CN115724469B - Carbon-coated manganous-manganic oxide submicron spherical shell material and preparation method and application thereof - Google Patents
Carbon-coated manganous-manganic oxide submicron spherical shell material and preparation method and application thereof Download PDFInfo
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- 239000011257 shell material Substances 0.000 title claims abstract description 128
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 134
- 239000004005 microsphere Substances 0.000 claims abstract description 130
- 239000000839 emulsion Substances 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 73
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 238000006479 redox reaction Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims description 148
- 239000004793 Polystyrene Substances 0.000 claims description 84
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 70
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229930192474 thiophene Natural products 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 45
- 238000003786 synthesis reaction Methods 0.000 abstract description 45
- 239000011572 manganese Substances 0.000 abstract description 28
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 204
- 229910021642 ultra pure water Inorganic materials 0.000 description 60
- 239000012498 ultrapure water Substances 0.000 description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- 238000003756 stirring Methods 0.000 description 46
- 229920000767 polyaniline Polymers 0.000 description 40
- 229920000128 polypyrrole Polymers 0.000 description 40
- 238000001816 cooling Methods 0.000 description 29
- 238000000967 suction filtration Methods 0.000 description 28
- 238000005406 washing Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000003999 initiator Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 16
- 238000010000 carbonizing Methods 0.000 description 15
- 235000019993 champagne Nutrition 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 239000003112 inhibitor Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 238000007789 sealing Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000001132 ultrasonic dispersion Methods 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 238000000197 pyrolysis Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 239000011149 active material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 229920000123 polythiophene Polymers 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a carbon-coated manganous-manganic oxide submicron spherical shell material and a preparation method and application thereof, belonging to the technical field of composite material synthesis and electrode material preparation. The carbon-coated manganous-manganic oxide submicron spherical shell material is prepared according to the following steps: taking water as a solvent, taking PS microsphere emulsion as a template, adding a conductive polymer monomer A and an ammonium persulfate aqueous solution A, and carrying out in-situ polymerization reaction at normal temperature to obtain conductive polymer @ PS microspheres; dispersing the precursor into water, adding potassium permanganate solution, and performing oxidation-reduction reaction at normal temperature to generate a conductive polymer coated manganese dioxide precursor material; and (3) in an inert gas atmosphere, pyrolyzing the conductive polymer coated manganese dioxide precursor material at 400-550 ℃ to obtain the carbon coated manganese tetraoxide submicron spherical shell material. The material is used as a water-based zinc ion battery positive electrode composite material, and improves the cycling stability and the multiplying power performance of the manganese-based material while improving the reversible capacity of the manganese-based material.
Description
Technical Field
The invention relates to the technical field of composite material synthesis and electrode material preparation, in particular to a carbon-coated trimanganese tetroxide submicron spherical shell material, and a preparation method and application thereof.
Background
Traditional fossil energy sources such as coal, petroleum and natural gas make great contribution to the rapid development of human society, but also cause a series of serious problems such as resource exhaustion and environmental pollution. Therefore, in recent years, the development of a break-through has been focused on green, sustainable, efficient new energy, and secondary batteries in energy storage and conversion systems are the most prominent ones.
For the secondary battery using the organic electrolyte, the secondary battery has the safety problems of inflammability, toxicity and the like, and the aqueous battery adopts the aqueous solution as the electrolyte, so that the secondary battery has higher safety and environmental friendliness, accords with the development concept of high-capacity green energy storage, and becomes a research hot spot in recent years. Among metals stably existing in water, zinc has the lowest potential, is cheap and easy to obtain, and the water-based zinc ion battery is expected to become a novel energy storage device for large-scale application. Heretofore, many materials such as manganese-based oxides, vanadium-based oxides, cobalt-based oxides, nickel-based oxides, prussian blue-based compounds, and the like have been tried as positive electrode active materials for aqueous zinc ion batteries by researchers. Among the materials, manganese element has abundant reserves, safety, no toxicity, low price, various variable valence states and easy preparation of oxides, and has more possibility as a zinc ion battery anode material.
Unlike containing Mn 4+ MnO of (2) 2 System, mn 3 O 4 Mn is present at the same time in 2+ And Mn of 3+ Has excellent redox properties due to its defect-rich characteristics (such as holes, holes and electrons), and can be used as a positive electrode materialIn a variety of energy storage systems. The theoretical specific capacity of the zinc ion battery is about 469mAh/g, and the specific capacity is higher than MnO 2 (308 mAh/g) 50%, and is an electrode material with application prospect; but the conductivity is poor, the volume expansion is serious, and the electrode is pulverized, the structure is collapsed and the capacity is attenuated in the charge and discharge process. In Mn 3 O 4 The improvement of the rate performance and the cycle stability of the water-based zinc ion battery serving as the positive electrode is needed.
Disclosure of Invention
Aiming at the problems, the invention provides the carbon-coated trimanganese tetroxide submicron spherical shell material, and the preparation method and the application thereof, and the carbon-coated trimanganese tetroxide submicron spherical shell material is used as a water-based zinc ion battery positive electrode composite material, so that the reversible capacity of the manganese-based material is improved, and meanwhile, the cycle stability and the multiplying power performance of the manganese-based material are improved.
The first object of the invention is to provide a preparation method of a carbon-coated manganous-manganic oxide submicron spherical shell material, which comprises the following steps:
step 1, taking water as a solvent, taking PS microsphere emulsion as a template, adding a conductive polymer monomer A and an ammonium persulfate aqueous solution A, and carrying out in-situ polymerization reaction at normal temperature to obtain conductive polymer@PS microspheres;
Step 2, dispersing all conductive polymer@PS microspheres prepared in the step 1 in water to obtain conductive polymer@PS microsphere emulsion, adding a potassium permanganate solution into the conductive polymer@PS microsphere emulsion, and performing oxidation-reduction reaction at normal temperature to generate a conductive polymer coated manganese dioxide precursor material;
and 3, pyrolyzing the manganese dioxide precursor material coated by the conductive polymer prepared in the step 2 at 400-550 ℃ in an inert gas atmosphere to obtain the carbon-coated trimanganese tetroxide submicron spherical shell material.
Preferably, in the step 1, the reaction time of the in-situ polymerization reaction is 2-3 hours; the proportion of the PS microsphere emulsion, the water, the conductive polymer monomer A and the ammonium persulfate aqueous solution A is 60 mL-80 mL:15 mL-20 mL: 400-500. Mu.L: 10 mL-15 mL;
the concentration of the ammonium persulfate aqueous solution A is 0.7-0.8M.
Preferably, in the step 2, the reaction time of the oxidation-reduction reaction is 2-3 hours; the molar ratio of the conductive polymer monomer A in the step 1 to the potassium permanganate in the step 2 is 2-1:1; the concentration of the potassium permanganate is 0.05-0.08M;
the ratio of the conductive polymer monomer in step 1 to the water in step 2 is 400 to 500. Mu.L: 50-100mL.
Preferably, in the step 3, the temperature is increased to 400-550 ℃ at 5-10 ℃/min, and the pyrolysis time is 10min-3h.
Preferably, after the redox reaction in step 2 is completed, the conductive polymer monomer B and the ammonium persulfate aqueous solution B are added in an ice bath environment to perform in-situ polymerization reaction to obtain the conductive polymer coated manganese dioxide precursor material.
Preferably, after the redox reaction of step 2 is completed, the addition ratio of the conductive polymer monomer B, the ammonium persulfate aqueous solution B, and the potassium permanganate is 400 μl to 800 μl:10 mL-20 mL:40 mL-60 mL, the concentration of ammonium persulfate aqueous solution B is 0.35-0.4M;
the in-situ polymerization reaction time is 2-3h.
Preferably, the conductive polymer monomer A is one of pyrrole monomer, aniline monomer and thiophene monomer;
the conductive polymer monomer B is the same as the conductive polymer A, and is one of pyrrole monomer, aniline monomer and thiophene monomer.
The second purpose of the invention is to provide the carbon-coated trimanganese tetroxide submicron spherical shell material prepared by the preparation method.
The third object of the invention is to provide the application of the carbon-coated manganous manganic oxide submicron spherical shell material in the anode material of the water-based metal battery, which is characterized in that the water-based metal battery is any one of water-based zinc, potassium, magnesium, aluminum and calcium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
(1) Preparation of a spherical shell structured Conductive Polymer (CP) acting as a reducing agent for reducing Potassium permanganate to DioxidManganese, CP@MnO prepared in situ 2 Calcining under inert gas atmosphere, carbonizing CP part, adding MnO 2 Further reduced to Mn 3 O 4 Obtaining the carbon-coated trimanganese tetroxide submicron spherical shell with adjustable diameter. The spherical shell structure has excellent contractibility, and can greatly contain Mn in the charge and discharge processes 3 O 4 The lattice distortion of the battery is improved; the coating of the carbon-based material can improve the conductivity of the composite material, and meanwhile, the specific surface area is larger, so that more active sites are exposed, and the reversible capacity and the rate capability of the battery are improved;
(2) The CP is rich in nitrogen, sulfur and other miscellaneous elements, the number of active sites of oxidation-reduction reaction of the anode material in the charge-discharge process is increased, the conductivity of the material is improved after carbonization, and the spherical shell structure of the material has the advantages of excellent anti-expansion property, high mechanical strength, large specific surface area and the like;
(3) The two carbon-coated manganous-manganic oxide submicron spherical shell materials provided by the invention can be used as positive electrode materials in lithium ion batteries, metal-air batteries, super capacitors and water-based zinc ion batteries. The metal-air battery is any one of a zinc-air battery, an aluminum-air battery, a magnesium-air battery and a lithium-air battery;
(4) The two materials are used for the water-based zinc ion battery anode material, and the discharge specific capacity of the water-based zinc ion battery anode material can reach 450mAh/g at the current density of 0.5A/g; the current density is increased, and when the current density is 10A/g, the discharge specific capacity can reach 200mAh/g at the highest, so that the high-power high-voltage high-power battery has excellent rate capability;
(5) The double-layer carbon-coated trimanganese tetroxide material in example 2 has a first-cycle specific capacity of 184mAh/g at a high current density of 50A/g, and a specific capacity of 125mAh/g after 5000 cycles, and an initial capacity retention rate of 68%.
Drawings
FIG. 1 is a diagram of the synthesis mechanism of the preparation of carbon-coated trimanganese tetroxide submicron spherical shell material according to the invention;
FIG. 2 is a scanning electron microscope image of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 1 of the invention, wherein FIG. 2a is a 10000-fold enlarged picture, and FIG. 2b is a 100000-fold enlarged picture;
FIG. 3 is an EDS image of a carbon coated manganous-manganic oxide submicron spherical shell material prepared in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 2 of the invention, wherein FIG. 4a is a magnified 30000-fold image, and FIG. 4b is a magnified 60000-fold image;
FIG. 5 is an EDS image of a carbon coated manganous-manganic oxide submicron spherical shell material prepared in example 2 of the present invention;
FIG. 6 is an XRD diffraction pattern of a carbon coated trimanganese tetroxide submicron spherical shell material prepared in example 1 of the invention;
FIG. 7 is an XRD diffraction pattern of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 2 of the invention;
FIG. 8 shows the carbon-coated trimanganese tetroxide submicron spherical shell materials prepared in example 1 and example 2, respectively, obtained by pyrolysis at 450℃according to the invention, as the active material of the positive electrode material, zinc sheet as the negative electrode, znSO 4 The solution is the multiplying power performance of the water system zinc ion battery assembled by the electrolyte;
FIG. 9 is a charge-discharge curve corresponding to the rate capability of FIG. 8;
FIG. 10 is a discharge cycle chart of a double-layer carbon-coated trimanganese tetroxide submicron spherical shell material obtained by pyrolysis at 450 ℃ under the argon atmosphere prepared in the embodiment 2 of the invention;
FIG. 11 is an XRD diffraction pattern of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 5 of the invention;
FIG. 12 shows a carbon-coated active material as a cathode material, zinc flakes as an anode, znSO, prepared in example 5 of the present invention 4 The solution is the cycle performance of the water-based zinc ion battery assembled by the electrolyte.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified. In addition, PS represents polystyrene, PANI represents polyaniline, PTh represents polythiophene, and CP directs the conductive polymer.
The PS microsphere emulsion used in the invention is prepared according to the following steps:
step a, using styrene as a raw material, extracting with sodium hydroxide solution, removing polymerization inhibitor in the styrene solution, extracting with ultrapure water, adjusting the pH value of the solution to 7-8, and obtaining the styrene solution which is changed from colorless to clear champagne for later use, wherein in the step a, the volume ratio of the styrene to the sodium hydroxide solution to the ultrapure water is 20-30:160-240:160-240; the concentration of the sodium hydroxide solution is 2M;
Step b, adding a styrene solution into ultrapure water serving as a solvent, heating to 70-80 ℃, and adding K 2 S 2 O 8 And (b) carrying out polymerization reaction on the initiator, standing, cooling, filtering and removing impurities to obtain PS microsphere emulsion, wherein in the step (b), the reaction temperature of the polymerization reaction is 50-80 ℃, the reaction is carried out for 5-6 hours under the nitrogen atmosphere, and the addition amount ratio of the ultrapure water, the styrene solution and the potassium persulfate is 192-240 mL:16mL:0.22-0.35g.
For PS microsphere emulsion, PS microsphere can be directly purchased to prepare.
Example 1
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 70 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PPy@PS microspheres
And (3) diluting 60mL of the PS microsphere emulsion prepared in the first step to 75mL by using ultrapure water, adding 400 mu L of pyrrole monomer under magnetic stirring, stirring for 5min, adding 10mL of 0.8M ammonium persulfate aqueous solution, and stirring for 2h at normal temperature.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PPy@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of@PPy spherical shell structural material
And uniformly dispersing all the PPy@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain PPy@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is added into the PPy@PS microsphere emulsion drop by drop, after reacting for 2 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 @ppy spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the material with the spherical shell structure @ PPy to 450 ℃ at 5 ℃/min under argon atmosphere, pyrolyzing at high temperature for 2 hours to remove polystyrene while carbonizing polypyrrole, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetroxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 2
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator was stirred at 1000r/min for 10min, then the rotation speed was reduced to 300r/min, and stirring was continued for 6h at 70℃under nitrogen atmosphere. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PPy@PS microspheres
60mL of the PS microsphere emulsion prepared in the first step is diluted to 75mL by ultrapure water, 400 mu L of pyrrole monomer is added under magnetic stirring, stirring is carried out for 5min, 10mL of 0.8M ammonium persulfate aqueous solution is added, and stirring is carried out for 2 hours.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PPy@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of@PPy spherical shell structural material
And uniformly dispersing all the PPy@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain PPy@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is dropwise added into the PPy@PS microsphere emulsion, after 3 hours of reaction, 400 mu L of pyrrole monomer and 10mL of 0.4M ammonium persulfate aqueous solution are continuously added into the reaction solution under the ice bath environment, the mixture is stirred and reacted for 2 hours, and the mixture is subjected to suction filtration, washing, drying and grinding to obtain PPy@MnO 2 @ppy submicron sphere material.
Taking PPy@MnO 2 Heating up to 450 ℃ at 5 ℃/min under argon atmosphere, pyrolyzing for 2 hours at high temperature to remove polystyrene while carbonizing polypyrrole, naturally cooling down to room temperature in a tube furnace, and taking out to obtain a carbon-coated trimanganese tetraoxide submicron spherical shell material, which is marked as C@Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 3
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, together with 16mL of the above-treated styrene solution, followed by 0.35. 0.35g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 50 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PPy@PS microspheres
80mL of the PS microsphere emulsion prepared in the first step is diluted to 100mL by ultrapure water, 450 mu L of pyrrole monomer is added under magnetic stirring, stirring is carried out for 5min, 15mL of 0.7M ammonium persulfate aqueous solution is added, and stirring is carried out for 3 hours at normal temperature.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PPy@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of@PPy spherical shell structural material
And uniformly dispersing all the PPy@PS microspheres prepared in the previous step by using 70mL of ultrapure water to obtain PPy@PS microsphere emulsion. Under the stirring condition, 60mL of 0.08M potassium permanganate solution is added into the PPy@PS microsphere emulsion drop by drop, after reaction for 3 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 @ppy spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Spherical shell @ PPyHeating the structural material to 400 ℃ at 10 ℃/min under argon atmosphere, pyrolyzing at high temperature for 3 hours to remove polystyrene while carbonizing polypyrrole, naturally cooling to room temperature in a tube furnace, and taking out to obtain a carbon-coated trimanganese tetroxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 4
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 50℃and then added with 0.35. 0.35g K 2 S 2 O 8 The initiator was stirred at 1000r/min for 10min, then the rotation speed was reduced to 300r/min, and stirring was continued for 6h at 50℃under nitrogen. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PANI@PS microspheres
80mL of the PS microsphere emulsion prepared in the first step is diluted to 100mL by ultrapure water, 400 mu L of aniline monomer is added under magnetic stirring, stirring is carried out for 5min, 15mL of 0.7M ammonium persulfate aqueous solution is added, and stirring is carried out for 3h.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PANI@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of @ PANI spherical shell structural material
And uniformly dispersing all the PANI@PS microspheres prepared in the previous step by using 70mL of ultrapure water to obtain the PANI@PS microsphere emulsion. 50mL of 0.08M potassium permanganate solution is added into the PANI@PS microsphere emulsion dropwise under the stirring condition, and after 3 hours of reaction, the solution is dissolved in an ice bath environmentAdding 500 mu L of aniline monomer and 20mL of 0.35M ammonium persulfate aqueous solution continuously, stirring and reacting for 3h, and carrying out suction filtration, washing, drying and grinding to obtain PANI@MnO 2 PANI submicron sphere material.
Taking PANI@MnO 2 Heating up to 400 ℃ at 10 ℃/min under argon atmosphere, pyrolyzing for 3 hours at high temperature to remove polystyrene while carbonizing polyaniline, naturally cooling down to room temperature in a tube furnace, and taking out to obtain a carbon-coated trimanganese tetraoxide submicron spherical shell material, which is marked as C@Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 5
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 70 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PANI@PS microspheres
And (3) diluting 60mL of the PS microsphere emulsion prepared in the first step to 75mL by using ultrapure water, adding 400 mu L of aniline monomer under magnetic stirring, stirring for 5min, adding 10mL of 0.8M ammonium persulfate aqueous solution, and stirring for 2h at normal temperature.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PANI@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of @ PANI spherical shell structural material
And uniformly dispersing all the PANI@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain the PANI@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is added into the PANI@PS microsphere emulsion drop by drop, after reacting for 2 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 PANI spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the spherical shell structural material of @ PANI to 450 ℃ at 5 ℃/min under argon atmosphere, pyrolyzing at high temperature for 2 hours to remove polystyrene while carbonizing polyaniline, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetroxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 6
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
192mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 80℃and then added with 0.22. 0.22g K 2 S 2 O 8 The initiator was stirred at 1000r/min for 10min, then the rotation speed was reduced to 300r/min, and stirring was continued for 5h at 80℃under nitrogen. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PTh@PS microspheres
70mL of the PS microsphere emulsion prepared in the first step is diluted to 87mL by ultrapure water, 400 mu L of thiophene monomer is added under magnetic stirring, stirring is carried out for 5min, 12mL of 0.75M ammonium persulfate aqueous solution is added, and stirring is carried out for 2.5h.
And carrying out suction filtration and washing on the reacted solution to obtain black precipitate PTh@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of PTh spherical shell structural material
And uniformly dispersing all PTh@PS microspheres prepared in the previous step by using 60mL of ultrapure water to obtain PTh@PS microsphere emulsion. Under the stirring condition, 60mL of 0.08M potassium permanganate solution is dropwise added into the PTh@PS microsphere emulsion, after 2.5h of reaction, 600 mu L of thiophene monomer and 15mL of 0.37M ammonium persulfate aqueous solution are continuously added into the reaction solution under the ice bath environment, the reaction is stirred for 2.5h, and the PTh@MnO is obtained through suction filtration, washing, drying and grinding 2 The @ PTh submicron sphere material.
Taking PTh@MnO 2 Heating the temperature of the material at 8 ℃/min to 550 ℃ under argon atmosphere, performing high-temperature pyrolysis for 2.5h to remove polystyrene while carbonizing polythiophene, naturally cooling to room temperature in a tube furnace, and taking out to obtain a carbon-coated trimanganese tetraoxide submicron spherical shell material, which is marked as C@Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 7
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
192mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 60℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 5.5h under the nitrogen atmosphere at 60 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PTh@PS microspheres
60mL of the PS microsphere emulsion prepared in the first step is diluted to 75mL by ultrapure water, 450 mu L of thiophene monomer is added under magnetic stirring, stirring is carried out for 5min, 15mL of 0.8M ammonium persulfate aqueous solution is added, and stirring is carried out for 3 hours at normal temperature.
And carrying out suction filtration and washing on the reacted solution to obtain black precipitate PTh@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of PTh spherical shell structural material
And uniformly dispersing all PTh@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain PTh@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is added into the PTh@PS microsphere emulsion drop by drop, after reacting for 3 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 A PTh spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the material with the spherical shell structure at 5 ℃/min to 500 ℃ under the argon atmosphere, pyrolyzing at high temperature for 2h to remove polystyrene while carbonizing polythiophene, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated manganous-manganic oxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 8
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
192mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 60℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator is stirred for 10min at a speed of 1000r/min, and then reducedThe rotation speed is 300r/min, the temperature is 60 ℃ under the nitrogen atmosphere, and the stirring is continued for 5.5h. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PTh@PS microspheres
60mL of the PS microsphere emulsion prepared in the first step is diluted to 75mL by ultrapure water, 500 mu L of thiophene monomer is added under magnetic stirring, stirring is carried out for 5min, 15mL of 0.8M ammonium persulfate aqueous solution is added, and stirring is carried out for 3h.
And carrying out suction filtration and washing on the reacted solution to obtain black precipitate PTh@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of PTh spherical shell structural material
And uniformly dispersing all PTh@PS microspheres prepared in the previous step by using 100mL of ultrapure water to obtain PTh@PS microsphere emulsion. Under the stirring condition, 60mL of 0.06M potassium permanganate solution is dropwise added into the PTh@PS microsphere emulsion, after 3h of reaction, 600 mu L of thiophene monomer and 10mL of 0.35M ammonium persulfate aqueous solution are continuously added into the reaction solution under the ice bath environment, the mixture is stirred and reacted for 3h, and PTh@MnO is obtained through suction filtration, washing, drying and grinding 2 The @ PTh submicron sphere material.
Taking PTh@MnO 2 Heating to 500 ℃ at 5 ℃/min under argon atmosphere, pyrolyzing for 2 hours at high temperature to remove polystyrene while carbonizing polythiophene, naturally cooling to room temperature in a tube furnace, and taking out to obtain a carbon-coated trimanganese tetraoxide submicron spherical shell material, which is marked as C@Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 9
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 70 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PANI@PS microspheres
And (3) diluting 60mL of the PS microsphere emulsion prepared in the first step to 75mL by using ultrapure water, adding 400 mu L of aniline monomer under magnetic stirring, stirring for 5min, adding 10mL of 0.8M ammonium persulfate aqueous solution, and stirring for 2h at normal temperature.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PANI@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of @ PANI spherical shell structural material
And uniformly dispersing all the PANI@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain the PANI@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is added into the PANI@PS microsphere emulsion drop by drop, after reacting for 2 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 PANI spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the spherical shell structural material of @ PANI to 450 ℃ at 5 ℃/min under argon atmosphere, pyrolyzing at high temperature for 1h to remove polystyrene while carbonizing polyaniline, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetroxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 10
The first step: synthesis of Polystyrene (PS) microspheres
24mL of styrene is placed in a pear-shaped separating funnel, and the styrene is extracted with 220mL of 2M NaOH solution for three times, so that the polymerization inhibitor in the styrene solution is removed. Then 220mL of ultrapure water is used for extraction, the pH value of the styrene solution is regulated to 7-8, at the moment, the styrene solution is changed from colorless to clear champagne, and the solution is placed in a reagent bottle and is properly stored for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator was stirred at 1000r/min for 10min, then the rotation speed was reduced to 300r/min, and stirring was continued for 6h at 70℃under nitrogen atmosphere. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PANI@PS microspheres
60mL of the PS microsphere emulsion prepared in the first step is diluted to 75mL by ultrapure water, 400 mu L of aniline monomer is added under magnetic stirring, stirring is carried out for 5min, 10mL of 0.8M ammonium persulfate aqueous solution is added, and stirring is carried out for 2 hours.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PANI@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of @ PANI spherical shell structural material
And uniformly dispersing all the PANI@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain the PANI@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is dropwise added into the PANI@PS microsphere emulsion, after 3 hours of reaction, 400 mu L of aniline monomer and 10mL of 0.4M ammonium persulfate aqueous solution are continuously added into the reaction solution under the ice bath environment, the mixture is stirred and reacted for 2 hours, and PANI@MnO is obtained through suction filtration, washing, drying and grinding 2 PANI submicron sphere material.
Taking PANI@MnO 2 Heating up to 450 ℃ at 5 ℃/min under argon atmosphere, carrying out high-temperature pyrolysis for 10min to remove polystyrene while carbonizing polyaniline, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetraoxide submicron spherical shell material, which is marked as C@Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 11
The first step: synthesis of Polystyrene (PS) microspheres
30mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 240mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 240mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 70 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PTh@PS microspheres
And (3) diluting 60mL of the PS microsphere emulsion prepared in the first step to 75mL by using ultrapure water, adding 400 mu L of thiophene monomer under magnetic stirring, stirring for 5min, adding 10mL of 0.8M ammonium persulfate aqueous solution, and stirring for 2h at normal temperature.
And carrying out suction filtration and washing on the reacted solution to obtain black precipitate PTh@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of PTh spherical shell structural material
And uniformly dispersing all PTh@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain PTh@PS microsphere emulsion. Under the stirring condition, 40mL of 0.07M potassium permanganate solution is added into the PTh@PS microsphere emulsion drop by drop, after reacting for 2 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 A PTh spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the material with the spherical shell structure at 5 ℃/min to 450 ℃ under the argon atmosphere, pyrolyzing at high temperature for 1h to remove polystyrene while carbonizing polythiophene, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetroxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 12
The first step: synthesis of Polystyrene (PS) microspheres
20mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 160mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then 160mL of ultrapure water is used for extraction, the pH value of the styrene solution is regulated to 7-8, at the moment, the styrene solution is changed from colorless to clear champagne, and the solution is placed in a reagent bottle and is properly stored for standby.
240mL of ultrapure water was added to the three-necked flask, and 16mL of the above-treated styrene solution was simultaneously added thereto, heated to 70℃and then added with 0.28. 0.28g K 2 S 2 O 8 The initiator was stirred at 1000r/min for 10min, then the rotation speed was reduced to 300r/min, and stirring was continued for 6h at 70℃under nitrogen atmosphere. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PTh@PS microspheres
60mL of the PS microsphere emulsion prepared in the first step is diluted to 75mL by ultrapure water, 400 mu L of thiophene monomer is added under magnetic stirring, stirring is carried out for 5min, 10mL of 0.8M ammonium persulfate aqueous solution is added, and stirring is carried out for 2 hours.
And carrying out suction filtration and washing on the reacted solution to obtain black precipitate PTh@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of PTh spherical shell structural material
And uniformly dispersing all PTh@PS microspheres prepared in the previous step by using 50mL of ultrapure water to obtain PTh@PS microsphere emulsion. 40mL of 0.07M potassium permanganate solution is added into the PTh@PS microsphere emulsion dropwise under the stirring condition, and after 3 hours of reaction, the mixture is cooled in an ice bathContinuously adding 400 mu L of thiophene monomer and 10mL of 0.4M ammonium persulfate aqueous solution into the reaction solution under the environment, stirring and reacting for 2 hours, and obtaining PTh@MnO through suction filtration, washing, drying and grinding 2 The @ PTh submicron sphere material.
Taking PTh@MnO 2 Heating to 450 ℃ at 5 ℃/min under argon atmosphere, performing high-temperature pyrolysis for 10min to remove polystyrene while carbonizing polythiophene, naturally cooling to room temperature in a tube furnace, and taking out to obtain a carbon-coated trimanganese tetraoxide submicron spherical shell material, which is denoted as C@Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 13
The first step: synthesis of Polystyrene (PS) microspheres
25mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 200mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 200mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, together with 16mL of the above-treated styrene solution, followed by 0.35. 0.35g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 50 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PPy@PS microspheres
80mL of the PS microsphere emulsion prepared in the first step is diluted to 100mL by ultrapure water, 500 mu L of pyrrole monomer is added under magnetic stirring, the mixture is stirred for 5min, 15mL of 0.7M ammonium persulfate aqueous solution is added, and the mixture is stirred for 3 hours at normal temperature.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PPy@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of@PPy spherical shell structural material
And uniformly dispersing all the PPy@PS microspheres prepared in the previous step by using 70mL of ultrapure water to obtain PPy@PS microsphere emulsion. Under the stirring condition, 60mL of 0.07M potassium permanganate solution is added into the PPy@PS microsphere emulsion drop by drop, after reacting for 3 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 @ppy spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the material with the spherical shell structure at 10 ℃/min to 400 ℃ under argon atmosphere, performing high-temperature pyrolysis for 10min to remove polystyrene while carbonizing polypyrrole, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetraoxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
Example 14
The first step: synthesis of Polystyrene (PS) microspheres
30mL of styrene was placed in a pear-shaped separating funnel, and the styrene was extracted three times with 240mL of 2M NaOH solution to remove the polymerization inhibitor from the styrene solution. Then extracting with 240mL of ultrapure water, adjusting the pH value of the styrene solution to 7-8, changing the color of the styrene solution from colorless to clear champagne, and placing the styrene solution in a reagent bottle for proper storage for standby.
240mL of ultrapure water was added to the three-necked flask, together with 16mL of the above-treated styrene solution, followed by 0.35. 0.35g K 2 S 2 O 8 The initiator is stirred for 10min at the rotating speed of 1000r/min, then the rotating speed is reduced to 300r/min, and the initiator is stirred for 6h under the nitrogen atmosphere at 50 ℃. And transferring the PS emulsion in the three-neck flask into a 500mL beaker, sealing, and naturally cooling in a dark place. After standing overnight, further performing ultrasonic dispersion for 30min, and filtering to remove insoluble substances to obtain PS microsphere emulsion.
And a second step of: synthesis of PPy@PS microspheres
80mL of the PS microsphere emulsion prepared in the first step is diluted to 100mL by ultrapure water, 500 mu L of pyrrole monomer is added under magnetic stirring, the mixture is stirred for 5min, 15mL of 0.7M ammonium persulfate aqueous solution is added, and the mixture is stirred for 3 hours at normal temperature.
And carrying out suction filtration and washing on the solution after the reaction to obtain black precipitate PPy@PS microspheres.
And a third step of: mnO (MnO) 2 Synthesis of@PPy spherical shell structural material
And uniformly dispersing all the PPy@PS microspheres prepared in the previous step by using 70mL of ultrapure water to obtain PPy@PS microsphere emulsion. Under the stirring condition, 60mL of 0.07M potassium permanganate solution is added into the PPy@PS microsphere emulsion drop by drop, after reacting for 3 hours at normal temperature, the MnO can be obtained by suction filtration, washing and drying 2 @ppy spherical shell structural material.
Fourth step: preparation of carbon-coated manganous-manganic oxide submicron spherical shell material
The MnO obtained in the third step 2 Heating the material with the spherical shell structure @ PPy to 400 ℃ at 10 ℃/min under argon atmosphere, pyrolyzing at high temperature for 1h to remove polystyrene while carbonizing polypyrrole, naturally cooling to room temperature in a tube furnace, and taking out to obtain the carbon-coated trimanganese tetroxide submicron spherical shell material, which is marked as Mn 3 O 4 And @ C submicron spherical shell structure material.
The invention refers to a carbon-coated trimanganese submicron spherical shell material prepared by the method shown in the figure 1, wherein Mn is prepared 3 O 4 The diameter of the carbon submicron spherical shell structure material is about 300nm, wherein 1 refers to a hollow sphere formed by pyrolysis of PS and volatilization of PS, 2 refers to a spherical shell carbon layer formed by high-temperature carbonization of CP, and is rich in nitrogen element, 3 refers to a high-temperature pyrolysis manganese dioxide spherical layer, and the spherical shell carbon layer is converted into a manganese tetraoxide spherical layer after deoxidization; preparing C@Mn 3 O 4 The diameter of the material with the submicron spherical shell structure at @ C is about 320nm, wherein 1 refers to a hollow sphere formed by pyrolysis of PS and volatilization of PS, 2 refers to a spherical shell carbon layer formed by high-temperature carbonization of CP, and is rich in nitrogen element, 3 refers to a manganese dioxide spherical layer obtained by pyrolysis of manganese dioxide spherical layer, and the manganese dioxide spherical layer is converted into a manganese tetraoxide spherical layer after deoxidization. 4 refers to a spherical shell carbon layer formed by high-temperature carbonization of CP, and is rich in nitrogen.
FIG. 2 is a scanning electron microscope image of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 1 of the invention, and it can be seen from FIG. 2 that the spherical shell material obtained has a uniform size, a diameter of about 300nm, and Mn 3 O 4 The nano particles are uniformly attached to the surface of the spherical shell.
FIG. 3 is an EDS image of a carbon coated manganous-manganic oxide submicron spherical shell material prepared in example 1 of the present invention; as can be seen from FIG. 3, the spherical shell material prepared is uniform, and the C and N elements and Mn contained in the PPy derivative 3 O 4 Mn and O elements in the alloy are uniformly distributed.
Fig. 4 is a scanning electron microscope image of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 2 of the invention, and it can be seen from fig. 4 that the diameter of the spherical shell with the double carbon layer is slightly larger than that of the spherical shell with the single carbon layer in fig. 2, and the spherical shell has uniform size and diameter of about 320nm.
FIG. 5 is an EDS image of a carbon coated manganous-manganic oxide submicron spherical shell material prepared in example 2 of the present invention; as can be seen from fig. 5, C, N, mn, O four elements are uniformly distributed, and the content of Mn and O is slightly reduced compared with the single carbon layer spherical shell due to double-layer carbon coating.
FIG. 6 shows XRD diffraction patterns of the carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 1 of the invention, and it can be seen from FIG. 6 that the single-layer carbon-coated spherical shell material prepared by calcining at 450 ℃ is identical to the standard card Mn 3 O 4 One-to-one correspondence of characteristic peaks of (a).
FIG. 7 is an XRD diffraction pattern of a carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 2 of the invention, and it can be seen from FIG. 6 that the spherical shell material prepared by calcination at 450℃is identical to the standard card Mn 3 O 4 One-to-one correspondence of characteristic peaks of (a).
FIG. 8 shows the carbon-coated trimanganese tetroxide submicron spherical shell materials prepared in example 1 and example 2, respectively, obtained by pyrolysis at 450℃according to the invention, as the active material of the positive electrode material, zinc sheet as the negative electrode, znSO 4 As can be seen from FIG. 8, mn is given to the rate capability of the aqueous zinc ion battery assembled by using the solution as the electrolyte 3 O 4 The initial discharge specific capacity of the aqueous zinc ion battery taking the submicron spherical shell of @ C as an active substance is 260mAh/g under the current density of 0.5A/g, when the high current density is 10A/g, the discharge specific capacity reaches 120mAh/g, and when the current density returns to 1A/g, the discharge specific capacity reaches 355mAh/g, so that excellent rate capability is shown; and double pairLayer carbon coated active material C@Mn 3 O 4 The conductivity of the @ C submicron spherical shell is further improved, and the discharge specific capacity of the assembled water-based zinc ion battery is up to 200mAh/g when the high current density is 10A/g, so that the assembled water-based zinc ion battery has excellent rate capability.
Fig. 9 is a charge-discharge curve corresponding to the rate performance of fig. 8, and it can be seen from fig. 9 that the aqueous zinc ion battery assembled by using two spherical shell materials as active materials has a low battery overpotential, and the invention has an obvious effect on improving the conductivity and stability of the active materials due to the design of the spherical shell structure and the coating of the carbon material. C@Mn 3 O 4 Comparative Mn at C 3 O 4 The @ C submicron spherical shell has higher rate capability and lower resistance and internal resistance.
FIG. 10 shows a double-layer carbon-coated trimanganese tetroxide submicron spherical shell material prepared by pyrolysis at 450 ℃ in argon atmosphere as an active material of a positive electrode material, a zinc sheet as a negative electrode, and ZnSO according to the embodiment 2 of the invention 4 The solution is a discharge cycle chart of the water-based zinc ion battery assembled by the electrolyte, and as can be seen from fig. 10, the initial specific capacity of the water-based zinc ion battery reaches 184mAh/g under the current density of 50A/g, and after 5000 cycles, the initial capacity retention rate reaches 68%, so that the water-based zinc ion battery has a great application prospect. The invention greatly improves the cycle stability of the battery for the design of the active material structure.
FIG. 11 is an XRD diffraction pattern of a carbon-coated trimanganese tetraoxide submicron spherical shell material prepared in example 5 of the invention, and it can be seen from FIG. 11 that a single-layer carbon-coated spherical shell material prepared by calcining at 450℃is prepared in combination with standard card Mn 3 O 4 One-to-one correspondence of characteristic peaks of (a).
FIG. 12 is a graph showing the carbon-coated trimanganese tetroxide submicron spherical shell material prepared in example 5 of the invention as an active material of the positive electrode material, zinc sheets as the negative electrode, znSO 4 The solution is the circulation performance of the water system zinc ion battery assembled by the electrolyte, and as can be seen from fig. 12, under the current of 0.5mA, the capacity of the water system zinc ion battery is slowly increased along with the infiltration of the electrolyte in the spherical shell material, and the water system zinc ion battery tends to be stable after reaching 100 circles.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (6)
1. The preparation method of the carbon-coated manganous-manganic oxide submicron spherical shell material is characterized by comprising the following steps of:
step 1, taking water as a solvent, taking polystyrene microsphere emulsion as a template, adding a conductive polymer monomer A and an ammonium persulfate aqueous solution A, and performing in-situ polymerization reaction at normal temperature to obtain conductive polymer@polystyrene microspheres; the reaction time of the in-situ polymerization reaction is 2-3h; the proportion of the polystyrene microsphere emulsion, the water, the conductive polymer monomer A and the ammonium persulfate aqueous solution A is 60 mL-80 mL:15 mL-20 mL:400 mu L-500 mu L:10 mL-15 mL; the concentration of the ammonium persulfate aqueous solution A is 0.7-0.8mol/L; the conductive polymer monomer A is one of pyrrole monomer, aniline monomer and thiophene monomer;
step 2, dispersing all conductive polymer@polystyrene microspheres prepared in the step 1 in water to obtain conductive polymer@polystyrene microsphere emulsion, adding potassium permanganate solution into the conductive polymer@polystyrene microsphere emulsion, and performing oxidation-reduction reaction at normal temperature to generate a conductive polymer coated manganese dioxide precursor material; the reaction time of the oxidation-reduction reaction is 2-3h; the molar ratio of the conductive polymer monomer A in the step 1 to the potassium permanganate in the step 2 is 2-1:1; the concentration of the potassium permanganate is 0.05-0.08mol/L; the ratio of the conductive polymer monomer A in step 1 to the water in step 2 is 400 to 500. Mu.L: 50-100mL;
And 3, heating the conductive polymer coated manganese dioxide precursor material prepared in the step 2 to 400-550 ℃ at a speed of 5-10 ℃/min under the atmosphere of inert gas, and pyrolyzing for 10min-3h to obtain the carbon coated manganese tetraoxide submicron spherical shell material.
2. The method for preparing the carbon-coated manganous-manganic oxide submicron spherical shell material according to claim 1, which is characterized by further comprising the steps of adding a conductive polymer monomer B and an ammonium persulfate aqueous solution B in an ice bath environment after the oxidation-reduction reaction in the step 2 is completed, and performing in-situ polymerization reaction to obtain the conductive polymer-coated manganese dioxide precursor material.
3. The preparation method of the carbon-coated manganous-manganic oxide submicron spherical shell material according to claim 2, which is characterized in that after the oxidation-reduction reaction in the step 2 is completed, the addition ratio of the conductive polymer monomer B, the ammonium persulfate aqueous solution B and the potassium permanganate is 400-600 mu L:10 mL-20 mL: 40-60 mL, wherein the concentration of the ammonium persulfate aqueous solution B is 0.35-0.4mol/L;
the in-situ polymerization reaction time is 2-3h.
4. The method for preparing a carbon-coated trimanganese tetroxide spherical shell material according to claim 3, wherein the conductive polymer monomer B is the same as the conductive polymer A, and the conductive polymer monomer B is one of pyrrole monomer, aniline monomer and thiophene monomer.
5. A carbon-coated trimanganese tetroxide submicron spherical shell material prepared by the preparation method of any one of claims 1 to 3.
6. The use of the carbon-coated trimanganese tetroxide submicron spherical shell material according to claim 5 in a positive electrode material in an aqueous metal battery, wherein the aqueous metal battery is any one of aqueous zinc, potassium, magnesium, aluminum and calcium ion batteries.
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| CN111785942A (en) * | 2020-07-17 | 2020-10-16 | 北京大学深圳研究生院 | Water-based zinc ion battery positive electrode material and preparation method and application thereof |
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| CN108520944A (en) * | 2018-03-12 | 2018-09-11 | 华南理工大学 | A kind of nitrogen-doped carbon cladding mangano-manganic oxide composite material and preparation method and application |
| CN111785942A (en) * | 2020-07-17 | 2020-10-16 | 北京大学深圳研究生院 | Water-based zinc ion battery positive electrode material and preparation method and application thereof |
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| Title |
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| Morphology-controlled synthesis of polystyrene-Mn3O4 nanocomposites using surfactant and their application for watertreatment;Jun-Hwan Park et al;《Colloids and Surfaces A: Physicochemical and Engineering Aspects》;第441卷;第340-345页 * |
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