CN109346334A - A kind of Novel Titanium dioxide and manganese dioxide composite material and preparation method thereof - Google Patents
A kind of Novel Titanium dioxide and manganese dioxide composite material and preparation method thereof Download PDFInfo
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- CN109346334A CN109346334A CN201811344520.9A CN201811344520A CN109346334A CN 109346334 A CN109346334 A CN 109346334A CN 201811344520 A CN201811344520 A CN 201811344520A CN 109346334 A CN109346334 A CN 109346334A
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- titanium dioxide
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- manganese dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 29
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 29
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 29
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 22
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012545 processing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000002070 nanowire Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 deionized water Ester Chemical class 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the preparation methods of a kind of Novel Titanium dioxide and manganese dioxide composite material, comprising: Step 1: butyl titanate is added to the water, is configured to butyl titanate solution；Step 2: butyl titanate solution ultrasonic vibration is obtained the tio_2 suspension with alkyl after hydrolysis；Step 3: being filtered, washed to obtain titania powder after the tio_2 suspension with alkyl is carried out hydro-thermal process；Step 4: carrying out water-bath and Electric Pulse Treatment respectively after potassium permanganate and manganese sulfate are separately added into being configured to solution in water；Step 5: by titania powder with the liquor potassic permanganate after Electric Pulse Treatment and after manganese sulfate solution mixes, carry out hydro-thermal process, be filtered, washed, dry after obtain titanium dioxide and manganese dioxide composite material.The preparation method of Novel Titanium dioxide and manganese dioxide composite material provided by the invention, titanium dioxide and manganese dioxide composite material obtained are increased substantially relative to other manganese dioxide composite material face capacitors.
Description
Technical field
The invention belongs to electrode material preparation technical field, in particular to a kind of Novel Titanium dioxide and manganese dioxide are compound
Material and preparation method thereof.
Background technique
Manganese dioxide has many advantages, such as cheap, environmental-friendly, rich and easy to get, is mainly used in electrode of super capacitor
Material, lithium ion battery etc., have a good application prospect, and become one of research hotspot in recent years.Preparation at present
The method of manganese dioxide is relatively more, mainly there is oxidation-reduction method, electrodeposition process, microemulsion method and sol-gel method etc..But this
All there is some disadvantages for a little methods, such as: purity is lower, takes a long time, operates that relative complex, efficiency is more low.
Moreover, common manganese dioxide is as electrode material, conductivity is lower, the effective active matter within the short time
Utilization rate is low, causes actual capacitance relatively low.Studies have shown that manganese dioxide can obtain better capacitive character by modified
Can, most common method of modifying be doped with other materials it is compound.Titanium dioxide is a kind of semiconductor material and environment friend
Good, when selecting titanium dioxide to carry out compound tense to manganese dioxide, the electric property of manganese dioxide is significantly improved.
Summary of the invention
The object of the present invention is to provide the preparation methods of a kind of Novel Titanium dioxide and manganese dioxide composite material, use
Hydro-thermal method, during the preparation process using pulsed magnetic field as auxiliary, preparation process is simple, and titanium dioxide and manganese dioxide obtained are multiple
Condensation material is increased substantially relative to other manganese dioxide composite material face capacitors.
It is a still further object of the present invention to provide a kind of Novel Titanium dioxide and manganese dioxide composite materials, have higher
Face capacitor, super capacitor material can be used as.
Technical solution provided by the invention are as follows:
A kind of preparation method of Novel Titanium dioxide and manganese dioxide composite material, comprising:
Butyl titanate solution is configured to Step 1: butyl titanate is added to the water；
Step 2: reaction is hydrolyzed in the butyl titanate solution ultrasonic vibration, the titanium dioxide with alkyl is obtained
Suspension；
Step 3: being filtered after the tio_2 suspension with alkyl is carried out hydro-thermal process, washing obtains dioxy
Change titanium powder；
It is configured to liquor potassic permanganate Step 4: potassium permanganate is added to the water, manganese sulfate is added to the water and is configured to sulphur
The liquor potassic permanganate and the manganese sulfate solution are carried out water-bath and Electric Pulse Treatment by sour manganese solution respectively；
Step 5: by after the titania powder and Electric Pulse Treatment liquor potassic permanganate and manganese sulfate solution it is mixed
It closes, obtains titanium dioxide after pouring into reaction kettle progress hydro-thermal process, suction filtration, washing, drying after mixing and manganese dioxide is multiple
Condensation material.
Preferably, in the step 2, the time of hydrolysis is 15~30min.
Preferably, in the step 3, the temperature of hydro-thermal process is 100~200 DEG C, and the hydro-thermal time is 0.5~5h.
Preferably, in the step 4, bath temperature is 70~90 DEG C, and the time is 15~30min.
Preferably, in the step 4, the frequency of Electric Pulse Treatment is 3~5Hz, 200~600V of voltage, time 30
~90s.
Preferably, in the step 5, hydrothermal temperature is 100~200 DEG C, and the hydro-thermal time is 0.5~7h.
Preferably, in the step 5,3~12h is aged after hydro-thermal process, then filtered.
A kind of Novel Titanium dioxide and manganese dioxide composite material, it is multiple using the Novel Titanium dioxide and manganese dioxide
It is prepared by the preparation method of condensation material.
The beneficial effects of the present invention are:
(1) preparation method of Novel Titanium dioxide and manganese dioxide composite material provided by the invention, using hydro-thermal method,
Using pulsed magnetic field as auxiliary in preparation process, high-performance titanium dioxide and manganese dioxide composite material obtained are relative to other
Manganese dioxide composite material face capacitor increases substantially.
(2) offer Novel Titanium dioxide of the invention and manganese dioxide composite material preparation method, it is simple process, at low cost
It is honest and clean, be conducive to industrial mass production.
Detailed description of the invention
Fig. 1 is the SEM figure of titanium dioxide made from the embodiment of the present invention 1 and manganese dioxide composite material.
Fig. 2 is the SEM figure of titanium dioxide made from the embodiment of the present invention 2 and manganese dioxide composite material.
Fig. 3 is the SEM figure of titanium dioxide made from the embodiment of the present invention 3 and manganese dioxide composite material.
Fig. 4 is the SEM figure of titanium dioxide made from the embodiment of the present invention 4 and manganese dioxide composite material.
Fig. 5 is the SEM figure of titanium dioxide made from the embodiment of the present invention 5 and manganese dioxide composite material.
Fig. 6 is the SEM figure of α type manganese dioxide made from comparative example 1 of the present invention.
Fig. 7 is the SEM figure of titanium dioxide made from comparative example 2 of the present invention and manganese dioxide composite material.
Fig. 8 is the XRD spectrum of sample made from various embodiments of the present invention and comparative example.
Fig. 9 is sample electrode made from various embodiments of the present invention and comparative example in 2mA cm-2Constant current charge-discharge curve.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
The present invention provides the preparation methods of a kind of Novel Titanium dioxide and manganese dioxide composite material, including walk as follows
It is rapid:
Metatitanic acid fourth is made into Step 1: the butyl titanate that 15mL concentration is 0.3mol/L is added in 135mL deionized water
Ester solution；
Step 2: reaction is hydrolyzed in 15~30min of butyl titanate solution ultrasonic vibration obtained in step 1, obtain
Tio_2 suspension with alkyl；
Step 3: the tio_2 suspension with alkyl is carried out hydro-thermal process, hydrothermal temperature is 100~200 DEG C, water
The hot time is 0.5~5h；It after the completion of hydro-thermal process, filters, wash, be dried to obtain titania powder；
It is made into liquor potassic permanganate Step 4: 0.316g potassium permanganate is added in 40mL deionized water, by 0.453g
Manganese sulfate is added in 40mL deionized water and is made into manganese sulfate solution；By the liquor potassic permanganate and the manganese sulfate solution point
Not carry out water bath processing, bath temperature be 70~90 DEG C, the time be 15~30min；
Step 5: two kinds of solution of gained in step 4 are carried out Electric Pulse Treatment respectively；It is 3 that Electric Pulse Treatment, which applies frequency,
~5Hz, 200~600V of voltage, time are 30~90s；
Step 6: will be obtained in step 3 the potassium manganate solution in titania powder and step 5 after Electric Pulse Treatment with
And manganese sulfate solution mixing；After mixing, it pours into and carries out hydro-thermal process in reaction kettle；The temperature of hydro-thermal process is 100~200
DEG C, the hydro-thermal time is 0.5~7h；
Step 7: by after hydro-thermal process solution be aged 3~12h, filtered, washed, be dried to obtain titanium dioxide and
Manganese dioxide composite material.
Embodiment 1
(1) 15mL butyl titanate (0.3mol/L) is added in 135mL deionized water and is configured to solution；
(2) reaction is hydrolyzed in step (1) acquired solution ultrasonic vibration 15min；Suspension is taken to carry out hydro-thermal process, temperature
Degree is 100 DEG C, time 0.5h；
(3) it after the completion of hydro-thermal, is filtered, washed, is dried to obtain titania powder；
(4) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to permanganic acid in 40mL deionized water
Potassium solution and manganese sulfate solution；
(5) two kinds of solution (liquor potassic permanganate and manganese sulfate solution) that step (4) obtains are subjected to water bath processing respectively,
Temperature is 70 DEG C, time 15min；
(6) the resulting liquor potassic permanganate of step (5) and manganese sulfate solution are subjected to Electric Pulse Treatment respectively；Frequency is
3Hz, voltage 200V, time 30s；
(7) two kinds of solution mixing in the titania powder and step (6) obtained step (3) after Electric Pulse Treatment
Afterwards, it pours into and carries out hydro-thermal process in reaction kettle, temperature is 100 DEG C, time 0.5h；
(8) solution after step (7) hydro-thermal process is aged 3h, is filtered, washs, is dried to obtain titanium dioxide and two
Manganese oxide composite material.
As shown in Figure 1, agglomeration occurs in composite material obtained in embodiment 1, crystallinity is slightly worse, but still can be used as electricity
Capacity materials use.
Embodiment 2
(1) 15mL butyl titanate (0.3mol/L) is added in 135mL deionized water and is configured to solution；
(2) reaction is hydrolyzed in step (1) acquired solution ultrasonic vibration 20min；Suspension is taken to carry out hydro-thermal process, temperature
Degree is 150 DEG C, time 3h；
(3) it after the completion of hydro-thermal, filters, wash, be dried to obtain titania powder；
(4) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to solution in 40mL deionized water；
(5) two kinds of solution (liquor potassic permanganate and manganese sulfate solution) that step (4) obtains are subjected to water bath processing respectively,
Temperature is 80 DEG C, time 20min；
(6) the resulting liquor potassic permanganate of step (5) and manganese sulfate solution are subjected to Electric Pulse Treatment respectively；Frequency is
4Hz, voltage 400V, time 60s；
(7) two kinds of solution mixing in the titania powder and step (6) obtained step (3) after Electric Pulse Treatment
Afterwards, it pours into and carries out hydro-thermal process in reaction kettle, temperature is 180 DEG C, time 5h；
(8) solution after step (7) hydro-thermal process is aged 6h, is filtered, washs, is dried to obtain titanium dioxide and two
Manganese oxide composite material.
As shown in Fig. 2, composite powder obtained dispersion tends to uniformly, can be clearly seen that compound in embodiment 2
Material is by two kinds of structure compositions, the crystallinity enhancing of titanium dioxide and manganese dioxide.
Embodiment 3
(1) 15mL butyl titanate (0.3mol/L) is added in 135mL deionized water and is configured to solution；
(2) reaction is hydrolyzed in step (1) acquired solution ultrasonic vibration 30min；Suspension is taken to carry out hydro-thermal process, temperature
Degree is 200 DEG C, time 5h；
(3) it after the completion of hydro-thermal, is filtered, washed, is dried to obtain titania powder；
(4) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to solution in 40mL deionized water；
(5) two kinds of solution (liquor potassic permanganate and manganese sulfate solution) that step (4) obtains are subjected to water bath processing respectively,
Temperature is 90 DEG C, time 30min；
(6) the resulting liquor potassic permanganate of step (5) and manganese sulfate solution are subjected to Electric Pulse Treatment respectively；Frequency is
5Hz, voltage 600V, time 90s；
(7) after the two solution mixing in the titania powder and step (6) obtained step (3) after Electric Pulse Treatment,
It pours into and carries out hydro-thermal process in reaction kettle, temperature is 200 DEG C, time 7h；
(8) by after step (7) hydro-thermal process solution be aged 12h, filtered, washed, be dried to obtain titanium dioxide and
Manganese dioxide composite material.
As shown in figure 3, composite material obtained in embodiment 3 is made of nanometer rods and nano particle, manganese dioxide crystal form
For α type.
Embodiment 4
(1) 15mL butyl titanate (0.3mol/L) is added in 135mL deionized water and is configured to solution；
(2) reaction is hydrolyzed in step (1) acquired solution ultrasonic vibration 30min；Suspension is taken to carry out hydro-thermal process, temperature
Degree is 200 DEG C, time 5h；
(3) it after the completion of hydro-thermal, is filtered, washed, is dried to obtain titania powder；
(4) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to solution in 40mL deionized water；
(5) two kinds of solution (liquor potassic permanganate and manganese sulfate solution) that step (4) obtains are subjected to water bath processing respectively,
Temperature is 90 DEG C, time 30min；
(6) two kinds of solution obtained by step (5) are subjected to Electric Pulse Treatment respectively；Frequency is 3Hz, voltage 400V, time
90s；
(7) two kinds of solution mixing in the titania powder and step (6) obtained step (3) after Electric Pulse Treatment
Afterwards, it pours into and carries out hydro-thermal process in reaction kettle, temperature is 200 DEG C, time 7h；
(8) by after step (7) hydro-thermal process solution be aged 12h, filtered, washed, be dried to obtain titanium dioxide and
Manganese dioxide composite material.
As shown in figure 4, embodiment 4 has obtained the preferable titania nanoparticles of pattern and manganese dioxide nanowire, receive
Rice grain diameter is in 541nm or so, and nanorod length is in 400nm or so；The crystallinity of composite material is preferable at this time.
Embodiment 5
(1) 15mL butyl titanate (0.3mol/L) is added in 135mL deionized water and is configured to solution；
(2) reaction is hydrolyzed in step (1) acquired solution ultrasonic vibration 30min；Suspension is taken to carry out hydro-thermal process, temperature
Degree is 200 DEG C, time 5h；
(3) it after the completion of hydro-thermal, is filtered, washed, is dried to obtain titania powder；
(4) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to solution in 40mL deionized water；
(5) two kinds of solution (liquor potassic permanganate and manganese sulfate solution) that step (4) obtains are subjected to water bath processing respectively,
Temperature is 90 DEG C, time 30min；
(6) two kinds of solution obtained by step (5) are subjected to Electric Pulse Treatment respectively；Frequency is 4Hz, voltage 200V, time
90s；
(7) two kinds of solution mixing in the titania powder and step (6) obtained step (3) after Electric Pulse Treatment
Afterwards, it pours into and carries out hydro-thermal process in reaction kettle, temperature is 200 DEG C, time 7h；
(8) by after step (7) hydro-thermal process solution be aged 12h, filtered, washed, be dried to obtain titanium dioxide and
Manganese dioxide composite material.
As shown in figure 5, titania nanoparticles obtained in embodiment 5 are smaller, diameter is 331.5nm or so；Dioxy
Change manganese nano wire to reduce, manganese dioxide strength reduction, but still can be used as capacitance material use.
Comparative example 1
(1) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to solution in 40mL deionized water；
(2) two kinds of solution for obtaining step (1) carry out water bath processing respectively, and temperature is 90 DEG C, time 30min；
(3) two kinds of solution of step (2) are mixed, pours into and carries out hydro-thermal process in reaction kettle, temperature is 200 DEG C, the time
For 7h；
(4) step (3) solution is filtered, manganese dioxide powder can be obtained in washing, drying.
As shown in fig. 6, manganese dioxide powder pattern shows as nano wire, length is in 500nm or so.Manganese dioxide is α type
And crystallinity is preferable.
Comparative example 2
(1) 15mL butyl titanate is added to wiring solution-forming in 135mL deionized water；
(2) reaction is hydrolyzed in step (1) acquired solution ultrasonic vibration 30min, suspension is taken to carry out hydro-thermal process, temperature
Degree is 200 DEG C, time 5h；
(3) it after the completion of hydro-thermal, is filtered, washed, titania powder can be obtained；
(4) it is added separately to 0.316g potassium permanganate and 0.453g manganese sulfate to be configured to solution in 40mL deionized water；
(5) two kinds of solution for obtaining step (4) carry out water bath processing respectively, and temperature is 90 DEG C, time 30min；
(6) two kinds of solution after the powder of step (3) and step (5) water bath processing are mixed, pours into reaction kettle and carries out
Hydro-thermal process, temperature are 200 DEG C, time 7h；
(7) it filters, washs after step (6) solution being aged 12h, titanium dioxide and manganese dioxide can be obtained in drying
Composite material.
As shown in fig. 7, the composite material for not carrying out pulse processing that comparative example 2 obtains, the graininess of titanium dioxide is poor,
Agglomerates unfavorable its of getting together comes into full contact with electrolyte.Nanometer short bar structure is presented in manganese dioxide simultaneously, and largely covers
In titanium dioxide surface, the diameter of titanium dioxide granule is further increased.From figure 8, it is seen that in comparative example 2, dioxy
Change manganese to be suppressed in the growth of each crystal face.
In conclusion as shown in figs. 1-7, using field emission scanning electron microscope (Sigma-500) to each embodiment and
Sample obtained in comparative example is scanned, the results showed that with the addition of pulsed magnetic field, is received inside titanium dioxide by what is crimped
Rice piece constitutes nanosphere, and manganese dioxide is changed into a nanometer stub by nano wire.
As shown in figure 8, using the X-ray diffractometer of model D/max-2500, to gained in each embodiment and comparative example
Sample carry out structural analysis, the results showed that with the addition of pulsed magnetic field, the knot of titanium dioxide and manganese dioxide composite material
Crystalline substance enhancing.
As shown in figure 9, by sample obtained in each embodiment and comparative example and acetylene black, polytetrafluoroethylene (PTFE) (PTFE) with matter
The ratio mixing than 75:20:5 is measured, ethanol in proper amount is added, ultrasonic mixing 20min is equably scratched with blade 1cm × 1cm's
In nickel foam, after drying, flakiness is pushed in 10MPa pressure, sample electrode is made.
Using sample electrode as working electrode, saturated calomel electrode (SCE) is reference electrode, and platinum electrode is auxiliary electrode, by
3mol/L KOH solution is the electrification that electrolyte forms that three-electrode system uses Shanghai Chen Hua Instrument Ltd. CHI660D model
It learns work station and carries out electrochemical property test, electro-chemical test is carried out to material using constant current charge-discharge.Test result shows real
It applies after electrode is made in titanium dioxide and manganese dioxide composite material obtained in a 1-5, in 2mA cm-2Current density under, face
Capacitance is respectively 1376mF cm-2、1440mF cm-2、3376mF cm-2、6564mF cm-2With 1327mF cm-2, comparative example 1
With 2 in after electrode is made in material obtained, in 2mA cm-2Current density under, face capacitance is respectively 656mF cm-2With
720mF cm-2.Electrode made of embodiment 4 is compared with comparative example 1 and 2, and 90% and 89% has been respectively increased in face capacitor.
In conclusion titanium dioxide provided by the invention and manganese dioxide composite material preparation method, supplemented by electric pulse
It helps, is made of nanosphere inside titanium dioxide the nanometer sheet crimped, manganese dioxide is changed into a nanometer stub by nano wire；Composite wood
The crystallinity of material enhances.Electro-chemical test shows to prepare titanium dioxide and titanium dioxide using pulse auxiliary law produced by the present invention
Manganese composite material, in 2mA cm-2Current density under, face capacitance can reach 6564mF cm-2, carried out with comparative example 1 and 2
90% and 89% has been respectively increased in comparison, face capacitor.Face capacitor for other manganese dioxide composite materials improves
48% or so.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (8)
1. the preparation method of a kind of Novel Titanium dioxide and manganese dioxide composite material, which comprises the steps of:
Butyl titanate solution is configured to Step 1: butyl titanate is added to the water；
Step 2: reaction is hydrolyzed in the butyl titanate solution ultrasonic vibration, the titanium dioxide suspending with alkyl is obtained
Liquid；
Step 3: being filtered after the tio_2 suspension with alkyl is carried out hydro-thermal process, washing obtains titanium dioxide
Powder；
It is configured to liquor potassic permanganate Step 4: potassium permanganate is added to the water, manganese sulfate is added to the water and is configured to manganese sulfate
The liquor potassic permanganate and the manganese sulfate solution are carried out water-bath and Electric Pulse Treatment by solution respectively；
Step 5: by the mixing of liquor potassic permanganate and manganese sulfate solution after the titania powder and Electric Pulse Treatment,
It is poured into after reaction kettle carries out hydro-thermal process, suction filtration, washing, drying after mixing and obtains titanium dioxide and manganese dioxide composite wood
Material.
2. the preparation method of Novel Titanium dioxide according to claim 1 and manganese dioxide composite material, which is characterized in that
In the step 2, the time of hydrolysis is 15~30min.
3. the preparation method of Novel Titanium dioxide according to claim 2 and manganese dioxide composite material, which is characterized in that
In the step 3, the temperature of hydro-thermal process is 100~200 DEG C, and the hydro-thermal time is 0.5~5h.
4. the preparation method of Novel Titanium dioxide according to claim 3 and manganese dioxide composite material, which is characterized in that
In the step 4, bath temperature is 70~90 DEG C, and the time is 15~30min.
5. the preparation method of Novel Titanium dioxide according to claim 3 or 4 and manganese dioxide composite material, feature exist
In in the step 4, the frequency of Electric Pulse Treatment is 3~5Hz, 200~600V of voltage, 30~90s of time.
6. the preparation method of Novel Titanium dioxide according to claim 1 and manganese dioxide composite material, which is characterized in that
In the step 5, hydrothermal temperature is 100~200 DEG C, and the hydro-thermal time is 0.5~7h.
7. the preparation method of Novel Titanium dioxide according to claim 6 and manganese dioxide composite material, which is characterized in that
In the step 5,3~12h is aged after hydro-thermal process, then filtered.
8. a kind of Novel Titanium dioxide and manganese dioxide composite material, which is characterized in that using such as claim 1-7 any one
It is prepared by the preparation method of the Novel Titanium dioxide and manganese dioxide composite material.
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| CN106024401A (en) * | 2016-05-06 | 2016-10-12 | 华中师范大学 | Manganese dioxide composite material and flexible supercapacitor prepared therefrom |
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| CN114796486A (en) * | 2022-03-21 | 2022-07-29 | 华南理工大学 | Preparation method and application of platinum/titanium dioxide @ manganese dioxide-polyethyleneimine composite anticancer nanomaterial |
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