CN102760583A - Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method - Google Patents
Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method Download PDFInfo
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Abstract
The invention discloses a hollow honeycomb MnO2/C micro nanosphere and microrod preparation method. The preparation method comprises the following steps: (1) purifying carbon material; (2) adding manganese salt into deionized water, adding the purified carbon material after resolution, then adding potassium permanganate and mixing, and transposing the mixture in a hydro-thermal reaction kettle; (3) placing the hydro-thermal reaction kettle into a baking oven, and cooling the mixture to the ambient temperature after reaction for 1-15 hours under the hydro-thermal condition to obtain a hydro-thermal reaction product; and (4) repeatedly washing and filtering the hydro-thermal reaction product through the deionized water, then drying the obtained product, taking out the dried product and grinding to obtain hollow honeycomb MnO2/C micro nanospheres and microrod materials shaped like bird' nests for super capacitors. The preparation method adopts a simple preparation technology, achieves short synthesis time and can prepare the hollow honeycomb MnO2/C micro nanospheres and microrod materials. The hollow honeycomb MnO2/C micro nanospheres are porous on the surface, adopt special hollow structures and have the diameter of about 500nm; and the microrod MnO2 has the diameter of about 30nm and the length of about 5um.
Description
Technical field
The present invention relates to the electrochemical material preparation field, be specifically related to that a kind of specific capacity is big, good rate capability, have extended cycle life and the ultracapacitor of low price, environmental protection with the cellular MnO of hollow
2The preparation method of/C micro-nano ball and micron bar.
Background technology
Along with the day by day enhancing of various countries to the growing and environmental consciousness of energy demand, it is particularly urgent that the development and utilization of the environment-protecting clean energy seems.Ultracapacitor is as a kind of novel energy-storing device; Because have that power density is big, charge-discharge velocity is fast, broad application temperature range, have extended cycle life, advantages such as coefficient of safety is high, non-maintaining, economic environmental protection; All be widely used in fields such as mobile communication, information technology, Aero-Space and science and techniques of defence; The particularly rise of environmental-protecting type electric automobile, ultracapacitor has shown unprecedented application prospect.RuO
2In the water system acid solution, have ratio electric capacity, and good invertibity is arranged, yet cost an arm and a leg and toxicity itself has limited its application up to 720 F/g.And MnO
2Low because of its cost, the source is wide, chemical property is good and environmentally friendly, its active electrode material as ultracapacitor has great application prospect.
MnO in theory
2Ratio electric capacity can reach 1370 F/g, but MnO
2The theoretical capacity utilance is on the low side, trace it to its cause be because: 1, MnO
2Be semi-conducting material, its poorly conductive; 2, MnO
2Energy storage be surface reaction, cause " a large amount of " interior active material not make full use of.Therefore, powder MnO
2The ratio capacitance range great majority of electrode are 100-300 F/g, far below theoretical value; And MnO
2The ratio electric capacity of membrane electrode then can reach 600-700 F/g.Although MnO
2Membrane electrode is more higher than electric capacity, but works as the active material increase of unit are, and after film thickened, it was very fast to descend than electric capacity, therefore, and MnO
2The membrane electrode area is not higher than electric capacity.
For these reasons, synthetic have a cellular MnO of hollow
2/ C micro-nano ball and micron bar material are the effective ways that improves its theoretical capacity utilance.The particularity of this structure, make its hollow structure as the electrolyte storage pool to shorten the ions diffusion distance, interconnective cellular porous structure provides ion transport passage fast, and its specific area is increased severely, thereby has produced conventional MnO
2The not available skin effect of material, small-size effect can increase discharge capacity in electrode reaction, hydro thermal method is the micro-nano MnO of a kind of preparation
2One of the most frequently used method.
Summary of the invention
The object of the present invention is to provide that a kind of specific capacity is big, good rate capability, have extended cycle life and the ultracapacitor of low price, environmental protection with the cellular MnO of hollow
2The preparation method of/C micro-nano ball and micron bar.
Technical scheme of the present invention is: the cellular MnO of a kind of hollow
2The preparation method of/C micro-nano ball and micron bar, its step is following:
(1) material with carbon element purifying: at first material with carbon element is carried out dry distillation charring, argon shield, carbonization temperature is 800-900 ℃; Carbonization time 10-14 h is put into the material with carbon element that bakes in the agate mortar then, with the potassium hydroxide mixed grinding; The mass ratio of material with carbon element and potassium hydroxide is 1:4-6; After in tube furnace, carrying out activation at last, cool to room temperature obtains the material with carbon element that purifying is crossed;
(2) manganese salt is added in the deionized water, magnetic agitation, the dissolving back adds the material with carbon element that purifying is crossed in the step (1); Add potassium permanganate and stirring again, transposition is in hydrothermal reaction kettle afterwards, and potassium permanganate is 0.1 ~ 10:1 with the ratio of the amount of substance of manganese salt; The adding quality of material with carbon element is 0.1 ~ 20% of a manganese salt quality; With the manganese dioxide quality is benchmark, and the addition of material with carbon element is 1 ~ 15% of a manganese dioxide amount, and the addition of deionized water is that to make the filling rate of hydrothermal reaction kettle be 10 ~ 90%;
(3) hydrothermal reaction kettle is placed baking oven,, obtain the hydro-thermal reaction product being cooled to room temperature behind reaction 1 ~ 15 h under 100 ~ 200 ℃ of thermostatted water heat conditions;
(4) the hydro-thermal reaction product is filtered with the deionized water cyclic washing; Remove fully and the pH of cleaning solution is 7 until unreacted reactant; Then with products therefrom dry 8 ~ 24 h under 60 ~ 150 ℃ the condition in baking oven; Be ground to 800 ~ 1600 orders after the taking-up, promptly obtain ultracapacitor with the cellular MnO of hollow
2/ C micro-nano ball and bird-nest type micron bar material.
Said material with carbon element is bamboo charcoal, active carbon or graphite oxide.
Said manganese salt is manganese chloride, manganese sulfate or manganese acetate.
The invention has the beneficial effects as follows: material with carbon element bamboo charcoal, active carbon or graphite oxide after the activation of the present invention have abundant aperture; And specific area is big; Bamboo charcoal or active carbon or graphite oxide evenly mix with manganese salt; Make made sample have that conductivity is better, the big characteristics of specific area, have the advantage of high power capacity, big multiplying power, long-life and low price and environmental protection when using as the ultracapacitor positive electrode.The cellular MnO of hollow that the present invention is prepared
2/ C micro-nano ball and micron bar material and active carbon are formed analog capacitor, and specific discharge capacity reaches 255 F/g, 170 F/g, 133 F/g, 105 F/g, 88 F/g respectively under 100 mA/g, 150 mA/g, 200 mA/g, 250 mA/g, 300 mA/g current densities.Preparation technology of the present invention is simple, and generated time is short, and preparing of success has the cellular MnO of hollow
2/ C micro-nano ball and micron bar material.This material has very unique distinction: (1) material with carbon element bamboo charcoal or active carbon or graphite oxide itself are exactly favorable conductive agent and electroactive material, and have abundant aperture and big specific area, and its introducing can not reduce MnO
2Capacity.(2) thin layer bamboo charcoal or active carbon or graphite oxide are coated on MnO on the one hand
2Particle surface has improved the conductivity between the particle; On the other hand, a part of bamboo charcoal or active carbon or graphite oxide can remain in MnO
2The conductivity of granule interior has been improved in inside, thereby its high rate performance is significantly improved.(3) the cellular MnO of hollow
2/ C micro-nano ball presents porous surface, the special construction of inner hollow, about 500 nm of the diameter of micro-nano ball; Micron bar MnO
2Diameter be about 30 nm, length is about 5 μ m, this special pattern and structure make it have bigger specific area, help the performance of its electrical property.
Description of drawings
Fig. 1 is the prepared cellular MnO of hollow of the embodiment of the invention 7
2/ C micro-nano ball and bird-nest type micron bar SEM figure;
Fig. 2 is that the embodiment of the invention 2 prepared bird-nest type micron bar SEM scheme;
Fig. 3 is the prepared cellular MnO of hollow of the embodiment of the invention 5
2/ C micro-nano ball SEM figure;
Fig. 4 is the prepared cellular MnO of hollow of the embodiment of the invention 9
2/ C micro-nano ball and bird-nest type micron bar SEM figure;
Fig. 5 is the XRD figure of the embodiment of the invention 2, embodiment 5, embodiment 7, embodiment 9 prepared samples;
Fig. 6 is the cellular MnO of the embodiment of the invention 9 prepared hollows
2Make super capacitor material after/C micro-nano ball and the bird-nest type micron bar buck at the different cyclic voltammetry curves of sweeping under the speed;
Fig. 7 is the cellular MnO of the embodiment of the invention 6 prepared hollows
2Make the charging and discharging curve of super capacitor material under the different electric current density after/C micro-nano ball and the bird-nest type micron bar buck.
Embodiment
Embodiment 1
Press the ratio 4:1 and the MnO of amount of substance
23% difference weighing potassium permanganate, manganese chloride and the graphite oxide of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds graphite oxide, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 40%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 120 ℃ of thermostatted water thermal response 3 h of baking oven.Make product through washing, dry, promptly get the cellular MnO of hollow
2/ C micro-nano ball.
Press the ratio 1:1 and the MnO of amount of substance
25% respectively weighing potassium permanganate, manganese chloride and bamboo charcoal of amount is transferred to manganese chloride magnetic agitation in the beaker that deionized water is housed, and fully the dissolving back adds bamboo charcoal, slowly add potassium permanganate again and stir, afterwards transposition in hydrothermal reaction kettle, filling rate 60%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 150 ℃ of thermostatted water thermal response 6 h of baking oven.Make product through washing, dry, promptly get bird-nest type MnO
2/ C micron bar material.
Embodiment 3
Press the ratio 0.25:1 and the MnO of amount of substance
29% difference weighing potassium permanganate, manganese chloride and the active carbon of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds active carbon, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 80%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 150 ℃ of thermostatted water thermal response 6 h of baking oven.Make product through washing, dry, promptly get bird-nest type MnO
2/ C micron bar material.
Embodiment 4
Press the ratio 0.5:1 and the MnO of amount of substance
212% difference weighing potassium permanganate, manganese chloride and the active carbon of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds active carbon, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 60%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 180 ℃ of thermostatted water thermal response 9 h of baking oven.Make product through washing, dry, promptly get bird-nest type MnO
2/ C micron bar.
Press the ratio 2:1 and the MnO of amount of substance
27% difference weighing potassium permanganate, manganese chloride and the graphite oxide of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds graphite oxide, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 80%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 120 ℃ of thermostatted water thermal response 6 h of baking oven.Make product through washing, dry, promptly get the cellular MnO of hollow
2/ C micro-nano ball.
Embodiment 6
Press the ratio 6:1 and the MnO of amount of substance
23% respectively weighing potassium permanganate, manganese chloride and bamboo charcoal of amount is transferred to manganese chloride magnetic agitation in the beaker that deionized water is housed, and fully the dissolving back adds bamboo charcoal, slowly add potassium permanganate again and stir, afterwards transposition in hydrothermal reaction kettle, filling rate 40%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 150 ℃ of thermostatted water thermal response 3 h of baking oven.Make product through washing, dry, promptly get bird-nest type MnO
2/ C micron bar.
Embodiment 7
Press the ratio 0.125:1 and the MnO of amount of substance
25% difference weighing potassium permanganate, manganese chloride and the graphite oxide of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds graphite oxide, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 40%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 150 ℃ of thermostatted water thermal response 12 h of baking oven.Make product through washing, dry, promptly get the cellular MnO of hollow
2/ C micro-nano ball and bird-nest type MnO
2/ C micron bar.
Embodiment 8
Press the ratio 0.25:1 and the MnO of amount of substance
27% respectively weighing potassium permanganate, manganese chloride and bamboo charcoal of amount is transferred to manganese chloride magnetic agitation in the beaker that deionized water is housed, and fully the dissolving back adds bamboo charcoal, slowly add potassium permanganate again and stir, afterwards transposition in hydrothermal reaction kettle, filling rate 80%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 120 ℃ of thermostatted water thermal response 6 h of baking oven.Make product through washing, dry, promptly get the cellular MnO of hollow
2/ C micro-nano ball.
Embodiment 9
Press the ratio 5:1 and the MnO of amount of substance
25% difference weighing potassium permanganate, manganese chloride and the active carbon of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds active carbon, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 40%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 180 ℃ of thermostatted water thermal response 9 h of baking oven.Make product through washing, dry, promptly get the cellular MnO of hollow
2/ C micro-nano ball and bird-nest type micron bar.
Press the ratio 1:1 and the MnO of amount of substance
212% difference weighing potassium permanganate, manganese chloride and the graphite oxide of amount; Manganese chloride is transferred to magnetic agitation in the beaker that deionized water is housed, fully the dissolving back adds graphite oxide, slowly adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards, filling rate 60%.Be cooled to room temperature after then hydrothermal reaction kettle being placed 150 ℃ of thermostatted water thermal response 3 h of baking oven.Make product through washing, dry, promptly get the cellular MnO of hollow
2/ C micro-nano ball.
Embodiment 11
The cellular MnO of a kind of hollow
2The preparation method of/C micro-nano ball and micron bar, its step is following:
(1) bamboo charcoal purifying: at first bamboo charcoal is carried out dry distillation charring, argon shield, carbonization temperature is 800 ℃; Carbonization time 10 h are put into the bamboo charcoal that bakes in the agate mortar then, with the potassium hydroxide mixed grinding; The mass ratio of bamboo charcoal and potassium hydroxide is 1:4; After in tube furnace, carrying out activation at last, cool to room temperature obtains the bamboo charcoal that purifying is crossed;
(2) manganese salt is added in the deionized water; Magnetic agitation, the dissolving back adds the bamboo charcoal that purifying is crossed in the step (1), adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards; Potassium permanganate is 0.1:1 with the ratio of the amount of substance of manganese chloride, and the adding quality of bamboo charcoal is 0.1% of a manganese chloride quality, and the addition of deionized water is that to make the filling rate of hydrothermal reaction kettle be 10%;
(3) hydrothermal reaction kettle is placed baking oven,, obtain the hydro-thermal reaction product being cooled to room temperature behind reaction 1 h under 100 ℃ of thermostatted water heat conditions;
(4) the hydro-thermal reaction product is filtered with the deionized water cyclic washing; Remove fully and the pH=7 of cleaning solution until unreacted reactant; With products therefrom dry 8 h under 60 ℃ the condition in baking oven, be ground to 800 orders after the taking-up then, promptly obtain ultracapacitor with the cellular MnO of hollow
2/ C micro-nano ball.
Embodiment 12
The cellular MnO of a kind of hollow
2The preparation method of/C micro-nano ball and micron bar, its step is following:
(1) activated carbon purification: at first active carbon is carried out dry distillation charring, argon shield, carbonization temperature is 900 ℃; Carbonization time 14 h are put into the active carbon that bakes in the agate mortar then, with the potassium hydroxide mixed grinding; The mass ratio of active carbon and potassium hydroxide is 1:6; After in tube furnace, carrying out activation at last, cool to room temperature obtains the active carbon that purifying is crossed;
(2) manganese sulfate is added in the deionized water; Magnetic agitation, the dissolving back adds the active carbon that purifying is crossed in the step (1), adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards; Potassium permanganate is 0.1 ~ 10 with the ratio of the amount of substance of manganese sulfate, and the adding quality of active carbon is 20% of a manganese sulfate quality, and the addition of deionized water is that to make the filling rate of hydrothermal reaction kettle be 90%;
(3) hydrothermal reaction kettle is placed baking oven,, obtain the hydro-thermal reaction product being cooled to room temperature behind reaction 15 h under 200 ℃ of thermostatted water heat conditions;
(4) the hydro-thermal reaction product is filtered with the deionized water cyclic washing; Remove fully and the pH=7 of cleaning solution until unreacted reactant; With products therefrom dry 24 h under 150 ℃ the condition in baking oven, be ground to 1600 orders after the taking-up then, promptly obtain ultracapacitor and use bird-nest type MnO
2/ C micron bar material.
Embodiment 13
The cellular MnO of a kind of hollow
2The preparation method of/C micro-nano ball and micron bar, its step is following:
(1) graphite oxide material purifying: at first graphite oxide is carried out dry distillation charring, argon shield, carbonization temperature is 800-900 ℃; Carbonization time 10-14 h is put into the graphite oxide that bakes in the agate mortar then, with the potassium hydroxide mixed grinding; The mass ratio of graphite oxide and potassium hydroxide is 1:4-6; After in tube furnace, carrying out activation at last, cool to room temperature obtains the graphite oxide that purifying is crossed;
(2) manganese acetate is added in the deionized water; Magnetic agitation, the dissolving back adds the graphite oxide that purifying is crossed in the step (1), adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards; Potassium permanganate is 0.1 ~ 10:1 with the ratio of the amount of substance of manganese acetate, and the adding quality of graphite oxide is 0.1 ~ 20% of a manganese acetate quality, and the addition of deionized water is that to make the filling rate of hydrothermal reaction kettle be 10 ~ 90%;
(3) hydrothermal reaction kettle is placed baking oven,, obtain the hydro-thermal reaction product being cooled to room temperature behind reaction 1 ~ 15 h under 100 ~ 200 ℃ of thermostatted water heat conditions;
(4) the hydro-thermal reaction product is filtered with the deionized water cyclic washing; Remove fully and the pH=7 of cleaning solution until unreacted reactant; Then with products therefrom dry 8 ~ 24 h under 60 ~ 150 ℃ the condition in baking oven; Be ground to 800 ~ 1600 orders after the taking-up, promptly obtain ultracapacitor with the cellular MnO of hollow
2/ C micro-nano ball.
Embodiment 14
The cellular MnO of a kind of hollow
2The preparation method of/C micro-nano ball and micron bar, its step is following:
(1) material with carbon element purifying: at first material with carbon element is carried out dry distillation charring, argon shield, carbonization temperature is 800-900 ℃; Carbonization time 10-14 h is put into the material with carbon element that bakes in the agate mortar then, with the potassium hydroxide mixed grinding; The mass ratio of material with carbon element and potassium hydroxide is 1:4-6; After in tube furnace, carrying out activation at last, cool to room temperature obtains the material with carbon element that purifying is crossed;
(2) manganese salt is added in the deionized water; Magnetic agitation, the dissolving back adds the material with carbon element that purifying is crossed in the step (1), adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards; Potassium permanganate is 0.1 ~ 10:1 with the ratio of the amount of substance of manganese salt, and the adding quality of material with carbon element is 0.1 ~ 20% of a manganese salt quality, and the addition of deionized water is that to make the filling rate of hydrothermal reaction kettle be 10 ~ 90%;
(3) hydrothermal reaction kettle is placed baking oven,, obtain the hydro-thermal reaction product being cooled to room temperature behind reaction 1 ~ 15 h under 100 ~ 200 ℃ of thermostatted water heat conditions;
(4) the hydro-thermal reaction product is filtered with the deionized water cyclic washing; Remove fully and the pH=7 of cleaning solution until unreacted reactant; Then with products therefrom dry 8 ~ 24 h under 60 ~ 150 ℃ the condition in baking oven; Be ground to 800 ~ 1600 orders after the taking-up, promptly obtain ultracapacitor with the cellular MnO of hollow
2/ C micro-nano ball and bird-nest type micron bar material.
Said material with carbon element is bamboo charcoal, active carbon or graphite oxide.
Said manganese salt is manganese chloride, manganese sulfate or manganese acetate.
Among the present invention, Fig. 1-4 test condition: adopt how much patterns of the JSM-6490LV type sem observation sample of company of NEC, the size of powder particle, the distribution of particle.
Fig. 1 and Fig. 4 be the embodiment of the invention 7 with the prepared hollow of embodiment 9 cellular with bird-nest type micron bar SEM figure.Can find out the existing bird-nest type micron bar of sample that makes under embodiment 7 and embodiment 9 conditions by figure, MnO is arranged again
2Micro-nano ball, and the hollow porous surface of ball.MnO
2The existence of micron bar can make and form better conductive path between the manganese dioxide micro-nano ball.No matter be bird-nest type micron bar or MnO
2Micro-nano ball, this particular structural make material have bigger specific area, help the giving full play to of chemical property of material.Fig. 2 is that the embodiment of the invention 2 prepared bird-nest type micron bar SEM scheme, and interts alternately between rod and the rod, and pattern is similar to Bird's Nest; Fig. 3 is the prepared cellular MnO of hollow of the embodiment of the invention 5
2/ C micro-nano ball SEM figure is the accumulation type between ball and the ball, arrange closely.Therefore, the MnO of this special construction
2Material improves its chemical property possibly.
Fig. 5 test condition: adopt the MnO of Rigaku D/max2400 type X-ray diffractometer to being synthesized
2/ bamboo charcoal composite material carries out material phase analysis and crystal structure characterizes.
Fig. 5 compares with PDF card (44-0141), has almost shown all α-MnO
2The characteristic peak of crystal is so its product is α-MnO
2, characteristic peak is more obvious, shows that the sample crystal formation is good.
Fig. 6 test condition:
MnO with preparation
2, super conductive carbon powder and ptfe emulsion process electrode by certain mass than with an amount of absolute ethyl alcohol mixing, three-electrode system is adopted in the cyclic voltammetric test, is auxiliary electrode with the active carbon, Ag/AgCl is a reference electrode, the Na of 1 mol/L
2SO
4Be electrolyte, link to each other with salt bridge between reference electrode and the electrolytic cell.Produce RST5000 type electrochemical workstation in Zhengzhou and carry out the cyclic voltammetric test.
Fig. 6 is the cellular MnO of the embodiment of the invention 9 prepared hollows
2Make super capacitor material after/C micro-nano ball and the bird-nest type micron bar buck at the different cyclic voltammetry curves of sweeping under the speed.The negative electrode of cyclic voltammetry curve, anodic process are symmetrical about zero base line, rectangle is better, shows good capacitance characteristic.Along with the increase of sweeping speed, curve still keeps good rectangle, and illustrative material has high rate performance preferably, is fit to discharging and recharging under the big multiplying power.
Fig. 7 test condition:
MnO with preparation
2, super conductive carbon powder and ptfe emulsion process electrode by certain mass than with an amount of absolute ethyl alcohol mixing, three-electrode system is adopted in the cyclic voltammetric test, is auxiliary electrode with the active carbon, Ag/AgCl is a reference electrode, the Na of 1 mol/L
2SO
4Be electrolyte, link to each other with salt bridge between reference electrode and the electrolytic cell.On the product NEWARE 5 V/10 mA cell testers of Shenzhen, test charging and discharging curve.
Fig. 7 is the cellular MnO of the embodiment of the invention 9 prepared hollows
2Make the charging and discharging curve of super capacitor material under the different electric current density after/C micro-nano ball and the bird-nest type micron bar buck.Charging and discharging curve is isosceles triangle basically, has shown good capacitance characteristic.Along with the increase of current density, discharge capacity reduces, and this is that electrochemical polarization and concentration polarization increase because current density increases.
Claims (3)
1. cellular MnO of hollow
2The preparation method of/C micro-nano ball and micron bar is characterized in that its step is following:
(1) material with carbon element purifying: at first material with carbon element is carried out dry distillation charring, argon shield, carbonization temperature is 800-900 ℃; Carbonization time 10-14 h is put into the material with carbon element that bakes in the agate mortar then, with the potassium hydroxide mixed grinding; The mass ratio of material with carbon element and potassium hydroxide is 1:4-6; After in tube furnace, carrying out activation at last, cool to room temperature obtains the material with carbon element that purifying is crossed;
(2) manganese salt is added in the deionized water; Magnetic agitation, the dissolving back adds the material with carbon element that purifying is crossed in the step (1), adds potassium permanganate again and also stirs; Transposition is in hydrothermal reaction kettle afterwards; Potassium permanganate is 0.1 ~ 10:1 with the ratio of the amount of substance of manganese salt, and the adding quality of material with carbon element is 0.1 ~ 20% of a manganese salt quality, and the addition of deionized water is that to make the filling rate of hydrothermal reaction kettle be 10 ~ 90%;
(3) hydrothermal reaction kettle is placed baking oven,, obtain the hydro-thermal reaction product being cooled to room temperature behind reaction 1 ~ 15 h under 100 ~ 200 ℃ of thermostatted water heat conditions;
(4) the hydro-thermal reaction product is filtered with the deionized water cyclic washing; Until the pH of cleaning solution is 7; With products therefrom dry 8 ~ 24 h under 60 ~ 150 ℃ the condition in baking oven, be ground to 800 ~ 1600 orders after the taking-up then, promptly obtain ultracapacitor with the cellular MnO of hollow
2/ C micro-nano ball and bird-nest type micron bar material.
2. the cellular MnO of hollow according to claim 1
2The preparation method of/C micro-nano ball and micron bar is characterized in that: said material with carbon element is bamboo charcoal, active carbon or graphite oxide.
3. the cellular MnO of hollow according to claim 1
2The preparation method of/C micro-nano ball and micron bar is characterized in that: said manganese salt is manganese chloride, manganese sulfate or manganese acetate.
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| CN108793257A (en) * | 2018-07-19 | 2018-11-13 | 江苏理工学院 | A kind of porous MnO2The preparation method of/graphite composite |
| CN109637812A (en) * | 2018-11-29 | 2019-04-16 | 深圳清华大学研究院 | Carbon-based manganese oxide composite material, preparation method, electrode slice and capacitor |
| CN109859953A (en) * | 2017-11-30 | 2019-06-07 | 北京化工大学 | A kind of preparation method of bamboo matrix activated carbon/manganese aerogel composite |
| CN113019359A (en) * | 2021-02-05 | 2021-06-25 | 中国科学院合肥物质科学研究院 | MnO (MnO)2Preparation method and application of triangular plate Fenton catalyst |
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| CN103910386B (en) * | 2014-01-16 | 2015-11-18 | 广东工业大学 | A kind of preparation method and application of Manganse Dioxide of hollow structure |
| CN103910386A (en) * | 2014-01-16 | 2014-07-09 | 广东工业大学 | Preparation method and use of manganese dioxide having hollow structure |
| CN104465130A (en) * | 2014-12-16 | 2015-03-25 | 吉林大学 | Method for preparing super capacitor electrode material |
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| CN107275112A (en) * | 2017-08-15 | 2017-10-20 | 中国工程物理研究院激光聚变研究中心 | Irradiation method prepares MnO2The method of doping bamboo charcoal based super capacitor electrode material |
| CN109859953A (en) * | 2017-11-30 | 2019-06-07 | 北京化工大学 | A kind of preparation method of bamboo matrix activated carbon/manganese aerogel composite |
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| CN109637812A (en) * | 2018-11-29 | 2019-04-16 | 深圳清华大学研究院 | Carbon-based manganese oxide composite material, preparation method, electrode slice and capacitor |
| CN109637812B (en) * | 2018-11-29 | 2021-01-12 | 深圳清华大学研究院 | Preparation method of carbon-based manganese oxide composite material |
| CN113019359A (en) * | 2021-02-05 | 2021-06-25 | 中国科学院合肥物质科学研究院 | MnO (MnO)2Preparation method and application of triangular plate Fenton catalyst |
| CN113019359B (en) * | 2021-02-05 | 2023-03-10 | 中国科学院合肥物质科学研究院 | MnO (MnO) 2 Preparation method and application of triangular-plate Fenton-like catalyst |
| CN114735675A (en) * | 2022-03-30 | 2022-07-12 | 山东大学 | Based on fullerene C60Porous carbon material dually doped with fullerene derivative and preparation method and application thereof |
| CN114735675B (en) * | 2022-03-30 | 2023-06-16 | 山东大学 | Fullerene C-based 60 Porous carbon material binary doped with fullerene derivative, and preparation method and application thereof |
| CN114749150A (en) * | 2022-04-28 | 2022-07-15 | 南开大学 | Biochar loaded manganese oxide composite material and preparation method and application thereof |
| CN115331976A (en) * | 2022-08-18 | 2022-11-11 | 贵州大学 | Preparation method and application of transition metal oxide hollow superstructure electrode material |
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