CN101546651A - Nano graphite sheet/manganese dioxide doped composite material and preparation method thereof - Google Patents
Nano graphite sheet/manganese dioxide doped composite material and preparation method thereof Download PDFInfo
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- CN101546651A CN101546651A CN200910071963A CN200910071963A CN101546651A CN 101546651 A CN101546651 A CN 101546651A CN 200910071963 A CN200910071963 A CN 200910071963A CN 200910071963 A CN200910071963 A CN 200910071963A CN 101546651 A CN101546651 A CN 101546651A
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Abstract
The invention relates to a nano graphite sheet/manganese dioxide doped composite material and a preparation method thereof. The composite material consists of a nano graphite sheet and manganese dioxide doped nano granules evenly deposited on the surface of the nano graphite sheet, wherein the diameter of the nano graphite sheet is 100 nm to 50 mu m, and the thickness of the nano graphite sheet is 1nm to 200 nm; the diameter of the manganese dioxide doped nano granules is 3 to 100 nm, a manganese dioxide crystalline structure is a delta one-layer structure, other components are doped in the manganese dioxide nano granules, and the doped components are one or a random proportional mixture of more than two of transition metal elements such as copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, tin, cadmium and the like or rare-earth elements such as yttrium, lanthanum, praseodymium, cerium, neodymium, europium and the like; and the proportion of the manganese metal to the doped metal is 1:0-0.3. The weight ratio of the nano graphite sheet to the doped manganese dioxide is 1:0.01-100. The nano graphite sheet/manganese dioxide doped composite material not only has high specific capacity, but also has low internal resistance and good cyclical stability. The method has low cost, is simple, and is easy for industrialized production.
Description
(1) technical field
The present invention relates to the preparation of nano material, belong to material science, be specifically related to a kind of nano graphite sheet/manganese dioxide doped composite material and preparation method thereof.
(2) background technology
Ultracapacitor (Supercapacitor), also claim electrochemical capacitor (Electrochemical capacitor), it is a kind of novel energy-storing element between traditional capacitor and battery that grows up 60～seventies of 20th century, it has than higher energy density of traditional capacitor and the power density higher than secondary cell, have extended cycle life, can discharge and recharge by instantaneous large-current, at computer, digital product, portable phone, electric vehicle, there is wide application prospect aspect such as Aero-Space and national defense industry, has been subjected to people's extensive concern in recent years.According to the difference of energy storage mechanism, ultracapacitor can be divided into two types: double electric layer capacitor (Electricaldouble-layer capacitor) and Faraday pseudo-capacitance device (Pseudocapacitor).The former is based on the electric double layer that electrode (active carbon with high specific surface area)/electrolyte interface separation of charge produces, the latter is on the surface of electrode or the body two dimension or accurate two-dimensional space in mutually, electroactive material carries out underpotential deposition, highly reversible chemical adsorption desorption or redox reaction takes place, and produces the electric capacity relevant with the electrode charging potential.Under the situation of identical electrodes area, its capacity is tens times of electric double layer capacitance.
Because MnO
2With low cost, aboundresources, environmentally friendly, theoretical specific capacity is high (～1370F g
-1, be the focus that people study in recent years as electrode material for super capacitor always.In recent years, the manganese dioxide of various crystal formations (α, beta, gamma and λ) is used for electrode material for super capacitor by wide coverage.But, because its poorly conductive, in actual applications its capacity have only theoretical capacity 1/5 or 1/6 (J.PowerSources 178 (2008) 483 for S.B.Ma, et al.; C.Wan, et al., Electrochim.Acta 52 (2007) 3061; R.K.Sharma, et al., J.Power Sources 173 (2007) 1024).By with MnO
2With material with carbon elements such as carbon nano-tube, carbon blacks and conducting polymer is compound can improve its conductivity and then improve its chemical property, for example Chinese patent CN 1261387C report is 290F/g with carbon nano-tube and its specific capacity of the compound back of amorphous manganese dioxide, and internal resistance has only 0.7 Ω.Yet though the carbon nano-tube good conductivity costs an arm and a leg, this has just limited the commercial Application of this composite material.Nano graphite flakes is newfound in the last few years nano-carbon material, this material specific area height, and good conductivity, and wide material sources can prepare from native graphite, are the extraordinary conductive fillers of place of carbon nanotubes therefore.Also can improve the stable crystal form of manganese dioxide to a certain extent by some hetero-atoms that in manganese dioxide, mix in addition, and then improve the cycle life that it discharges and recharges.The bibliographical information that nano graphite flakes and manganese dioxide doped composite material are not also arranged at present as yet.
(3) summary of the invention
The object of the present invention is to provide a kind of specific capacity height, internal resistance is low, a kind of nano graphite sheet/manganese dioxide doped composite material of good cycling stability.The present invention also aims to provide that a kind of cost is low, the preparation method simple, be easy to the preparation method of the nano graphite sheet/manganese dioxide doped composite material of suitability for industrialized production.
Nano graphite sheet/manganese dioxide doped composite material of the present invention has following feature: this material is made up of at the dopping manganese dioxide nano particle on nano graphite flakes surface nano graphite flakes and uniform deposition; Wherein the diameter of nano graphite flakes is 100nm～50 μ m, and thickness is 1nm～200nm; Dopping manganese dioxide particle diameter size is 3～100nm, the manganese dioxide crystalline structure is δ-layer structure, wherein be doped with other constituent element in the manganese dioxide nano particle, described other constituent element is the one or more kinds of arbitrary proportion mixtures among copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, cadmium, tin, yttrium, lanthanum, Praseodymium, cerium, the Nv Huo Eu, and the ratio of manganese metal and doping metals is 1:0.01～0.3; The weight ratio of nano graphite flakes and manganese dioxide or dopping manganese dioxide is 1:0.01～100.
Nano graphite sheet/manganese dioxide doped composite material provided by the invention can adopt following method preparation:
The preparation method one:
(1), to be scattered in the distilled water solution preparation concentration be the aqueous dispersions of the nano graphite flakes of 0.001～0.1g/mL by ultrasonic with nano graphite flakes:
(2), the soluble-salt of water-soluble manganous salt and doping metals is dissolved in the nano graphite flakes dispersion liquid that previous step obtains suddenly by manganese and doping constituent element weight ratio 1: 0.01～0.3, described other constituent element is the one or more kinds of arbitrary proportion mixtures among copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, cadmium, tin, yttrium, lanthanum, Praseodymium, cerium, the Nv Huo Eu; Wherein manganese salt and doped metal salt are 0.01～100:1 by the ratio of manganese dioxide and its gross weight of blended metal oxide and nano graphite flakes;
(3), under agitation the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide is joined in the mixture that step obtains, wherein the mol ratio of alkali and manganese and doping metals is 3～8:1; Control reaction temperature is 10～80 ℃, and reaction 0.5～6h is warming up to 100 ℃ then, continues aging 6～100h, filter, washing and with the solid product that obtains in 70～150 ℃ of oven dry, promptly get target product.
The preparation method two:
(1), to be scattered in the distilled water solution preparation concentration be the aqueous dispersions of the nano graphite flakes of 0.001～0.1g/mL by ultrasonic with nano graphite flakes;
(2), the soluble-salt of potassium permanganate and doping metals is dissolved in the nano graphite flakes dispersion liquid that previous step obtains by manganese and doping constituent element weight ratio 1:0.01～0.3, described other constituent element is the one or more kinds of arbitrary proportion mixtures among copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, tin, cadmium, yttrium, lanthanum, Praseodymium, cerium, the Nv Huo Eu; Wherein potassium permanganate and doped metal salt are 0.01～100:1 by the ratio of manganese dioxide and its gross weight of blended metal oxide and nano graphite flakes;
(3) the resulting mixed liquor of previous step is placed microwave heating equipment 400～2000W, microwave heating 1～30min promptly obtains the brownish black precipitation;
(4), brownish black sedimentation and filtration, the washing that will go up a rapid gained, promptly get nano graphite flakes/manganese dioxide composite material in 70～150 ℃ of oven dry.
Compared with prior art, the present invention has following advantage:
The nano graphite sheet/manganese dioxide doped composite material that the present invention is prepared, owing to be dispersed in to the manganese dioxide nano uniform particles nano graphite flakes surface of good conductivity, therefore not only effectively improve the specific area of manganese dioxide, reduced the internal resistance of composite material simultaneously.Be entrained in the stability that hetero-atom between its lattice also can improve layered manganese oxide in addition.As electrode material, not only the internal resistance of composite material significantly reduces, and the specific capacity height of material with this composite material, good cycling stability, this lower cost for material, the preparation method simply is easy to commercialization and large-scale production, therefore has the wide industrial application prospect.
(4) description of drawings
Fig. 1 is the schematic diagram of the prepared nano graphite sheet/manganese dioxide doped combination electrode material of the present invention.Wherein: 1 is nano graphite flakes, and 2 is dopping manganese dioxide.
Fig. 2 is the XRD spectra of the prepared nano graphite sheet/manganese dioxide doped combination electrode material of the embodiment of the invention 2.
Fig. 3 is the stereoscan photograph of the prepared nano graphite sheet/manganese dioxide doped combination electrode material of the embodiment of the invention 2.
Fig. 4 is the cycle life curve of the prepared nano graphite sheet/manganese dioxide doped combination electrode material of the embodiment of the invention 2 and comparative example 1 and 2 prepared electrode materials.
(5) embodiment
The present invention is further illustrated below in conjunction with specific embodiment:
(diameter is 500nm～10 μ m, and thickness is 1nm～50nm) by being scattered in preparation nano graphite flakes dispersion liquid in the 100mL distilled water in ultrasonic 2 hours with the 0.1g nano graphite flakes.Manganese chloride and the 0.001g ferric trichloride of 0.001g are dissolved in the above-mentioned dispersion liquid, add the 100mL aqueous solution that contains 0.0023g NaOH then.Stir down that control reaction temperature is 10 ℃ of reactions 6 hours, be warming up to 100 ℃ then, continue aging 6h, filter, washing and with the solid product that obtains in 150 ℃ of oven dry, promptly get target product.Wherein the weight ratio of the manganese dioxide of doping iron and nano graphite flakes is 0.01:1, and the average grain diameter of manganese dioxide is 10nm, and XRD characterizes it and is the δ layer structure, and the high-resolution-ration transmission electric-lens photo can be seen its layer structure.
(B) preparation of electrode and performance test
Be mixed into paste by following composition: nano graphite flakes/manganese dioxide composite electrode material (80wt%), conductive carbon black (10wt%), polytetrafluoroethylene (PTFE, 5wt%), distilled water (5wt%).Nano graphite flakes/manganese dioxide composite-like electrode material and the conductive carbon black mode by mechanical oscillation is fully mixed, add distilled water and PTFE emulsion successively, and stir even, collector adopts foaming metal nickel, the electrode lug adopts metallic nickel, and lug adopts the spot welding mode to be connected with collector; With above-mentioned mixed cream by hand or mechanical system be coated with prior sanction well and in the collector of soldering polar ear, to be coated with pole piece that cream finishes at 110 ℃ of vacuumize 10h, electrode (1cm is made in pole piece compacting after will drying on the hydraulic press behind the burr through paring off the edge then
2).With 1mol L
-1Na
2SO
4Be electrolyte, adopt three-electrode system, cyclic voltammetry is measured the ratio electric capacity of composite material, and AC impedence method is measured its internal resistance.Gained the results are shown in table 1.
Embodiment 2
(diameter is 5 μ m～50 μ m, and thickness is 30nm～200nm) by being scattered in preparation nano graphite flakes dispersion liquid in the 100mL distilled water in ultrasonic 2 hours with the 1g nano graphite flakes.Manganese acetate and the 2g cerous nitrate of 19.92g are dissolved in the above-mentioned dispersion liquid, add the 200mL aqueous solution that contains 23.04g NaOH then.Stir down that control reaction temperature is 80 ℃ of reactions 0.5 hour, be warming up to 100 ℃ then, continue aging 50h, filter, washing and with the solid product that obtains in 70 ℃ of oven dry, promptly get target product.Wherein the weight ratio of dopping manganese dioxide and nano graphite flakes is 10:1, and the average grain diameter of dopping manganese dioxide is 20nm.XRD characterizes it and is the δ layer structure, and the high-resolution-ration transmission electric-lens photo can be seen its layer structure.The preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 3
(diameter is 100nm～500nm, and thickness is 10nm～30nm) by being scattered in preparation nano graphite flakes dispersion liquid in the 100mL distilled water in ultrasonic 2 hours with the 1g nano graphite flakes.With the manganese nitrate of 20g, 1g cobalt nitrate and 2g lanthanum nitrate are dissolved in the above-mentioned dispersion liquid, add the 200mL aqueous solution that contains 25g NaOH then.Stir down that control reaction temperature is 60 ℃ of reactions 3 hours, be warming up to 100 ℃ then, continue aging 2h, filter, washing and with the solid product that obtains in 100 ℃ of oven dry, promptly get target product.Wherein the weight ratio of dopping manganese dioxide and nano graphite flakes is 12:1, and the average grain diameter of mixing manganese dioxide is 5nm.XRD characterizes it and is δ layer structure (Fig. 2), and the high-resolution-ration transmission electric-lens photo can be seen its layer structure (Fig. 4,5).The preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 4
(diameter is 1 μ m～5 μ m, and thickness is 10nm～100nm) by being scattered in preparation nano graphite flakes dispersion liquid in the 100mL distilled water in ultrasonic 2 hours with the 0.5g nano graphite flakes.The potassium permanganate of 18g and 5g nickel nitrate be dissolved in the above-mentioned dispersion liquid stir, placing power then is that the microwave heating equipment of 2000W heats 1min; After reaction finished, with the sedimentation and filtration washing that obtains, 150 ℃ of dryings promptly got nano graphite flakes/manganese dioxide composite electrode material.Wherein the weight ratio of dopping manganese dioxide and nano graphite flakes is 25:1, and the average grain diameter of dopping manganese dioxide is 100nm.XRD characterizes it and is the δ layer structure, and the high-resolution-ration transmission electric-lens photo can be seen its layer structure.The preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 5
(diameter is 1 μ m～5 μ m, and thickness is 10nm～100nm) by being scattered in preparation nano graphite flakes dispersion liquid in the 100mL distilled water in ultrasonic 2 hours with the 0.5g nano graphite flakes.The potassium permanganate of 25g and 2g ferric nitrate and 3g yttrium nitrate be dissolved in the above-mentioned dispersion liquid stir, placing power then is that the microwave heating equipment of 400W heats 30min; After reaction finished, with the sedimentation and filtration washing that obtains, 150 ℃ of dryings promptly got nano graphite flakes/manganese dioxide composite electrode material.The weight ratio of wherein mixing manganese dioxide and nano graphite flakes is 30:1, and the average grain diameter of dopping manganese dioxide is 100nm.XRD characterizes it and is the δ layer structure, and the high-resolution-ration transmission electric-lens photo can be seen its layer structure.The preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
The comparative example 1
This embodiment is the comparative example of embodiment 2, and manganese acetate and the 2g cerous nitrate of 19.92g is dissolved in the above-mentioned dispersion liquid, adds the 200mL aqueous solution that contains 23.04g NaOH then.Stir down that control reaction temperature is 80 ℃ of reactions 0.5 hour, be warming up to 100 ℃ then, continue aging 50h, filter, washing and with the solid product that obtains in 70 ℃ of oven dry, promptly get target product.The preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
The comparative example 2
This embodiment is the comparative example of embodiment 2, and (diameter is 5 μ m～50 μ m, and thickness is 30nm～200nm) by being scattered in preparation nano graphite flakes dispersion liquid in the 100mL distilled water in ultrasonic 2 hours with the 1g nano graphite flakes.The manganese acetate of 19.92g is dissolved in the above-mentioned dispersion liquid, adds the 200mL aqueous solution that contains 23.04g NaOH then.Stir down that control reaction temperature is 80 ℃ of reactions 0.5 hour, be warming up to 100 ℃ then, continue aging 50h, filter, washing and with the solid product that obtains in 70 ℃ of oven dry, promptly get target product.The preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Used nano graphite flakes all adopts disclosed literature method preparation among the above embodiment
[1]Chen?G，Wu?D，WengW，Wu?C.Exfoliation?of?graphite?flake?and?itsnanocomposites.Carbon?2003；41(3)：619-21.
[2]Stankovich?S，Dikin?DA，Piner?RD，Kohlhaas?KA，Kleinhammes?A，et?al.Synthesis?of?graphene-based?nanosheets?via?chemical?reduction?of?exfoliatedgraphite?oxide.Carbon?2007；45:1558-65
The test result of each embodiment of table 1
| Embodiment | Than electric capacity (Fg -1) | Internal resistance (Ω) |
| |
358 | 0.45 |
| Embodiment 2 | 309 | 0.71 |
| Embodiment 3 | 337 | 0.38 |
| Embodiment 4 | 321 | 0.59 |
| Embodiment 5 | 345 | 0.23 |
| Embodiment 6 | 323 | 0.27 |
| The comparative example 1 | 226 | 2.5 |
| The comparative example 2 | 266 | 0.56 |
Claims (5)
1, a kind of nano graphite sheet/manganese dioxide doped composite material is characterized in that: be made up of at the dopping manganese dioxide nano particle on nano graphite flakes surface nano graphite flakes and uniform deposition; The manganese dioxide crystalline structure is δ-layer structure, wherein be doped with other constituent element in the manganese dioxide nano particle, described other constituent element is the one or more kinds of arbitrary proportion mixtures among copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, cadmium, tin, yttrium, lanthanum, Praseodymium, cerium, the Nv Huo Eu, and the ratio of manganese metal and doping metals is 1:0.01～0.3; The weight ratio of nano graphite flakes and manganese dioxide or dopping manganese dioxide is 1:0.01～100.
2, nano graphite sheet/manganese dioxide doped composite material according to claim 1 is characterized in that: the diameter of nano graphite flakes is 100nm～50 μ m, and thickness is 1nm～200nm; Dopping manganese dioxide particle diameter size is 3～100nm.
3, the preparation method of the described nano graphite sheet/manganese dioxide doped composite material of a kind of claim 1 is characterized in that:
(1), to be scattered in the distilled water solution preparation concentration be the aqueous dispersions of the nano graphite flakes of 0.001～0.1g/mL by ultrasonic with nano graphite flakes:
(2), the soluble-salt of water-soluble manganous salt and doping metals is dissolved in the nano graphite flakes dispersion liquid that previous step obtains suddenly by manganese and doping constituent element weight ratio 1:0.01～0.3, described other constituent element is the one or more kinds of arbitrary proportion mixtures among copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, tin, cadmium, yttrium, lanthanum, Praseodymium, cerium, the Nv Huo Eu; Wherein manganese salt and doped metal salt are 0.01～100:1 by the ratio of manganese dioxide and its gross weight of blended metal oxide and nano graphite flakes;
(3), under agitation the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide is joined in the mixture that step obtains, wherein the mol ratio of alkali and manganese and doping metals is 3～8:1; Control reaction temperature is 10～80 ℃, and reaction 0.5～6h is warming up to 100 ℃ then, continues aging 6～100h, filter, washing and with the solid product that obtains in 70～150 ℃ of oven dry, promptly get target product.
4, the preparation method of nano graphite sheet/manganese dioxide doped composite material according to claim 3 is characterized in that: wherein the mol ratio of the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide and manganese and doping metals is 3～8:1.
5, the preparation method of the described nano graphite sheet/manganese dioxide doped composite material of a kind of claim 1, it is characterized in that: the preparation method of nano graphite sheet/manganese dioxide doped composite material is characterized in that:
(1), to be scattered in the distilled water solution preparation concentration be the aqueous dispersions of the nano graphite flakes of 0.001～0.1g/mL by ultrasonic with nano graphite flakes;
(2), the soluble-salt of potassium permanganate and doping metals is dissolved in the nano graphite flakes dispersion liquid that previous step obtains by manganese and doping constituent element weight ratio 1:0.01～0.3, described other constituent element is the one or more kinds of arbitrary proportion mixtures among copper, iron, cobalt, nickel, vanadium, zinc, molybdenum, cadmium, tin, yttrium, lanthanum, Praseodymium, cerium, the Nv Huo Eu; Wherein potassium permanganate and doped metal salt are 0.01～100:1 by the ratio of manganese dioxide and its gross weight of blended metal oxide and nano graphite flakes;
(3) the resulting mixed liquor of previous step is placed microwave heating equipment 400～2000W, microwave heating 1～30min promptly obtains the brownish black precipitation;
(4), brownish black sedimentation and filtration, the washing that will go up a rapid gained, promptly get nano graphite flakes/manganese dioxide composite material in 70～150 ℃ of oven dry.
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| CN113936925A (en) * | 2021-09-14 | 2022-01-14 | 佛山科学技术学院 | Bimetal ion doped manganese dioxide electrode and preparation method and application thereof |
| CN114711252A (en) * | 2022-04-22 | 2022-07-08 | 广东轻工职业技术学院 | Antibacterial packaging material and preparation method and application thereof |
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