CN104355334B - There is superelevation birnessite type manganese oxide powder body than capacitance characteristic and preparation method and application - Google Patents
There is superelevation birnessite type manganese oxide powder body than capacitance characteristic and preparation method and application Download PDFInfo
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Abstract
The present invention is a kind of to have superelevation birnessite type manganese oxide powder body than capacitance characteristic and preparation method and application.The described preferable chemical formula of manganese oxide powder body is M2xMnO2+x, in formula, M is the combination in any of Li, Na, K cation, and wherein x is between 0.1 0.5.Described manganese oxide raw powder's production technology is: controls the mol ratio of permanganate and organic-fuel, is added drop-wise in permanganate water solution by organic fuel solution；Be placed on heating in the middle of Muffle furnace, finally can obtain required described birnessite type manganese oxide powder body.Manganese oxide power production cheaper starting materials disclosed by the invention, equipment is simple, production efficiency is high, and more excellent than capacitance characteristic (at 1A g‑1Up to 1055F g under electric current density‑1), can be applicable to the fields such as ultracapacitor, lithium/sodium/Magnesium ion battery, ion exchange, photocatalytic water, of many uses.
Description
Technical field
The invention belongs to chemical field and the preparation of the manganese oxide in Material Field and application thereof, a kind of have superelevation birnessite type manganese oxide powder body than capacitance characteristic and preparation method and application.
Background technology
Ultracapacitor is the novel energy-storing element between traditional capacitor and battery, has the features such as high-power output, high charge-discharge efficiencies, long circulation life, has broad application prospects at the aspect such as mobile communication, electric automobile.At present, the research to ultracapacitor is concentrated mainly on raising unit volume energy storage density, and it is crucial for synthesizing new electrode active material.
Mainly there are material with carbon element, transition metal oxide, conducting polymer etc. present stage for the electrode material of ultracapacitor.These several electrode materials are individually present different pluses and minuses.Material with carbon element has that specific surface area is big, good chemical stability, in ultracapacitor, it is commonly used for electrode material forms electric double layer capacitance, but because its storage electric charge is essentially from electric double layer capacitance, therefore specific capacity is relatively low, and the raising of chemical property is extremely restricted；Conducting polymer is due to the constraint of this body structure etc., and its application in terms of electrode material for super capacitor is also limited；And transition metal oxide is by occurring reversible faraday to react at Cathode/Solution Interface, the Faraday pseudo-capacitance much larger than material with carbon element electric double layer capacitance can be produced, thus cause the broad interest of various countries' researcher.
RuO2Faraday pseudo-capacitance has a good chemical property, but RuO2Cost the highest, and pollute environment, therefore be difficult to extensively apply.Researcher the most actively finds cheap transition metal oxide and other compounds to substitute RuO2.Current research focuses primarily upon NiO, Co3O4And MnO2Etc. in cheap transition metal oxide system.Wherein NiO and Co3O4Because of its potential window relative narrower, energy density is relatively low, limits them and is applied to electrode material for super capacitor.MnO2Being then the transition metal oxide electrode material that receives significant attention of another kind, it has and RuO2Similar properties, and have aboundresources, cheap, advantages of environment protection and become ideal electrode material for super capacitor.
Prepare MnO at present2Method mainly have liquid-phase precipitation method, sol-gel process, electrochemical deposition method, low-temperature solid-phase method and hydro-thermal method etc., but the MnO that most methods prepares2As super capacitor material poor performance, it is primarily present specific discharge capacity low, the problems such as cyclical stability is poor.Which limits MnO2Large-scale application in ultracapacitor industry.
Summary of the invention
The invention aims to provide a kind of and there is the superelevation birnessite type manganese oxide powder body than capacitance characteristic, with and preparation method and application.The birnessite type manganese oxide powder body of the present invention has the ratio capacitance characteristic of superelevation (at 1A g-1Up to 1055F g under electric current density-1), and preparation method disclosed by the invention has raw materials for production are cheap, equipment is simple, production efficiency is high feature.
The present invention is achieved through the following technical solutions:
A kind of have the superelevation birnessite type manganese oxide powder body than capacitance characteristic, and its chemical general formula is M2xMnO2+x, a kind of or arbitrary proportion during M is Li, Na, K cation in formula several, wherein the value of x is 0.1≤x≤0.5.
Birnessite type manganese oxide raw powder's production technology of the present invention comprises the steps: that the mol ratio controlling permanganate and organic-fuel is 0.3-12, is dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 0.10-5.0mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 0.10-4.0mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 120-450 ° of C heating 0.2-5 hour；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying；Wherein, described permanganate is the several of a kind of or arbitrary proportion in potassium permanganate, sodium permanganate, high manganese lithium, and described organic-fuel is citric acid, glycine or carbamide.
Further, also doped with Fe, Co, Ni element, the conductivity improving material with this and electrochemical properties in described birnessite type manganese oxide powder body, wherein, doped chemical is 1:500-1:25 with the mol ratio of manganese element.Accordingly, in the mixed solution that described preparation method includes oriented aqueous solutions of organic acids and permanganate water solution, add the treatment process of Fe, Co, Ni inorganic salt.
Described birnessite type manganese oxide powder body is compounded with high conductivity nano material, wherein, birnessite type manganese oxide powder body and the mass ratio 1:2-500:1 of high conductivity nano material.Described high conductivity nano material is activated carbon, CNT, carbon fiber, Graphene, gold nanowire, conducting polymer etc..Accordingly, in the mixed solution that described preparation method includes oriented aqueous solutions of organic acids and permanganate water solution, add the treatment process of high conductivity nano material.
Birnessite type manganese oxide powder body of the present invention can apply to the fields such as ultracapacitor, lithium ion battery, sodium-ion battery, Magnesium ion battery, ion-exchanger, photocatalytic water, and range of application is wider.
Manganese oxide power production cheaper starting materials disclosed by the invention, equipment is simple, production efficiency is high, and more excellent than capacitance characteristic, at 1A g-1Under electric current density up to
1055F∙g-1, can be applicable to the fields such as ultracapacitor, lithium/sodium/Magnesium ion battery, ion exchange, photocatalytic water, of many uses.
Accompanying drawing explanation
The formula that Fig. 1 is obtained by embodiment 1 is K2Mn4O9The typical scan electromicroscopic photograph of manganese oxide powder body
Fig. 2 is K by the formula of embodiment 1 invention acquisition2Mn4O9The typical transmission electron micrograph of manganese oxide powder body
The K that Fig. 3 by the formula of embodiment 9 invention acquisition is2Mn4O9The typical scan electron micrograph of composite that formed of manganese oxide powder body and CNT
Fig. 4 is K by the formula of embodiment 9 invention acquisition2Mn4O9The typical transmission electron micrograph of composite that formed of manganese oxide powder body and CNT
The formula that Fig. 5 is obtained by embodiment 1 is K2Mn4O9The ratio electric capacity-charging and discharging currents density relationship curve of manganese oxide powder body.
The formula that Fig. 6 is obtained by embodiment 9 is K2Mn4O9Manganese oxide powder body and the ratio electric capacity-charging and discharging currents density relationship curve of carbon nano tube compound material.
Fig. 7 is Mn while being obtained by comparison example 13O4The ratio electric capacity-charging and discharging currents density relationship curve of manganese oxide powder body.
Detailed description of the invention
A kind of have the superelevation birnessite type manganese oxide powder body than capacitance characteristic, and its chemical general formula is M2xMnO2+x, a kind of or arbitrary proportion during M is Li, Na, K cation in formula several, wherein the value of x is 0.1≤x≤0.5.
The described superelevation that has than the birnessite type manganese oxide raw powder's production technology of capacitance characteristic is: the mol ratio controlling permanganate and organic-fuel is 0.3-12, is dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 0.10-5.0mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 0.10-4.0 mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 120-450 ° of C heating 0.2-5 hour；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying；Wherein, described permanganate is the several of a kind of or arbitrary proportion in potassium permanganate, sodium permanganate, high manganese lithium, and described organic-fuel is citric acid, glycine or carbamide.
When being embodied as, also doped with Fe, Co, Ni element, the conductivity improving material with this and electrochemical properties in described birnessite type manganese oxide powder body, wherein, doped chemical is 1:500-1:25 with the mol ratio of manganese element.Accordingly, in the mixed solution that described preparation method includes oriented aqueous solutions of organic acids and permanganate water solution, add the treatment process of Fe, Co, Ni inorganic salt.
Described birnessite type manganese oxide powder body is compounded with high conductivity nano material, wherein, birnessite type manganese oxide powder body and the mass ratio 1:2-500:1 of high conductivity nano material.Described high conductivity nano material is activated carbon, CNT, carbon fiber, Graphene, gold nanowire, conducting polymer etc..Accordingly, in the mixed solution that described preparation method includes oriented aqueous solutions of organic acids and permanganate water solution, add the treatment process of high conductivity nano material.
The present invention is expanded on further below in conjunction with specific embodiment, it should be explained that these embodiments are merely to illustrate the present invention rather than limit the scope of the invention.
Embodiment 1
Weigh 2.424g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 2
Weigh 0.182g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 120 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 3
Weigh 7.277g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 120 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 4
Weigh 3.609g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 5
Weigh 4.848g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 6
Weigh 0.182g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 450 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 7
Weigh 7.277g potassium permanganate (KMnO4) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 450 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 8
Weigh 3.609g potassium permanganate (KMnO4) and 25mg CNTs(10 wt%HNO3 reflux cooling process 12h, 60 ° of C in vacuum drying oven, place 12h) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 9
Weigh 3.609g potassium permanganate (KMnO4) and 50mg CNTs(10 wt%HNO3 reflux cooling process 12h, 60 ° of C in vacuum drying oven, place 12h) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 10
Weigh 3.609g potassium permanganate (KMnO4) and 100mg CNTs(10
Wt%HNO3 reflux cooling processes 12h, 60 ° of C and places 12h in vacuum drying oven) it is dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 11 doping metals Fe3+Ion K2Mn4O9Manganese oxide powder body
Weigh 3.609g potassium permanganate (KMnO4) and 3.705g iron chloride (FeCl3) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
Embodiment 12 doping metals Co2+The K of ion2Mn4O9Manganese oxide powder body
Weigh 3.609g potassium permanganate (KMnO4) and 2.596g zinc chloride (CoCl2) be dissolved in 90ml deionized water, magnetic agitation 10min, weigh 0.806g citric acid (C6H7O8·H2O) it is dissolved in the deionized water of 10ml, with dropper, citric acid solution is added drop-wise in potassium permanganate solution, dropping limit, limit is stirred, then precursor liquid is placed in atmosphere tube type stove under 250 ° of C, keeps 30min, it is cooled to room temperature and collects product, cleaning 3 times with deionized water, then 60 ° of C place 12h in vacuum drying oven.
The K of embodiment 13 coated with conductive polymer ppy2Mn4O9Manganese oxide powder body
On the basis of embodiment 2,1) weigh 0.187g K2Mn4O9Manganese oxide powder body；2) by 0.416g P-TSAC(p-methyl benzenesulfonic acid) it is dissolved in 30ml dehydrated alcohol, stir, be subsequently adding 0.1ml pyrroles (0.048mol/L) and add above-mentioned solution, stir 10min, form solution A；3) by 0.12gAPSC(Ammonium persulfate .) it is dissolved in the deionized water of 20ml, stir formation B solution；4) sample is uniformly spread out on filter paper, under the conditions of sucking filtration, drip 12 solution A with dropper, after 1min, drip 12 B solution, under dark condition, place 24h, with deionized water, ethanol purge, 60 ° of C vacuum are placed 24h.
The K of embodiment 14 coated with conductive polymer P AN2Mn4O9Manganese oxide powder body
On the basis of embodiment 2,1) weigh two parts of 0.5 gram of manganese oxide sample；2) weigh 100ml1 mol/L nitric acid, be divided equally into two deciles, 0.5705 gram of Ammonium persulfate. of a addition, form solution A；Another part adds aniline 0.1826mL, forms solution B；3) 0.5 gram of manganese oxide sample is laid on filter paper, after by solution A, B mix and blend, after 26 minutes, mixed liquor graduates into light green color；Under the conditions of sucking filtration, with dropper, mixed liquor is dripped to manganese oxide sample surfaces, after adding about 30ml mixed liquor, stop dropping, and with a large amount of deionized water rinsing samples.Air is reset and is placed in 30min, be then placed in baking oven 50 degree dry.
Comparison example 1
0.79g potassium permanganate (KMnO4) is dissolved in 20ml deionized water, is added dropwise over 10ml 0.4mol/L
MnSO4 solution, stirring 24h makes it react abundant, collects pitchy sample, deionized water, ethanol purge, places 6h under 80 ° of C.
Embodiment 15
Having superelevation than the birnessite type manganese oxide raw powder's production technology of capacitance characteristic is: the mol ratio controlling sodium permanganate and sodium permanganate is 12, is dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 3.5mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 1.5mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 450 ° of C heating 4 hours；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying.
Embodiment 16
Having superelevation than the birnessite type manganese oxide raw powder's production technology of capacitance characteristic is: the mol ratio controlling high manganese lithium and citric acid is 4, is dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 2mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 0.10mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 300 ° of C heating 0.2 hour；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying.
Embodiment 17
Having superelevation than the birnessite type manganese oxide raw powder's production technology of capacitance characteristic is: the mol ratio controlling potassium permanganate and carbamide is 0.3, is dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 0.10mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 4.0mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 200 ° of C heating 2 hours；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying.
Embodiment 18
Having superelevation than the birnessite type manganese oxide raw powder's production technology of capacitance characteristic is: the mol ratio controlling sodium permanganate and carbamide is 8, is dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 5.0mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 3.0mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 120 ° of C heating 5 hours；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying.
Claims (2)
1. one kind has the superelevation birnessite type manganese oxide raw powder's production technology than capacitance characteristic, it is characterized in that, comprise the steps: that the mol ratio controlling permanganate and organic-fuel is 0.3-12, be dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 0.10-5.0mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 0.10-4.0 mol/L；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 120-450 DEG C heating 0.2-5 hour；Finally can obtain described birnessite type manganese oxide powder body after vacuum drying, the chemical general formula of described birnessite type manganese oxide powder body is M2xMnO2+x, a kind of or arbitrary proportion during M is Li, Na, K cation in formula several, wherein the value of x is 0.1≤x≤0.5；Described permanganate is the several of a kind of or arbitrary proportion in potassium permanganate, sodium permanganate, high manganese lithium, and described organic-fuel is citric acid, glycine or carbamide.
2. one kind has the superelevation preparation method than the birnessite type manganese oxide adulterated powder of capacitance characteristic, it is characterized in that: comprise the steps: that the mol ratio controlling permanganate and organic-fuel is 0.3-12, be dropwise added drop-wise in the middle of the permanganate water solution that molar concentration is 0.10-5.0mol/L obtain mixed solution by the organic-fuel aqueous solution that molar concentration is 0.10-4.0 mol/L；Then adding Fe, Co, Ni inorganic salt in the mixed solution of organic-fuel aqueous solution and permanganate water solution, doped chemical is 1:500-1:25 with the mol ratio of manganese element；Then the container that will be equipped with gained mixed solution is placed in the Muffle furnace of 120-450 DEG C heating 0.2-5 hour；Finally can obtain described birnessite type manganese oxide adulterated powder after vacuum drying, wherein, the chemical general formula of birnessite type manganese oxide powder body is M2xMnO2+x, a kind of or arbitrary proportion during M is Li, Na, K cation in formula several, wherein the value of x is 0.1≤x≤0.5；Described permanganate is the several of a kind of or arbitrary proportion in potassium permanganate, sodium permanganate, high manganese lithium, and described organic-fuel is citric acid, glycine or carbamide.
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| CN106449147A (en) * | 2016-11-16 | 2017-02-22 | 广州大学 | CMS/MnO2/PPY (carbon microsphere/manganese dioxide/polypyrrole) composite electrode material, as well as preparation method and application thereof |
| CN107093739B (en) * | 2017-05-08 | 2020-07-21 | 东北大学 | Potassium manganese oxide for potassium ion battery anode material and preparation method thereof |
| CN108511729B (en) * | 2018-04-28 | 2020-08-11 | 北京化工大学常州先进材料研究院 | Preparation method of potassium birnessite as electrode material of potassium ion battery |
| CN109638277A (en) * | 2018-12-10 | 2019-04-16 | 桂林理工大学 | A kind of preparation method of Magnesium ion battery manganous oxide negative electrode material |
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