CN106298249B - A kind of K1.33Mn8O16Preparation method and application - Google Patents
A kind of K1.33Mn8O16Preparation method and application Download PDFInfo
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- CN106298249B CN106298249B CN201610828381.1A CN201610828381A CN106298249B CN 106298249 B CN106298249 B CN 106298249B CN 201610828381 A CN201610828381 A CN 201610828381A CN 106298249 B CN106298249 B CN 106298249B
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- colloidal sol
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- sylvite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of K1.33Mn8O16Preparation method and application.Manganous salt, sylvite and organic carboxyl acid are mixed with water, stirring reaction, obtains colloidal sol；The colloidal sol passes through drying and dewatering, obtains gel；The gel is by calcining, up to K1.33Mn8O16.The preparation method is simple and easy to do, has the advantages that green, environmentally friendly, safe and cost-effective honest and clean.The K of preparation1.33Mn8O16Electrode of super capacitor is made as electrode material, show high reversible the embedding de- behavior of potassium ion and can charge-discharge performance, 110Fg can be obtained under 0~1.2V‑1Specific capacitance, have the advantages that good reversibility and operating potential window are wide.
Description
Technical field
The present invention relates to K1.33Mn8O16Preparation method and K1.33Mn8O16Application in ultracapacitor, belongs to super
Technical field of capacitor preparation.
Background technology
In recent years, go deep into the rise of ultracapacitor and to electrode material for super capacitor research, embeddedization
Compound shows preferable chemical property as electrode material for super capacitor, attracts attention.Wherein, manganese base alkali
Metal ion inlaid scheme is because its raw material resources is enriched, cost is low and environmental-friendly and particularly noticeable.
At present, the manganese base alkali metal ion inlaid scheme as electrode material for super capacitor, it has been reported that have three
Tie up the LiMn of tunnel structure2O4, 3 × 2 with 3 × 1 Na for mixing tunnel structure4Mn9O18(Na0.44MnO2) and layer structure
NaMnO2、K0.19MnO2、K0.17MnO2、K0.15MnO2、K0.27MnO2·0.6H2O, etc..
K1.33Mn8O16It is a kind of artificial synthesized compound, its crystal structure and the cryptomelane formed in nature
(cryptomelane), hollandite (hollandite), square cesarolite (coronadite) are identical, are 2 × 2 one-dimensional tunnel knots
Structure, difference lies in only embedded K in its crystal tunnel with mineral crystal+A kind of ion, is embedded in without other foreign ions.
K1.33Mn8O16System by Strobel et al. most earlier than purpose of the nineteen eighty-two based on research, by be electrolysed under 778K potassium vanadate with
MnCO3Fused salt and obtain, and its crystal structure (Vicat J, Fanchon E, Strobel P, et are determined first
al.The structure of K1.33Mn8O16and cation ordering in hollandite-type
structures.Acta Crystallographica Section B,1986, 42(2):162-167.)。
Chinese patent CN 103288139A disclose one kind and prepare α-Fe2O3Hollow-core construction and α-Fe2O3/K1.33Mn8O16Receive
The method of rice noodles, is related to K1.33Mn8O16Preparation, which obtains K using hydro-thermal process potassium permanganate and ammonium fluoride1.33Mn8O16
Nano wire.The preparation K identical with the patent1.33Mn8O16The method of nano wire, is also found in other documents (Wu J, Wang J, Li
H,et al.Designed synthesis of hematite-based nanosorbents for dye
removal.Journal of Materials Chemistry A,2013,1(34):9837-9847；Wu J,Li H,Wang
J,et al.Swift adsorptive removal of Congo red from aqueous solution by
K1.33Mn8O16nanowires.Journal of Nanoscience&Nanotechnology,2013,13(8):5452-
5460)。
In addition, some documents also reported and K1.33Mn8O16Structure is identical such as AxMn8O16The preparation method of compound.Than
Such as, Yamamoto et al. is reported prepares Rb with hydro-thermal method1.5Mn8O16(Yamamoto N, Oka Y,Tamada O.Single
crystal growth and structure determination of Rb1.5Mn8O16 hollandite.Journal of
Mineralogical and Petrological Sciences,1990,15(2):41-49)；Takeuchi et al. is reported
One kind synthesis AgxMn8O16Method, be similarly to use hydro-thermal method (Takeuchi K J, Yau S Z, Menard M C, et
al.Synthetic control of composition and crystallite size of silver
hollandite,AgxMn8O16:Impact on electrochemistry.ACS applied materials &
interfaces,2012,4(10):5547-5554)；Lan et al. is described is prepared for Na using molten-salt growth method2-xMn8O16Nanometer
Rod (Lan C, Gong J, Liu S, et al.Synthesis and magnetic properties of single-
crystalline Na2-xMn8O16nanorods.Nanoscale Research Letters,2011,6: 133)。
On K1.33Mn8O16Application, removed, in addition to the application in terms of wastewater treatment in dyestuff except having reported, not yet
See K1.33Mn8O16Report as electrode material for super capacitor.
The content of the invention
K is obtained for the prior art1.33Mn8O16Technological means it is limited, existing electrolysis molten-salt growth method energy consumption is big, cost
Height, and hydro-thermal method realizes that large-scale production is had any problem, and the potassium permanganate with strong oxidizing property is used as raw material, it is hidden to there is safety
Suffer from；K is prepared based on sol-gel process the purpose of the invention is to provide one kind1.33Mn8O16Method, this method energy consumption
Low, cost is low, safety and environmental protection, can mass produce.
Another object of the present invention is to be to provide the K1.33Mn8O16As electrode material in ultracapacitor
Using the electrode of preparation has the advantages that higher specific capacitance, good reversibility, operating potential window are wide.
In order to realize above-mentioned technical purpose, the present invention provides a kind of K1.33Mn8O16Preparation method, this method is by two
Valency manganese salt, sylvite and organic carboxyl acid are mixed with water, in 40~80 DEG C of stirring reactions, obtain colloidal sol；The colloidal sol passes through 80~150
DEG C drying and dewatering, obtains gel；The gel is placed in 200~800 DEG C of temperature lower calcinations, to obtain the final product.
Preferable scheme, the ratio of sylvite, manganous salt and organic carboxyl acid is by K: Mn: the amount ratio of the material of organic carboxyl acid is
0.17~0.25: 1: 1~3 meterings.Most preferred scheme, sylvite (KHCO3), manganous salt (Mn (Ac)2·H2) and citric acid O
Ratio press K: Mn: the amount ratio of the material of organic carboxyl acid for 0.17: 1: 1 metering.
More preferably scheme, manganous salt include at least one of manganese acetate, manganese acetate hydrate and manganese carbonate.It is more excellent
Elect a hydration manganese acetate as.
More preferably scheme, sylvite include at least one in potassium acetate, potassium acetate hydrate, potassium carbonate and saleratus
Kind.More preferably potassium acetate or saleratus.
More preferably scheme, organic carboxyl acid include at least one of citric acid, tartaric acid and oxalic acid.More preferably lemon
Acid.
More preferably scheme, manganous salt, sylvite and organic carboxyl acid and water are reacted in 65~75 DEG C of stirrings, obtain colloidal sol.
Preferred reaction temperature is 70 DEG C.The time of stirring reaction is until various raw materials fully dissolve, and have a large amount of vitreosols
Formed, this belongs to the category that this technology personnel are appreciated that.
More preferably scheme, colloidal sol pass through 105~115 DEG C of drying and dewaterings.Preferred drying temperature is 110 DEG C.
More preferably scheme, gel are placed in 400~700 DEG C of temperature lower calcinations.Preferred calcining heat is 550 DEG C.Forge
The burning time is generally 2~12h, is suitably adjusted according to the size of calcining heat.
Present invention also offers the K1.33Mn8O16Application, which is by K1.33Mn8O16As electrode material application
In preparing ultracapacitor.
Preferable scheme, by K1.33Mn8O16, conductive agent and bonding agent mixing after, coating on a current collector, be made super electricity
Container electrode.
More preferably scheme, by K1.33Mn8O16(as active material), acetylene black (common conductive agent) and polytetrafluoroethylene (PTFE)
(common binding agent) is according to mass ratio K1.33Mn8O16：Acetylene black：Polytetrafluoroethylene (PTFE)=80:10~15:5~10 ratio is mixed
Close；Collector uses the 316L stainless (steel) wires of 300~400 mesh；Electrolyte is 0.1~0.64molL-1Potassium sulfate solution
Or 0.5~3.13molL-1Potassium nitrate aqueous solution.Further preferred solution is to use concentration as 0.5molL-1Sulphur
Sour aqueous solutions of potassium or 2molL-1Potassium nitrate aqueous solution.
Compared with the prior art, the advantageous effects that technical scheme is brought are：
1st, technical scheme, K is prepared using the oxidation pathway of Mn (II) → Mn (IV)1.33Mn8O16, rather than Mn
(VII) original route of going back of → Mn (IV) prepares K1.33Mn8O16, KMnO need to be used by avoiding conventional method4For raw material, and there is peace
The drawbacks of full hidden danger, thus preparation process has the advantages that security is more preferable.
2nd, technical scheme, using without Cl-Or NO3 -Manganous salt be raw material, avoid in calcination process
Because containing Cl-Or NO3 -HCl, NO of generation2Deng toxic and harmful gas the shortcomings that, thus preparation process have green, environmental protection it is excellent
Point.
3rd, technical scheme, realizes the preparation of colloidal sol and gel at a lower temperature, and in middle cryogenic conditions
Under roasted, realize K1.33Mn8O16Preparation, have the advantages that preparation process energy consumption is relatively low.
4th, technical scheme, the cost of material of use is cheap, preparation is simple and energy consumption is low, thus has
The advantages of having cost low and being adapted to large-scale production.
5th, technical scheme, the K of preparation1.33Mn8O16Electrode of super capacitor is used to prepare as electrode material,
Potassium ion with high reversible is embedding-de- behavior and can charge-discharge performance, 110Fg can be obtained under 0~1.2V-1Ratio electricity
The advantages that appearance, reversibility of electrode is good, and operating potential window is wide, K1.33Mn8O16It can be used as a kind of good electrode material
In ultracapacitor, K has been widened1.33Mn8O16Application range.
Brief description of the drawings
【Fig. 1】The K prepared for embodiment 11.33Mn8O16XRD diagram.
【Fig. 2】The K prepared for embodiment 21.33Mn8O16FTIR figure.
【Fig. 3】For K in embodiment 31.33Mn8O16Cathode is 1mVs in potential scan rate-1When, difference terminates scanning electricity
Cyclic voltammetry curve under gesture.
【Fig. 4】For K in embodiment 41.33Mn8O16For cathode when voltage range is 0~1.2V (vs.SCE), different electric currents are close
Charging and discharging curve under degree.
Embodiment
Present invention is more fully described in following embodiments, but is not intended to limit the protection domain of the claims in the present invention.
Embodiment 1
By a certain amount of Mn (Ac)2·H2O and citric acid (CA) mixing, the amount ratio for making material is Mn/CA=1, adds 60mL
Distilled water, is placed in heating and magnetic agitation in 70 DEG C of water-baths, mixture is fully dissolved.Added again into the solution a certain amount of
KHCO3, the amount ratio for making material is K/Mn=0.17, is sufficiently stirred after dissolving products therefrom through laser pen candling to be colourless
Bright colloidal sol.Colloidal sol is dried at 110 DEG C, obtains white gels.By the finely ground porcelain for being placed on 60cm × 90cm of above-mentioned gel
It is placed in boat and by the porcelain boat equipped with gel in Muffle furnace, with 8 DEG C of min-1Speed be warming up to 550 DEG C, and keep the temperature 6h.It is cold
To room temperature, porcelain boat is taken out, up to product.Products therefrom is subjected to thing on X-ray powder diffraction instrument (Dandong, Y-3000)
Facies analysis, test condition are：Tube current 25mA, voltage 40KV, slit width 2nm, 2 θ angular scan ranges are 10 °~80 °.Test
The result is shown in attached drawing 1.It will be noted from fig. 1 that the XRD diffraction maximums and K of product1.33Mn8O16Standard card (PDF#77-1796) one
Cause, it is K to show products therefrom1.33Mn8O16。
Embodiment 2
By a certain amount of MnCO3And citric acid (CA) mixing, the amount ratio for making material is Mn/CA=1, adds 70mL distillations
Water, is placed in heating and magnetic agitation in 60 DEG C of water-baths, mixture is fully dissolved.Added again into the solution a certain amount of
K2CO3, make the amount of material than K/Mn be 0.25, it is water white transparency to be sufficiently stirred after dissolving products therefrom through laser pen candling
Colloidal sol.Colloidal sol is dried at 110 DEG C, obtains white gels.By the finely ground porcelain boat for being placed on 60cm × 90cm of above-mentioned gel
In and the porcelain boat equipped with gel is placed in Muffle furnace, with 8 DEG C of min-1Speed be warming up to 650 DEG C, and keep the temperature 4h.It is cooled to
After room temperature, porcelain boat is taken out, up to product.The product proves that with the product in embodiment 1 be same substance through XRD analysis.Should
Product (Thermo scientific, Nicolet iS10) on FT-IR spectrometers carries out infrared spectrum analysis, test condition
For：Number of sample scan 32, resolution ratio 4.0, samples gain 8.0,400~4000 cm of wave number scanning range-1.Test result is shown in
Attached drawing 2.From fig. 2 it can be seen that in 400~700cm-1Occur 4 absworption peaks in wave-number range, respectively positioned at 694,594,
522 and 481cm-1, this is because caused by the lattice vibration of Mn-O, meet tunnel structure MnO2Characteristic infrared absorption, show institute
Obtaining product has one-dimensional tunnel structure.
Embodiment 3
By K prepared in embodiment 11.33Mn8O16Powder, acetylene black and polytetrafluoroethylene (PTFE) (PTFE) press 80:15:5
Mass ratio mixes, and after adding a small amount of distilled water and ethanol, lasting stirring, is in rubber pureed to mixture, is rolled into thickness
Degree about 10 μm of film, the thin slice that size is 1cm × 1cm is cut into by film, by thin slice with 300 under the pressure of 12MPa
Mesh 316L stainless (steel) wires pressure knot together, is placed in 120 DEG C of vacuum drying chambers dry 8h, electrode slice is made.Using platinum plate electrode as
To electrode, saturated calomel electrode is reference electrode, prepared K1.33Mn8O16Electrode is working electrode, with 0.5molL-1Sulphur
Sour potassium solution is electrolyte, and using CHI760d electrochemical workstations, setting potential scan rate is 1mVs-1, respectively 0~
0.1V (vs.SCE), 0~0.2V (vs.SCE), 0~0.3V (vs.SCE), 0~0.5V (vs.SCE), 0~0.6V (vs.
SCE), 0~0.7V (vs.SCE), 0~0.8V (vs.SCE), 0~0.9V (vs.SCE), 0~1.0V (vs.SCE) and 0~
Cyclic voltammetry is carried out in 1.1V (vs.SCE) potential range.Test result is shown in attached drawing 3.It can be seen in figure 3 that in difference
Terminate under scanning potential, K1.33Mn8O16It is almost mirror image pair that the cyclic voltammetry curve of cathode, which is showed along the transverse axis of zero crossing,
The symmetry of title, shows K1.33Mn8O16Just having the K of high reversible+Abjection-embedded performance.
Embodiment 4
According to the method preparation work electrode and assembling three-electrode system of embodiment 3, with 2molL-1Potassium nitrate solution is
Electrolyte, using CHI760d electrochemical workstations, respectively in 100,500 and 1000mAg-1Current density under carry out charge and discharge
Electrical testing.Test result is shown in attached drawing 4.It can be seen from figure 4 that K1.33Mn8O16Cathode shows good fake capacitance characteristic,
And charging and discharging curve is symmetrical, show that electrode material has good charge-discharge performance.
The explanation of above example is only the method and its core concept for helping to understand the present invention.It should be pointed out that for this
For the those of ordinary skill of technical field, without departing from the principle of the present invention, the present invention can also be carried out some
Improve and modification, these improvement and modification are fallen within the scope of the hereto appended claims.
Claims (7)
- A kind of 1. K1.33Mn8O16Preparation method, it is characterised in that：Manganous salt, sylvite and organic carboxyl acid are mixed with water, 40~80 DEG C of stirring reactions, obtain colloidal sol；The colloidal sol passes through 80~150 DEG C of drying and dewaterings, obtains gel；The gel is placed in 200~800 DEG C of temperature lower calcinations, to obtain the final product；The manganous salt includes at least one of manganese acetate, manganese acetate hydrate and manganese carbonate.
- 2. K according to claim 11.33Mn8O16Preparation method, it is characterised in that：Sylvite, manganous salt and organic carboxylic The ratio of acid presses K: Mn: the amount ratio of the material of organic carboxyl acid is 0.17~0.25: 1: 1~3 meterings.
- 3. K according to claim 1 or 21.33Mn8O16Preparation method, it is characterised in that：The sylvite includes acetic acid At least one of potassium, potassium acetate hydrate, potassium carbonate and saleratus.
- 4. K according to claim 1 or 21.33Mn8O16Preparation method, it is characterised in that：The organic carboxyl acid includes At least one of citric acid, tartaric acid and oxalic acid.
- 5. K according to claim 1 or 21.33Mn8O16Preparation method, it is characterised in that：Manganous salt, sylvite and organic Carboxylic acid is reacted with water in 65~75 DEG C of stirrings, obtains colloidal sol.
- 6. K according to claim 1 or 21.33Mn8O16Preparation method, it is characterised in that：Colloidal sol passes through 105~115 DEG C Drying and dewatering.
- 7. K according to claim 1 or 21.33Mn8O16Preparation method, it is characterised in that：Gel is placed in 400~700 DEG C Temperature lower calcination.
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