CN107799317A - Manganese dioxide@manganese dioxide sub-micron balls and preparation method thereof - Google Patents
Manganese dioxide@manganese dioxide sub-micron balls and preparation method thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- PUZPNGOUOAKZCU-UHFFFAOYSA-N [O-2].[O-2].O.O.[Mn+2].[Mn+2] Chemical compound [O-2].[O-2].O.O.[Mn+2].[Mn+2] PUZPNGOUOAKZCU-UHFFFAOYSA-N 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
- 229910006364 δ-MnO2 Inorganic materials 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
- H01G11/24—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of manganese dioxide@manganese dioxide sub-micron balls and preparation method thereof.Described sub-micron ball is in the structure of ringing a bell with Lacking oxygen on microcosmic, wherein, shell is assembled by the manganese dioxide nano particle with Lacking oxygen, and core is porous manganese dioxide.It is this that there is Lacking oxygen structure manganese dioxide manganese dioxide sub-micron spheroidal material of ringing a bell to have that porous, specific surface area is big, electric conductivity is good and constitutionally stable characteristic, it is 1 Ag in current density available for electrode material for super capacitor‑1When its specific capacitance reach 452.4 Fg‑1, high current density is 50 Ag‑1When its specific capacitance still a height of 316.1 Fg‑1, show good high rate performance；It is 10 Ag in current density‑1Under conditions of test its cycle performance, capability retention is up to 92.2 % after 10000 circles, has good cyclical stability.
Description
Technical field
The present invention relates to a kind of manganese dioxide@manganese dioxide sub-micron balls and preparation method thereof, belong to submicron material system
Standby field.
Background technology
The world today is faced with energy shortage and the hang-up of environmental pollution two.Falling sharply for fossil energy reserves promotes people to seek
The new energy and highly efficient energy storage device are looked for, the development of lithium secondary battery and ultracapacitor is increasingly closed by people
Note.Ultracapacitor is a kind of chemical energy storage device between traditional capacitor and secondary cell, by electrolyte ion
Intercalation and desorption carry out work between electrode material.Ultracapacitor has the characteristics of power density is big, discharge and recharge is rapid, is living
In be widely used.It is naturally of great interest as the electrode material for influenceing performance of the supercapacitor.
Electrode material for super capacitor mainly has three major types：Traditional carbon material, transition metal oxide（Hydroxide）With
Conducting polymer.Transition metal oxide mainly includes RuO2、CoO、Co3O4, NiO and MnO2, wherein MnO2Because its rich reserves,
Theoretical capacity is big and receives much concern.Gueon D etc. are that template is prepared for manganese dioxide nano-plates/CNT using CNT
Composite [Gueon D, Moon J H. MnO2 nanoflake-shelled carbon nanotube particles
for high-performance supercapacitors[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(3):2445-2453.], Shao J etc. are prepared for isomorphous manganese dioxide@with two one-step hydrothermals
Manganese dioxide Core-shell structure material [Shao J, Zhou X, Liu Q, et al. Mechanism analysis of the
capacitance contributions and ultralong cycling-stability of the isomorphous
MnO 2@ MnO 2 core/shell nanostructures for supercapacitors[J]. Journal of Materials Chemistry A, 2015, 3(11):6168-6176.], Zhipeng Ma etc. synthesize dioxy with hydro-thermal method
Change manganese nano wire, then manganese dioxide nano-plates are synthesized on surface with oxidizing process, obtain manganese dioxide nanowire@manganese dioxide nanos
Piece core shell structure [Ma Z, Shao G, Fan Y, et al. Construction of Hierarchical α-MnO2
Nanowires@ Ultrathin δ-MnO2 Nanosheets Core–Shell Nanostructure with
Excellent Cycling Stability for High-Power Asymmetric Supercapacitor
Electrodes[J]. ACS applied materials & interfaces, 2016, 8(14): 9050-9058.]。
Above-mentioned preparation method is complicated and cost is higher, while poor-performing, thus there is an urgent need to one kind can on a large scale, it is low cost, simple
Single synthetic method prepares high performance material.
The content of the invention
It is an object of the invention to provide a kind of there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls
Preparation method.
The technical solution for realizing the object of the invention is：Manganese dioxide@manganese dioxide sub-micron balls of the present invention,
Described sub-micron ball is in the structure of ringing a bell with Lacking oxygen on microcosmic, wherein, shell is by the manganese dioxide with Lacking oxygen
Nano particle assembles, and core is porous manganese dioxide.
The preparation method of above-mentioned manganese dioxide@manganese dioxide sub-micron balls, comprises the following steps：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
Constant temperature certain time after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
Further, in the first step, the mol ratio of sodium acid carbonate and manganese sulfate is 5:1；Be added dropwise ammoniacal liquor to pH value be 10 ~
11。
Further, in second step, potassium permanganate molar concentration is 0.03 ~ 0.04 M.
Further, in the 3rd step, watery hydrochloric acid molar concentration is 0.01 ~ 0.05 M.
Further, in the 4th step, the min of constant temperature 20 ~ 80 after rising to 240 ± 10 DEG C with 2 degree of heating rates per minute.
The present invention compared with prior art, the advantage is that：（1）This method can synthesize structure of ringing a bell at ambient temperature
Manganese dioxide@manganese dioxide sub-micron balls,（2）In reducing atmosphere（H2/N2）Under can quickly prepare and rung a bell knot with Lacking oxygen
Structure manganese dioxide@manganese dioxide sub-micron balls,（3）The material is used for electrode material for super capacitor, is 1 Ag in current density-1
When its specific capacitance be up to 452.4 Fg-1, high current density to 50 Ag-1When still have higher specific capacitance be 316.1 Fg-1,
Show good high rate performance.（4）It is 10 Ag in current density-1Under conditions of test its cycle performance, hold after 10000 circles
Amount conservation rate is up to 92.2 %, has good cyclical stability.
Brief description of the drawings
Fig. 1 is the synthesis mechanism figure of the present invention.
Fig. 2 is that prepared by present example 1 there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls
Transmission electron microscope and scanning electron microscope (SEM) photograph（Wherein a is the transmission electron microscope under relatively low multiplication factor, and b is high-resolution-ration transmission electric-lens figure, c, d
For scanning electron microscope (SEM) photograph）.
Fig. 3 is that prepared by present example 1-4 there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls
And the XRD diffraction spectrograms of presoma（MnO2@MnO2Representative is rung a bell structure manganese dioxide@manganese dioxide sub-micron balls, Vo-MnO2@
MnO2Representing, there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls, and suffix 1,2,3,4 represents to be heat-treated respectively
Time be 20,40,60,80min）.
Fig. 4 be prepared by present example 1 have Lacking oxygen ring a bell structure manganese dioxide@manganese dioxide sub-micron ball and
The nitrogen adsorption desorption isothermal curve of control sample.
Fig. 5 is that prepared by present example 1-4 there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls
And the charging and discharging curve (a) of control sample and volumetric properties figure (b).
Fig. 6 is that prepared by present example 1 there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls
Cyclical stability performance map.
Embodiment
Fig. 1 is the synthesis mechanism figure of the present invention, and in dual-solvent system, manganese carbonate is micro- by self assembly for ion
Ball, handled afterwards with potassium permanganate, outermost layer generation manganese dioxide simultaneously slightly expands, and inside is partially oxidized to obtain titanium dioxide
The compound of manganese/manganese carbonate, wash to obtain porous structure manganese dioxide@manganese dioxide sub-micron balls of ringing a bell by watery hydrochloric acid,
Finally processing obtains ringing a bell structure manganese dioxide@manganese dioxide sub-micron balls with Lacking oxygen under hydrogen/nitrogen atmosphere.
What the present invention prepared there is Lacking oxygen to ring a bell structure manganese dioxide@manganese dioxide sub-micron balls as super capacitor
Device electrode material has excellent chemical property, and this is mainly due to its unique nanostructured：First, oxygen in lattice structure
The electric conductivity of material in itself can be greatly improved in the presence in room, so as to improve its performance；Secondly, porous structure of ringing a bell is favourable
In the infiltration of electrolyte, the more avtive spot of exposure；Finally, the structure of ringing a bell of this stabilization can be born in charge and discharge process
Frequently stress variation and volumetric expansion, there is provided good cycle performance.
The present invention's there is Lacking oxygen structure manganese dioxide@manganese dioxide sub-micron balls of ringing a bell to be prepared by following steps：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
Constant temperature certain time after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
Embodiment 1：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
The min of constant temperature 40 after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
Fig. 2 is transmission electron microscope TEM and scanning electron microscope sem figure, it can be seen that structure of significantly ringing a bell, and outer shell is by nanometer
Particle forms.The specific surface area that Fig. 4 can obtain the sample is 259.83 m2g-1, had a distinct increment compared to control sample.Fig. 6 is
The stable circulation performance figure of the sample of example 1, it is 10 Ag in current density-1Under conditions of test its cycle performance, after 10000 circles
Capability retention is up to 92.2 %, has good cyclical stability.
Embodiment 2：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
The min of constant temperature 20 after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
Embodiment 3：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
The min of constant temperature 60 after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
Embodiment 4：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
The min of constant temperature 80 after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
Comparison example：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, manganese dioxide@manganese dioxide sub-micron balls are made.
Fig. 3 is the XRD spectrum of example 1 ~ 4 and comparison example, and analysis knows comparison example sample without Lacking oxygen, electric conductivity compared with
Difference, cause its performance also poor.Example 1 ~ 4 is with H2/N2Middle processing time increases, and Lacking oxygen gradually increases, more than 40 min
The crystal transfer of backward mangano-manganic oxide.Fig. 5 is example 1 ~ 4 and the specific volume spirogram of comparison example, it can be seen that the performance of example 1
Preferably, it is 1 Ag in current density-1When its specific capacitance reach 452.4 Fg-1, high current density is 50 Ag-1When its specific capacitance
Still more a height of 316.1 Fg-1, show good high rate performance.The performance of example 2 has been lifted compared to control sample, in electric current
Density is 1 Ag-1When its specific capacitance reach 360.3 Fg-1.The sample of example 3 and 4 is due to the oxidation three of transformation generation four of crystal formation
Manganese, its hydraulic performance decline are more.
Claims (6)
1. manganese dioxide@manganese dioxide sub-micron balls, it is characterised in that described sub-micron ball is in have Lacking oxygen on microcosmic
Structure of ringing a bell, wherein, shell is assembled by the manganese dioxide nano particle with Lacking oxygen, and core is porous titanium dioxide
Manganese.
2. the preparation method of manganese dioxide@manganese dioxide sub-micron balls as claimed in claim 1, it is characterised in that including with
Lower step：
The first step, sodium bicarbonate solution is quickly mixed with the water of manganese sulfate and the mixed solution of absolute ethyl alcohol, ammonia is added dropwise immediately
Water stirs 2 more than h；
Second step, disperse in deionized water, to add liquor potassic permanganate, stirring 1.0 ~ 2.0 after precipitation cleaning obtained by the first step
h；
3rd step, it is dispersed in after precipitation cleaning obtained by second step in watery hydrochloric acid, stirs 15 ~ 20 min；
4th step, dried after precipitation cleaning obtained by the 3rd step, in hydrogen/nitrogen atmosphere, with 2 degree of heating rate liters per minute
Constant temperature certain time after to 240 ± 10 DEG C, the manganese dioxide@manganese dioxide sub-micron balls are made.
3. preparation method as claimed in claim 2, it is characterised in that in the first step, the mol ratio of sodium acid carbonate and manganese sulfate
For 5:1；It is 10 ~ 11 that ammoniacal liquor to pH value, which is added dropwise,.
4. preparation method as claimed in claim 2, it is characterised in that in second step, potassium permanganate molar concentration be 0.03 ~
0.04 M。
5. preparation method as claimed in claim 2, it is characterised in that in the 3rd step, watery hydrochloric acid molar concentration is 0.01 ~ 0.05
M。
6. preparation method as claimed in claim 2, it is characterised in that in the 4th step, risen to 2 degree of heating rates per minute
The min of constant temperature 20 ~ 80 after 240 ± 10 DEG C.
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| CN109336212A (en) * | 2018-09-21 | 2019-02-15 | 中国地质大学（武汉） | A kind of manganese dioxide and sulphite system and preparation method thereof, application |
| CN109467129A (en) * | 2019-01-16 | 2019-03-15 | 济南大学 | It is a kind of to improve the preparation method of the super electrical property of manganese dioxide by changing atmosphere |
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| CN114392735A (en) * | 2022-02-08 | 2022-04-26 | 中国科学院城市环境研究所 | alpha-MnO2Catalyst, preparation method and application thereof |
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| CN109336212A (en) * | 2018-09-21 | 2019-02-15 | 中国地质大学（武汉） | A kind of manganese dioxide and sulphite system and preparation method thereof, application |
| CN109467129A (en) * | 2019-01-16 | 2019-03-15 | 济南大学 | It is a kind of to improve the preparation method of the super electrical property of manganese dioxide by changing atmosphere |
| CN110563047A (en) * | 2019-09-27 | 2019-12-13 | 岭南师范学院 | Manganese dioxide composite material and preparation method thereof |
| CN110563047B (en) * | 2019-09-27 | 2022-04-08 | 岭南师范学院 | Manganese dioxide composite material and preparation method thereof |
| CN111554515A (en) * | 2020-05-11 | 2020-08-18 | 周小飞 | MnO (MnO)2Supercapacitor electrode material for modifying biomass porous carbon and preparation method thereof |
| CN111620376A (en) * | 2020-06-05 | 2020-09-04 | 安徽大学 | High-activity flower-shaped manganese dioxide for polysulfide sealant vulcanization and preparation method thereof |
| CN111620376B (en) * | 2020-06-05 | 2023-04-25 | 安徽大学 | High-activity delta-shaped flower-shaped manganese dioxide for vulcanizing polysulfide sealant and preparation method thereof |
| CN111969225A (en) * | 2020-08-28 | 2020-11-20 | 河南师范大学 | Method for recycling waste acidic zinc-manganese primary battery material |
| CN114105226A (en) * | 2020-08-28 | 2022-03-01 | 南京理工大学 | Nickel-cobalt-manganese sulfide @ hollow mesoporous carbon sphere nano composite material and preparation method thereof |
| CN114105226B (en) * | 2020-08-28 | 2024-01-05 | 南京理工大学 | Nickel cobalt manganese sulfide@hollow mesoporous carbon sphere nanocomposite and preparation method thereof |
| CN114392735A (en) * | 2022-02-08 | 2022-04-26 | 中国科学院城市环境研究所 | alpha-MnO2Catalyst, preparation method and application thereof |
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