is multiple The specific capacitance of condensation material is 385F/g.
Example IV:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1)With graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, using improved Hummers methods prepare graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2)Take 1g steps(1)The GO of preparation, adds ultrasound 2hr under 20mL n-butanols, 200w power, obtains uniform GO and disperses Liquid;
(3)Using potassium permanganate and manganese acetate as raw material, weigh 1.6g potassium permanganate and 3.7g manganese acetates, add 10mL go from Sub- water, 0.6g dodecyl sodium sulfates add 20mL steps(2)The GO dispersion liquids of preparation, 20mL 0.15M Ni (NO3)2It is molten Liquid, ultrasonic 2hr forms uniform mixed solution, inserts water heating kettle, and controlling reaction temperature is 100 DEG C, and the sustained response time is 24hr, question response product is cooled to after room temperature, is removed separation, washing and is obtained compound precursor.
(4)In step(3)Obtained Ni dopen Nanos MnO2/ graphene complex presoma adds n-butanol and 0.25mg Lauryl sodium sulfate is made into the slurry that solid content is 10%, using cocurrent drying mode, and atomising device uses double-current method nozzle, Control orifice gas flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 200 DEG C, outlet temperature is 100 DEG C, outlet air is separated through one-level whirlpool and is vented, and obtains well mixed Ni doping MnO2/ graphene complex.
(5)Testing procedure(4)Obtained Ni doping MnO2Graphene content in/graphene nanocomposite material is 25%.
(6)Test obtained Ni dopen Nanos MnO2/ graphene nanocomposite material particle mean size is 12nm.
(7)Ni nanoparticle is adulterated MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF(It is dissolved in NMP In)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, is then scratched the nickel foam in 1 millimeters thick On, electrode plates are obtained after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, being filled in the glove box full of argon gas to test Battery, charge-discharge test is carried out with constant current, and charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is measured discharges first under 0.1C multiplying powers Specific capacity is more than 1320mAh/g.
(8)Using three-electrode system in 1M Na2SO4Prepared MnO is tested in the aqueous solution2/ graphene nanocomposite material Specific capacitance be 367F/g.
Embodiment five:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1)With graphite, potassium permanganate, H2SO4/H3PO4(9:And H 1)2O2For raw material, prepared using improved Hummers methods Graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2)Take 0.005g steps(1)The GO of preparation, adds ultrasound 0.5hr under 10mL deionized waters, 200w power, obtains Even GO deionized waters dispersion liquid;
(3)Using hydrogen peroxide and manganese sulfate as raw material, 0.1g hydrogen peroxide and 0.5g manganese sulfates are weighed, 30mL deionizations are added Water, 0.1g neopelexes add 10mL steps(2)The GO deionized water dispersion liquids of preparation, 20mL 0.001M's FeCl3Solution, ultrasonic 0.5hr forms uniform mixed solution, inserts water heating kettle, and controlling reaction temperature is 100 DEG C, continues anti- It is 24hr between seasonable, question response product is cooled to after room temperature, removes separation, washing and obtain compound precursor.
(4)In step(3)Obtained Fe doping MnO2/ graphene complex presoma adds deionized water and 0.45mg ten Dialkyl benzene sulfonic acids sodium is made into the slurry that solid content is 25%, using cocurrent drying mode, and atomising device uses double-current method nozzle, Control orifice gas flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 240 DEG C, outlet temperature is 130 DEG C, outlet air is separated through one-level whirlpool and is vented, and obtains well mixed Fe doping MnO2/ graphene complex.
(5)Testing procedure(4)Obtained Fe doping MnO2Graphene content in/graphene nanocomposite material is 2%.
(6)Measure Fe doping MnO2/ graphene nanocomposite material particle mean size is 40nm.
(7)By Fe dopen Nanos MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF binding agents press matter Amount compares 8.5:1:0.5 mixing, is made uniform slurry, is then scratched in 20 microns of thick nickel foams, through 120 DEG C of vacuum Electrode plates are obtained after drying, using lithium paper tinsel as to electrode, experimental cell is filled to obtain in the glove box full of argon gas, is entered with constant current Row charge-discharge test, charging/discharging voltage is 0.05 ~ 4.2V, and room temperature measures first discharge specific capacity under 0.1C multiplying powers and is more than 1600mAh/g。
(8)Using three-electrode system in 1M Na2SO4Prepared Fe doping MnO is tested in the aqueous solution2/ graphene nano is multiple The specific capacitance of condensation material is 498F/g.
Embodiment six:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1)With graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, improved Hummers is utilized Method prepares graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2)Take 0.05g steps(1)The GO of preparation, adds ultrasound 1hr under 20mL isopropanols, 200w power, obtains uniform GO points Dispersion liquid;
(3)Using hydrogen peroxide and manganese sulfate as raw material, 0.3g hydrogen peroxide and 1.25g manganese sulfates are weighed, 15mL deionizations are added Water, 0.1g polyvinyl alcohol adds 20mL steps(2)The GO dispersion liquids of preparation, 20mL 0.01M FeCl3Solution, ultrasonic 1hr, Uniform mixed solution is formed, water heating kettle is inserted, controlling reaction temperature is 140 DEG C, the sustained response time is 18hr, question response production Thing is cooled to after room temperature, is removed separation, washing and is obtained compound precursor.
(4)In step(3)Obtained Fe doping MnO2/ graphene complex presoma adds isopropanol and the poly- second of 0.85mg Enol is made into the slurry that solid content is 10%, using cocurrent drying mode, and atomising device uses double-current method nozzle, controls nozzle gas Body flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 180 DEG C, outlet temperature is 120 DEG C, and outlet is empty Gas is separated through one-level whirlpool and is vented, and obtains well mixed Fe doping MnO2/ graphene complex.
(5)Testing procedure(4)Obtained Fe doping MnO2Graphene content in/graphene nanocomposite material is 8%.
(6)Test obtained Fe doping MnO2/ graphene nanocomposite material particle mean size is 80nm.
(7)By surface modification Fe dopen Nanos MnO2/ graphene complex material, Super-P conductive carbon blacks,
PVDF(It is dissolved in NMP)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, then by it Blade coating obtains electrode plates in the nickel foam of 1 millimeters thick after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, full of argon Experimental cell is filled to obtain in the glove box of gas, charge-discharge test is carried out with constant current, charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is surveyed Obtain first discharge specific capacity under 0.1C multiplying powers and be more than 1570mAh/g.
(8)Using three-electrode system in 1M Na2SO4Prepared Fe doping MnO is tested in the aqueous solution2/ graphene nano is multiple The specific capacitance of condensation material is 479F/g.
Embodiment seven:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1) with graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, improved Hummers is utilized Method prepares graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2) 0.05g steps are taken(1)The GO of preparation, adds ultrasound 1hr under 20mL isopropanols, 200w power, obtains uniform GO points Dispersion liquid;
(3) using hydrogen peroxide and manganese sulfate as raw material, 0.5g hydrogen peroxide and 2.5g manganese sulfates are weighed, 15mL deionizations are added Water, 0.2g polysorbates add 20mL steps(2)The GO dispersion liquids of preparation, 20mL 0.04M FeCl3Solution, ultrasonic 1hr, Uniform mixed solution is formed, water heating kettle is inserted, controlling reaction temperature is 180 DEG C, the sustained response time is 12hr, question response production Thing is cooled to after room temperature, is removed separation, washing and is obtained compound precursor.
(4) in step(3)Obtained MnO2/ graphene complex presoma adds isopropanol and 1.25mg polysorbates (Tween)The slurry that solid content is 15% is made into, using cocurrent drying mode, atomising device uses double-current method nozzle, controls nozzle Gas flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 180 DEG C, outlet temperature is 100 DEG C, outlet Air is separated through one-level whirlpool and is vented, and obtains well mixed Fe doping MnO2/ graphene complex.
(5) testing procedure(4)Obtained Fe doping MnO2Graphene content in/graphene nanocomposite material is 12%.
(6) the Fe doping MnO that test is obtained2/ graphene nanocomposite material particle mean size is 30nm.
(7) by Fe dopen Nanos MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF(It is dissolved in NMP In)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, is then scratched the nickel foam in 1 millimeters thick On, electrode plates are obtained after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, being filled in the glove box full of argon gas to test Battery, charge-discharge test is carried out with constant current, and charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is measured discharges first under 0.1C multiplying powers Specific capacity is more than 1400mAh/g.
(8) using three-electrode system in 1M Na2SO4Prepared Fe doping MnO is tested in the aqueous solution2/ graphene nano is multiple The specific capacitance of condensation material is 436F/g.
Embodiment eight:
Prepare electrode material of lithium battery nanometer MnO2/ graphene complex, is carried out according to the following steps:
(1)With graphite, potassium permanganate, H2SO4/H3PO4(volume ratio 9:And H 1)2O2For raw material, using improved Hummers methods prepare graphite oxide(GO), the GO of gained is the laminated structure of 5 × 5 μm of multilayer;
(2)Take 3g steps(1)The GO of preparation, adds ultrasound 2hr under 30mL deionized waters, 200w power, obtains uniform GO and go Ion aqueous dispersions;
(3)Using potassium permanganate and manganese sulfate as raw material, weigh 1.5g potassium permanganate and 7.5g manganese sulfates, add 30mL go from Sub- water, 0.8g fatty acid sorbitans add 30mL steps(2)The GO deionized water dispersion liquids of preparation, 20mL 0.15M's FeCl3Solution, ultrasonic 2hr forms uniform mixed solution, inserts water heating kettle, and controlling reaction temperature is 250 DEG C, sustained response Time is 2hr, and question response product is cooled to after room temperature, removes separation, washing and obtains compound precursor.
(4)In step(3)Obtained Fe doping MnO2/ graphene complex presoma adds deionized water and 2.00mg fat Fat acid sorb is smooth(Span)The slurry that solid content is 20% is made into, using cocurrent drying mode, atomising device is sprayed using double-current method Mouth, control orifice gas flow and pressure and with peristaltic pump charging rate, inlet temperature is maintained at 220 DEG C, outlet temperature For 110 DEG C, outlet air is separated through one-level whirlpool and is vented, and obtains well mixed Fe doping MnO2/ graphene complex.
(5)Testing procedure(4)Obtained Fe doping MnO2Graphene content in/graphene nanocomposite material is 21%.
(6)Test obtained Fe doping MnO2/ graphene nanocomposite material particle mean size is 50nm.
(7)By Fe dopen Nanos MnO2/ graphene complex material, Super-P conductive carbon blacks, PVDF(It is dissolved in NMP In)Binding agent in mass ratio 8.5:1:0.5 mixing, is made uniform slurry, is then scratched the nickel foam in 1 millimeters thick On, electrode plates are obtained after being dried in vacuo through 120 DEG C, using lithium paper tinsel as to electrode, being filled in the glove box full of argon gas to test Battery, charge-discharge test is carried out with constant current, and charging/discharging voltage is 0.05 ~ 4.2V, and room temperature is measured discharges first under 0.1C multiplying powers Specific capacity is more than 1380mAh/g.
(8)Using three-electrode system in 1M Na2SO4Prepared Fe doping MnO is tested in the aqueous solution2/ graphene nano is multiple The specific capacitance of condensation material is 379F/g.

Claims (7)

1. a kind of hydrothermal reaction coupling spray pyrolysis MnO2The preparation method of/Graphene electrodes material, it is characterised in that this method is by following Step is carried out:
(1)The graphene oxide that first prepared by Hummer methods and manganese ion concentration for 0.1~1.5mol/l manganous salt and The aqueous solution mixing for the metal ion compound to be adulterated, graphene oxide is 1 with the mass ratio that manganese salt is combined:200~1:5, then Oxidant, dispersant and surfactant are added, ultrasonic disperse 30 ~ 120 minutes forms uniform mixed solution;
(2)Step(1)Obtained mixed solution is placed in water heating kettle, and regulation hydrothermal reaction process temperature is 100~250 DEG C, is held Continuous the hydro-thermal reaction time is 2~24hr, and reaction product is filtered, washed, presoma is obtained;
(3)By step(2)Obtained presoma adds dispersant and surfactant, before the addition of wherein surfactant is The 0.01~0.5% of weight is driven, is uniformly mixed, the mixed slurry that solid content is 5 ~ 25% is obtained, regulation import is temperature 150~240 DEG C, outlet temperature is 80~130 DEG C, carries out spray pyrolysis, obtains the MnO of ion doping2/ graphene nano is combined Electrode material.
2. hydrothermal reaction coupling spray pyrolysis MnO according to claim 12The preparation method of/Graphene electrodes material, its feature It is:The manganese salt compound is one kind in manganese chloride, manganese sulfate, manganese nitrate, manganese acetate and manganese oxalate.
3. hydrothermal reaction coupling spray pyrolysis MnO according to claim 12The preparation method of/Graphene electrodes material, its feature It is:Step(1)Described in doped metal ion be Li+、Mg2+、Al3+、Cr3+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、V2+、Sn4 +、Ti4+One or both of metal ion, doping is the 1~10% of manganese ion molar concentration.
4. hydrothermal reaction coupling spray pyrolysis MnO according to claim 12The preparation method of/Graphene electrodes material, its feature It is:Described step(1)In oxidant be KMnO4, H2O2、KClO3In one kind, addition in molar ratio be Mn2+Content 2/3 ~ 2.0 times.
5. hydrothermal reaction coupling spray pyrolysis MnO according to claim 12The preparation method of/Graphene electrodes material, its feature It is:Step(1)And step(3)In, the dispersant is deionized water, ethanol, n-butanol, isopropanol, pentaerythrite, poly- second One or both of glycol and polyethers, step(1)The addition of middle dispersant is to ensure that the mixed solution of step formation is dense Degree is between 0.01 ~ 1mol/l, step(3)The addition of middle dispersant is to ensure the solid content for the mixed slurry that the step is obtained Between 5 ~ 25%.
6. hydrothermal reaction coupling spray pyrolysis MnO according to claim 12The preparation method of/Graphene electrodes material, its feature It is:Step(1)And step(3)In, the surfactant is lauryl sodium sulfate, dodecyl sodium sulfate, dodecane Base benzene sulfonic acid sodium salt, polyethylene glycol, dioctyl succinate disulfonate acid, fatty acid sorbitan, polysorbate, polyoxyethylene, polyethylene Any one in alcohol, methyl anyl alcohol, polyacrylamide, fatty acid polyethylene glycol ester or two kinds, the total amount of adding of surfactant Respectively step(1)Manganese salt quality and step(3)The 0.01~0.5% of forerunner's weight.
7. hydrothermal reaction coupling spray pyrolysis MnO according to claim 12The preparation method of/Graphene electrodes material, its feature It is:Described obtained MnO2Graphene content in/Graphene electrodes material is 1.0~25%, particle mean size 10~ Between 80nm, obtained MnO2/ Graphene electrodes material first discharge specific capacity is more than 1300mAh/g, and specific capacitance is more than 360F/ g。
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