CN107946090B - A kind of high capacity cobalt ions intercalation porous manganese dioxide electrode material and preparation method thereof - Google Patents
A kind of high capacity cobalt ions intercalation porous manganese dioxide electrode material 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 184
- 238000009830 intercalation Methods 0.000 title claims abstract description 55
- 230000002687 intercalation Effects 0.000 title claims abstract description 51
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002055 nanoplate Substances 0.000 claims abstract description 22
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003780 insertion Methods 0.000 claims description 5
- 230000037431 insertion Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 21
- 230000005540 biological transmission Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-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
- -1 metals cation Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000005837 radical ions Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of high capacity cobalt ions intercalation porous manganese dioxide electrode materials and preparation method thereof.This method is to be heated to reflux after mixing two-dimensional layer manganese dioxide nano-plates dispersion liquid with Hexammine cobaltic chloride in the case where pH is 1~4 acid condition, obtains the porous manganese dioxide nano material of cobalt intercalation.This method, which closes cobalt intercalating ions using six ammoniums, can lose part amino molecule ligand, form a kind of strong oxidizer, in acid condition, it is in situ that part manganese dioxide main layer board is oxidized to soluble high manganese ion, form hole configurations, itself is reduced to cobalt ions, obtains cobalt ions intercalation porous manganese dioxide nano material；The density in hole on the controllable manganese dioxide nano-plates layer of this method, and then improve electrolyte ion transmission performance；Resulting materials, specific capacitance are up to 322~456Fg‑1, can be used as assembling high-energy density electrode material for super capacitor；This method reaction condition is mild, the time is short, raw material is easy to get, strong operability, and preparation cost is low.
Description
Technical field
The invention belongs to electrode material preparation technical fields, and in particular to a kind of high capacity cobalt ions intercalation porous silica
Manganese electrode material and preparation method thereof.
Background technique
Manganese dioxide makes it in catalysis, ion exchange, lithium ion battery and super due to its unique physicochemical properties
The multiple fields such as capacitor have broad application prospects.Manganese dioxide mineral species multiplicity, according to its basic assembling unit
Manganese dioxide, can be divided into tunnel-like manganese dioxide, layered manganese oxide and network by the difference of [MnO6] octahedron connection type
Shape manganese dioxide.Wherein layered manganese oxide is made of electropositive laminate main body with the interlayer cation with ion exchange, layer
Spacing is by interlayer cation type and moisture content.Layered manganese oxide is due to being suitble to hydration K with suitable interlamellar spacing+
Quick insertion/deintercalation of the ion in charge and discharge process.
The existing disclosed oxide for utilizing manganese has patent CN102306554A to disclose polyphenyl as electrode material
Thioether intercalation manganese dioxide electrode material, the material are using hexadecyltrimethylammonium chloride to manganese dioxide recombination, then with
Polyphenylene sulfide exchange reaction in organic solvent, obtains polyphenylene sulfide intercalation manganese dioxide nanocomposite, but the preparation
Method is related to multiple chemical reactions, and total preparation time is extremely long, and part reaction is required at 150~200 DEG C；
Patent CN103985563A discloses a kind of lithium intercalation manganese dioxide-titanium nitride nano pipe composite material, the material
Middle lithium intercalation is to use the mixed liquor of manganese acetate and lithium sulfate for electrolyte solution, and titanium nitride nano pipe is adopted as working electrode
Lithium intercalation manganese dioxide-titanium nitride nano pipe composite material is prepared with electrochemical intercalation-deposition reaction synthetic method；
《Cation Intercalation in Manganese Oxide Nanosheets:Effects on
Lithium and Sodium Storage " (Angew.Chem.Int.Ed., 2016, DOI:10.1002/
Anie.201605102) disclose and two-dimentional manganese dioxide nano-plates and various metals cation be subjected to self assembly, synthesis sun from
The three-dimensional MxMnO of sub- intercalation2(M=Li, Na, K, Co and Mg) cathode material, but metal cobalt ions functions only as in the document
Special adsorption, it is therefore an objective to change the spacing of layer and interlayer.
In the oxide of manganese, layered manganese oxide specific capacity with higher.However, since manganese dioxide interlayer is strong
Electrostatic attraction drastically reduces the specific surface area and pore volume of manganese dioxide so that being easy to stack between manganese dioxide lamella.
As electrode material for super capacitor, the active site for participating in electrochemical reaction is greatly reduced, electrolyte ion is hindered
Diffusion path.Therefore preparation is reunited less, porous structure manganese bioxide electrode material is of great significance.
Carbon material, metal ion etc. are inserted between manganese dioxide nano-plates layer by researcher, miscellaneous to form manganese dioxide
Change material to reunite to reduce, but since there are biggish interface resistances for the material of electrostatic assembly formation, electrochemical properties are not
It is ideal.In recent years, researcher is dedicated to preparing three-dimensional self-assembled material, to reduce the reunion of manganese bioxide material, it is made to the greatest extent may be used
Electrochemical reaction can be adequately participated in, improves its electrochemical properties, but effect is unobvious.
The existing disclosed document of inventor's retrieval, finds about the report base for preparing porous structure manganese dioxide nano-plates layer
Originally do not have, therefore, exploitation high capacity porous structure nano material of manganese dioxide new preparation technology is of great significance.
Summary of the invention
The purpose of the present invention is provide a kind of Gao Rong for deficiency existing for existing manganese bioxide electrode material preparation aspect
Cobalt ions intercalation porous manganese dioxide electrode material and preparation method thereof is measured, this method can be in metal ion intercalation manganese dioxide
Porous structure is introduced while nanometer layer wherein, which can provide a large amount of ion transmission channel, Er Qieyou for material
Effect increases the specific surface area of manganese bioxide material.
In order to achieve the object of the present invention, for the present inventor by a large number of experiments research and unremitting effort, final acquisition is as follows
Technical solution: a kind of preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material, by two-dimensional layer titanium dioxide
Manganese nanometer sheet is heated to reflux after mixing with Hexammine cobaltic chloride in the case where pH is 1~4 acid condition, and cobalt intercalation is obtained
Porous manganese dioxide nano material.
It is further preferred that the preparation side of high capacity cobalt ions intercalation porous manganese dioxide electrode material of the present invention
Method, by two-dimensional layer manganese dioxide nano-plates dispersion liquid and Hexammine cobaltic chloride by manganese dioxide: Hexammine cobaltic chloride rubs
You are than being 1: the ratio of (15~100) is mixed and is reacted under agitation, obtains the manganese dioxide of six cobaltammine ion insertions
Nanomaterial solution, washing disperse again, and adjusting pH is 1~4, and heated reflux later, cooling, washing, drying obtain cobalt
Ion insertion porous manganese dioxide nano material.
It is further preferred that the preparation side of high capacity cobalt ions intercalation porous manganese dioxide electrode material of the present invention
Method, the two-dimensional layer manganese dioxide nano-plates dispersion liquid and Hexammine cobaltic chloride are 1: 100 in molar ratio.
It is further preferred that the preparation side of high capacity cobalt ions intercalation porous manganese dioxide electrode material of the present invention
Method, the two-dimensional layer manganese dioxide nano-plates dispersion liquid concentration are 2~8mg/mL.
It is further preferred that the preparation side of high capacity cobalt ions intercalation porous manganese dioxide electrode material of the present invention
Method, the temperature that is heated to reflux is 80~100 DEG C, 2~3h of return time.
It is further preferred that the preparation side of high capacity cobalt ions intercalation porous manganese dioxide electrode material of the present invention
Method, the temperature that is heated to reflux is 100 DEG C, return time 2h.
It is further preferred that the preparation side of high capacity cobalt ions intercalation porous manganese dioxide electrode material of the present invention
Method, the two-dimensional layer manganese dioxide nano-plates dispersion liquid is by H2O2Aqueous solution is mixed with tetramethylammonium hydroxide aqueous solution
After MnCl is added2, stirring and ultrasound, are centrifugally separating to obtain two-dimensional layer manganese dioxide nano-plates dispersion liquid under room temperature.
The present invention also provides high capacity cobalt ions intercalation porous manganese dioxide electrode materials prepared by the above method.
The present invention compared with the existing technology, has the following technical effect that
(1) using under reflux condition, six cobaltammine intercalating ions can lose part amino molecule and match the method for the present invention
Body forms a kind of strong oxidizer, in acid condition, in situ that part manganese dioxide main layer board is oxidized to soluble permanganic acid
Radical ion forms hole configurations, itself is reduced to cobalt ions, obtains cobalt ions intercalation porous manganese dioxide nano material；
(2) by the comparison discovery of the material transmission electromicroscopic photograph such as Fig. 1~8, the method for the present invention passes through control titanium dioxide
Manganese nanometer sheet dispersion liquid and Hexammine cobaltic chloride in molar ratio, can on Effective Regulation manganese dioxide nano-plates layer hole density,
And then improve electrolyte ion transmission performance；
(3) the cobalt ions intercalation porous manganese dioxide nano material that the method for the present invention is prepared, specific capacitance be 322~
456F·g-1, can be used as assembling high-energy density electrode material for super capacitor；
(4) the method for the present invention reaction condition is mild, the time is short, raw material is easy to get, strong operability, and preparation cost is low.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 1；
Fig. 2 is the transmission electron microscope photo of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 1；
Fig. 3 is the high power transmission electron microscope photo of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 1；
Fig. 4 is the constant current charge-discharge curve of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 1；
Fig. 5 is the transmission electron microscope photo of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 2；
Fig. 6 is the transmission electron microscope photo of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 3；
Fig. 7 is the transmission electron microscope photo of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 4；
Fig. 8 is the transmission electron microscope photo of cobalt ions intercalation porous manganese dioxide nano material prepared by embodiment 5.
Specific embodiment
The present invention is described in further details with embodiment with reference to the accompanying drawing, but protection scope of the present invention is not limited to
The embodiment.
Inventor is introduced porosity into manganese dioxide nano layer if just think by the inspiration of porous graphene special construction
Meeting so that material occur what variation, be found through experiments that, which can improve electrolyte ion in material vertical direction
Transmission performance, a large amount of ion transmission channel can not only be provided, and the ratio table of manganese bioxide material can be effectively increased
Area can provide more redox reaction active sites in electrochemical reaction, reach optimization material electrochemical performance
Purpose.
Two-dimensional layer manganese dioxide nano-plates dispersion liquid is prepared using redox precipitation method in the embodiment of the present invention,
Specifically: the H for being 30% by mass fraction2O2Aqueous solution is uniformly mixed with the tetramethylammonium hydroxide aqueous solution of 0.6mol/L, institute
Obtain the MnCl that 0.3mol/L is added in mixed liquor under the conditions of stirring at normal temperature2·4H2In O aqueous solution, wherein H2O2Aqueous solution and tetramethyl
Base ammonium hydroxide aqueous solution, MnCl2·4H2The volume ratio of O aqueous solution is 1: 9: 5, and for 24 hours, ultrasonic 2h is centrifugated stirring at normal temperature,
The unstripped mud of lower layer is discarded, upper suspension is dialysed to neutrality, layered manganese oxide nanometer layer dispersion liquid is obtained, is diluted to
The concentration of manganese dioxide is 5mg/mL in manganese dioxide nano layer dispersion liquid.Existing disclosed other methods can certainly be passed through
Layered manganese oxide nanometer sheet is obtained, and then obtains dispersion liquid.
Embodiment 1
The dispersion of 3.48mL 5mg/mL manganese dioxide nano-plates is added in 100mL 0.2mol/L Hexammine cobaltic chloride solution
In liquid, 6h is stirred under room temperature, obtains the nano material of manganese dioxide of six cobaltammine ion insertions, and washing disperses again.It will
Gained dispersion liquid is heated to 100 DEG C, is 1 with the pH that hydrochloric acid adjusts reaction system, is heated to reflux 2h, natural cooling with this condition
To room temperature, decompression is filtered, and being washed with deionized water to filtrate is neutrality, and freeze-drying is prepared into the porous dioxy of cobalt ions intercalation
Change manganese nano material.
Products therefrom is characterized and is tested using X-ray diffractometer, transmission electron microscope and electrochemical workstation, is tied
Fruit sees Fig. 1~3.By the X-ray diffractogram of Fig. 1 it is found that products therefrom is layered manganese oxide.As it is clear from fig. 2 that manganese dioxide is received
Rice on piece has apparent porous structure.It can be seen that from the high power TEM photo of Fig. 3 and be dispersed with size on manganese dioxide nano-plates
The about hole of 4nm.The material being prepared in summary is the porous manganese dioxide nano material of cobalt ions intercalation.
By Fig. 4 constant current charge-discharge curve it is found that good symmetric figure is presented in the constant current charge-discharge curve of products therefrom
Shape illustrates its capacitive properties having had, and is 0.25Ag in current density-1When, specific discharge capacity reaches 454 Fg-1,
It can be used as electrode material for super capacitor.
Embodiment 2
100mL 0.04mol/L Hexammine cobaltic chloride solution, Qi Tabu are added into manganese dioxide nano-plates dispersion liquid
It is rapid same as Example 1, the porous manganese dioxide nano material of cobalt ions intercalation is prepared as shown in figure 5, after tested in electricity
Current density is 0.25Ag-1When, specific discharge capacity 368Fg-1。
Embodiment 3
100mL 0.1mol/L Hexammine cobaltic chloride solution, other steps are added into manganese dioxide nano-plates dispersion liquid
It is same as Example 1, the porous manganese dioxide nano material of cobalt ions intercalation is prepared as shown in fig. 6, after tested in electric current
Density is 0.25Ag-1When, specific discharge capacity 418Fg-1。
Embodiment 4
It is stirred at reflux 3h at 80 DEG C in the present embodiment, other steps are same as Example 1, and cobalt ions intercalation is prepared
Porous manganese dioxide nano material is as shown in fig. 7, be after tested 0.25Ag in current density-1When, specific discharge capacity is
347F·g-1。
Embodiment 5
It is stirred at reflux 2h at 90 DEG C in the present embodiment, other steps are same as Example 1, and cobalt ions intercalation is prepared
Porous manganese dioxide nano material is as shown in figure 8, be after tested 0.25Ag in current density-1When, specific discharge capacity is
355F·g-1。
Embodiment 6
In the present embodiment by the hydrochloric acid in embodiment 1 replace with respectively sulfuric acid, nitric acid and both according to molar ratio 1:1
Nitration mixture come adjust pH value of solution be 1, other conditions remain unchanged, and the porous manganese dioxide nanometer material of cobalt ions intercalation is prepared
Material, carries out electric performance test to it, is 0.25Ag in current density-1When, specific discharge capacity is respectively 449 Fg-1、
442F·g-1、456F·g-1, it is found through experiments that, under the premise of other conditions are constant, as long as pH is constant, then obtain
Material electrical property does not change substantially.
Comparative example 1
Inventor is found through experiments that, is inserted into ion [Co (NH3)6]3+By being heated at reflux release NH3Ligand, only in acid
Under the conditions of property, the Co of formation3+Just there is strong oxidizing property.
Therefore on the basis of embodiment 1, other conditions are constant for the comparative example, only change hydrochloric acid additional amount, adjust pH
Respectively 4,6, the material electrical property investigated, discovery are 0.25Ag in current density-1When, specific discharge capacity is respectively
322F·g-1、214F·g-1, therefore by the comparative example, inventor has found that the method for the present invention can only be in acid stronger environment
The lower material that can just obtain high quality specific capacity.
Comparative example 2
On the basis of embodiment 1, change manganese dioxide in reactant: Hexammine cobaltic chloride molar ratio, discovery, which is worked as, to rub
When you are than being 1:5, material is 0.25Ag in current density-1When, specific discharge capacity is respectively 225Fg-1, work as molar ratio
When for 1:150, material is 0.25Ag in current density-1When, specific discharge capacity is respectively 427Fg-1。
It is found through experiments that, when manganese dioxide: when Hexammine cobaltic chloride molar ratio is less than the scope of the invention, porous structure
It is unobvious, and when molar ratio it is bigger than normal exceed the scope of the invention when, the intercalating ions for being inserted into interlayer reach saturation, and hole density will not be bright
It is aobvious to increase, cause material specific capacitance not significantly increase.
Claims (8)
1. a kind of preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material, it is characterised in that: by two-dimensional layer
Shape manganese dioxide nano-plates dispersion liquid heats back after mixing with Hexammine cobaltic chloride in the case where pH is 1~4 acid condition
Stream, obtains the porous manganese dioxide nano material of cobalt ions intercalation.
2. the preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material according to claim 1, special
Sign is: by two-dimensional layer manganese dioxide nano-plates dispersion liquid and Hexammine cobaltic chloride by manganese dioxide: six ammino of tri-chlorination
Cobalt molar ratio is 1: the ratio of (15~100) is mixed and is reacted under agitation, obtains the dioxy of six cobaltammine ion insertions
Change manganese nano material dispersion liquid, washing disperses again, and adjusting pH is 1~4, heated reflux later, cooling, washing, drying,
Obtain cobalt ions intercalation porous manganese dioxide nano material.
3. the preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material according to claim 2, special
Sign is: the two-dimensional layer manganese dioxide nano-plates dispersion liquid and Hexammine cobaltic chloride are by manganese dioxide: six ammonia of tri-chlorination
The ratio that cobalt molar ratio is 1: 100 is closed to mix.
4. the preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material according to claim 2, special
Sign is: the two-dimensional layer manganese dioxide nano-plates dispersion liquid concentration is 2~8mg/mL.
5. the preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material according to claim 2, special
Sign is: the temperature that is heated to reflux is 80~100 DEG C, 2~3h of return time.
6. the preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material according to claim 5, special
Sign is: the temperature that is heated to reflux is 100 DEG C, return time 2h.
7. the preparation method of high capacity cobalt ions intercalation porous manganese dioxide electrode material according to claim 1, special
Sign is: the two-dimensional layer manganese dioxide nano-plates dispersion liquid is by H2O2Aqueous solution and tetramethylammonium hydroxide aqueous solution
MnCl is added after mixing2, stirring and ultrasound, are centrifugally separating to obtain two-dimensional layer manganese dioxide nano-plates dispersion liquid under room temperature.
8. a kind of system of any one according to claim 1~7 high capacity cobalt ions intercalation porous manganese dioxide electrode material
The high capacity cobalt ions intercalation porous manganese dioxide electrode material that Preparation Method is prepared.
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