CN113755012A - Preparation method and application of MnO2/PPy composite material with three-dimensional mesoporous microsphere structure - Google Patents
Preparation method and application of MnO2/PPy composite material with three-dimensional mesoporous microsphere structure Download PDFInfo
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- CN113755012A CN113755012A CN202111142164.4A CN202111142164A CN113755012A CN 113755012 A CN113755012 A CN 113755012A CN 202111142164 A CN202111142164 A CN 202111142164A CN 113755012 A CN113755012 A CN 113755012A
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000004005 microsphere Substances 0.000 title claims abstract description 39
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims description 47
- 238000002360 preparation method Methods 0.000 title claims description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002070 nanowire Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002073 nanorod Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910001868 water Inorganic materials 0.000 claims abstract description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910006648 β-MnO2 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- -1 Zinc ion Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- H01M4/624—Electric conductive fillers
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Abstract
The invention discloses MnO with a three-dimensional mesoporous microsphere structure2Firstly, PPy nano-wire is prepared by chemical oxidation polymerization, and MnO is synthesized in PPy nano-wire group by redox reaction with PPy nano-wire as template2Nano-rods to obtain MnO with a three-dimensional mesoporous microsphere structure2a/PPy composite material. When the composite material is used as a positive electrode of a zinc ion battery, excellent electricity is shownChemical property, and has a specific discharge capacity as high as 361.8 mAh/g. The raw materials used in the invention are renewable and environment-friendly, and have good application prospect in the aspect of large-scale energy storage of the water system zinc ion battery.
Description
Technical Field
The invention relates to the field of water-based zinc ion batteries, in particular to MnO with a three-dimensional mesoporous microsphere structure2A preparation method and application of a/PPy composite material.
Background
With the excessive consumption of fossil fuels, energy crisis and climate deterioration have become issues to be solved urgently in the world. Currently, a lithium ion battery, as a traditional energy storage device, is widely used in the fields of electrochemical energy storage, electric vehicles, flexible and wearable electronic devices, and the like due to its advantages of high energy density, long service life, and the like. However, due to the poor safety performance of lithium ion batteries and the increasing shortage of lithium resources, the development of new batteries with high specific energy and low cost will become an important research direction in the battery field.
Benefit from Zn2+Low redox potential (-0.76V vs. standard hydrogen electrode), high theoretical specific capacity (820mAh g/Zn-1) And good cycle stability, zinc ion batteries have become increasingly popular for research. Meanwhile, due to the outstanding influence of the anode material on the electrochemical performance of the zinc ion battery, various anode materials, such as manganese-based materials, vanadium-based materials, Prussian blue analogues, carbon materials, polymer materials and the like, are widely researched. Among these positive electrode materials, manganese-based materials are being intensively studied due to their relatively high energy density.
The manganese dioxide material belongs to one of manganese-based anode materials, the unique tunnel structure and the crystal form diversity of the manganese dioxide material can obviously improve the structure designability of the anode material of the zinc ion battery, and meanwhile, the manganese dioxide anode material is low in cost, environment-friendly and high in safety, so that the manganese dioxide anode material has a wide application prospect. However, the manganese dioxide cathode material has poor conductivity and low structural stability, thereby causing adverse effects on the rate capability and long-cycle stability of the zinc ion battery. At present, commercial manganese dioxide particles are large in size, poor in conductivity and low in charging and discharging specific capacity, and the phenomena of nonuniform dispersion and the like easily occur in the process of preparing an electrode by mixing the manganese dioxide particles with a conductive agent, so that the stable high-rate charging and discharging cycle performance is difficult to maintain under high current density. Therefore, the overall performance of the zinc ion battery can be effectively improved by modifying and optimizing the manganese dioxide material.
The method disclosed in chinese document CN110364693A optimizes the electrochemical performance of manganese dioxide material by using porous hollow nano three-dimensional conductive skeleton to be compounded with manganese dioxide. The porous hollow nano three-dimensional conductive framework is obtained by calcining the MOF material at high temperature, and the method not only consumes energy, but also has complex synthetic process and increases the cost of large-scale application. In the method disclosed in chinese document CN112582602A, a mechanical ball milling method is used to compound commercial manganese dioxide with graphite nanoplatelets. The composite material obtained by the ball milling method is unstable in composite state, and a zinc battery prepared by taking the composite material obtained by the invention as a positive electrode material has general electrochemical performance.
Disclosure of Invention
In view of the above, there is a need to provide MnO with a three-dimensional mesoporous microsphere structure having higher specific capacity and cycle stability2A preparation method and application of a/PPy composite material.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a three-dimensional mesoporous microsphere structure MnO2/PPy composite material comprises the following steps:
s1: synthesizing a PPy nanowire by using a chemical oxidative polymerization method by using a pyrrole monomer and an ammonium persulfate solution as raw materials and cetyl trimethyl ammonium bromide as a template;
s2: dispersing PPy nano-wires in deionized water, and then adding MnSO4•H2O, obtaining a mixed solution, and forming a PPy nanowire group in the mixed solution by the PPy nanowire;
s3: adding ammonium persulfate solution into the mixed solution under the stirring condition to obtain a mixture, and performing hydrothermal reaction to obtain MnSO4•H2MnO formed by thermal decomposition of O2Interpenetration and synthesis of MnO in PPy nanowire coils2Washing and drying the nano-rods to obtain MnO with a three-dimensional mesoporous microsphere structure2a/PPy composite material.
Further, in step S1, the molar ratio of pyrrole monomer to ammonium persulfate is 1: 1.2.
further, in step S1, the molar ratio of cetyltrimethylammonium bromide to pyrrole monomer is 1: 4.
further, in step S1, the temperature of the chemical oxidative polymerization method is 0-5 deg.CoC，The time period required was 4 hours.
Further, in step S2, the amount of PPy nanowire was 0.04g, and the amount of deionized water was 40 ml.
Further, in step S2, MnSO4•H2The amount of O was 4.6 mmol.
Further, in step S3, the amount of ammonium persulfate added was 9.2 mmol.
Further, in step S3, the hydrothermal reaction was carried out at 120 ℃ for 12 hours.
In order to solve the technical problems, the second technical scheme of the invention is as follows: the zinc ion battery anode is made of MnO with the three-dimensional mesoporous microsphere structure prepared by the method2a/PPy composite material.
In order to solve the technical problems, the third technical scheme of the invention is as follows: a zinc ion battery comprises a zinc ion battery body, wherein the positive electrode of the zinc ion battery body is the positive electrode of the zinc ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. MnO with three-dimensional mesoporous microsphere structure2The source of the raw materials of the/PPy composite material is wide, the synthesis method is simple and easy to operate, and the electrochemical performance of the manganese dioxide material can be obviously improved.
2. MnO with three-dimensional mesoporous microsphere structure2the/PPy composite material has a unique three-dimensional mesoporous microsphere structure, and is beneficial to the insertion/extraction of zinc ions in the charge and discharge process of a zinc ion battery.
3. MnO with three-dimensional mesoporous microsphere structure2PPy nanowires in/PPy composites are effective for MnO reduction2The nanorods are connected in series, so that the conductivity of the material is greatly improved.
4. The method is simple, convenient, easy to operate and recyclable, and the MnO with the three-dimensional mesoporous microsphere structure prepared by the method is utilized2The zinc ion battery using the/PPy composite material as the positive electrode material has high charge and discharge stability, low cost of raw materials, suitability for industrial production and wide application prospect in the aspect of zinc ion positive electrode materials.
In order to make the aforementioned and other objects, features and advantages of the invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 shows MnO with a three-dimensional mesoporous microsphere structure prepared in the first embodiment of the present invention2XRD pictures in the/PPy composite.
FIG. 2 shows MnO with a three-dimensional mesoporous microsphere structure prepared in the first embodiment of the present invention2And (3) low-magnification scanning electron microscope pictures in the/PPy composite material.
FIG. 3 shows MnO with a three-dimensional mesoporous microsphere structure prepared according to the first embodiment of the present invention2High magnification scanning electron microscope picture in the/PPy composite material.
FIG. 4 is pure MnO2MnO with three-dimensional mesoporous microsphere structure prepared in the first embodiment of the invention2The multiplying power performance of the/PPy composite material is compared with that of the other composite material.
FIG. 5 is pure MnO2MnO with three-dimensional mesoporous microsphere structure prepared in the first embodiment of the invention2And the charge and discharge performance of the 50 th circle and the 100 th circle in the long-cycle test of the/PPy composite material are compared.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
Example one
MnO with three-dimensional mesoporous microsphere structure2The preparation method of the/PPy composite material comprises the following steps:
s1: cetyl trimethyl ammonium bromide and pyrrole monomers are mixed in a molar ratio of 1:4 in 200ml of deionized water to form a first solution, and 44ml of 0.2mol/L ammonium persulfate solution is dropwise added into the first solution under magnetic stirring. Stirring for 4 hr, washing with deionized water and ethanol for three times, and washing at 60 deg.CoAnd (3) drying for 12 hours in vacuum at the temperature of C to obtain the PPy nanowire.
S2: 0.04g of the dried PPy nano-wire is weighed and dispersed in 40ml of deionized water, and the mixture is stirred by magnetic forceAdding 4.6mmol of MnSO into the dispersion liquid4•H2And O and 9.2mmol of ammonium persulfate to obtain a mixed solution, wherein the PPy nanowire forms a PPy nanowire group in the mixed solution.
S3: the mixed solution is stirred for 30min and transferred into a 50ml autoclave at 120 DEG CoHydrothermal treatment at C temperature for 12 hours, MnSO4•H2MnO formed by thermal decomposition of O2Interpenetration and synthesis of MnO in PPy nanowire coils2And (4) nanorods. Finally washing with deionized water and ethanol for three times, and washing at 60 deg.CoVacuum drying for 24 hours at the temperature of C to obtain MnO with a three-dimensional mesoporous microsphere structure2the/PPy composite material is ground and weighed, and then the mass product is filled into a weighing bottle for standby.
The XRD pattern of the composite material is shown in figure 1. The material has XRD diffraction peak and standard beta-MnO2The XRD patterns of the PPy nano-wire are corresponding, and the XRD diffraction peak of the PPy nano-wire is displayed at the same time. And compared with standard beta-MnO2The XRD pattern of the composite material has small shift of each XRD diffraction peak, which proves that MnO2Successful synthesis of the/PPy composite, and MnO2And PPy is not simply physical adsorption. The MnO2The scanning electron microscope pictures of the low power and the high power of the/PPy composite material are shown in the figure 2 and the figure 3. Can prove the present MnO2the/PPy composite material has a three-dimensional mesoporous microsphere structure and is composed of PPy nanowires and MnO2And (4) nano rods.
MnO with three-dimensional mesoporous microsphere structure prepared in example one2the/PPy composite material is used as a zinc ion battery anode material, and the rate capability and the charge-discharge cycle performance of the composite material are tested.
Example two
MnO with three-dimensional mesoporous microsphere structure prepared by using method2Zinc ion battery anode made of/PPy composite material
0.04g of conductive carbon black is added into 1g of N-methylpyrrolidone solution of polyvinylidene fluoride with the concentration of 2wt% at normal temperature and normal pressure to obtain a mixed solution. After stirring for 20min, 0.14g of MnO with the three-dimensional mesoporous microsphere structure prepared in the first embodiment is added into the mixed solution2And stirring the/PPy composite material for 4 hours to obtain uniformly mixed anode slurry. The stirring is finishedAnd then uniformly coating the obtained slurry on the surface of the titanium foil. And drying the coated titanium foil, and cutting into small wafers with the diameter of 14mm, namely the zinc ion battery anode.
Zinc ion battery manufactured by using zinc ion battery anode manufactured by using method
The zinc foil is cut into small 14mm pieces as the negative electrode material of the battery, 16mm glass filter paper is used as the positive and negative electrode separation membrane, and the mixed solution of 2M zinc sulfate and 0.1M manganese sulfate is used as the electrolyte to assemble the zinc ion battery.
Testing the rate capability of the prepared zinc ion battery
And (3) testing the rate capability of the prepared zinc ion battery at room temperature by using a newware battery testing system. The prepared zinc ion battery is clamped on a neware battery tester, and the current density of the first three circles of charge-discharge circulation is set to be 0.05A/g, so that the zinc ion battery is used as the activation process of the battery anode material. And then setting the current density to be 0.1, 0.2, 0.5, 1, 1.5, 2 and 3A/g in sequence, wherein the number of charging and discharging cycles is 20 circles under each current density, and finally resetting the current density to be 0.1A/g for 100 circles to obtain the rate performance map of the prepared zinc ion battery.
As shown in FIG. 4, the results show that MnO in the three-dimensional mesoporous microsphere structure prepared by the method of the invention2the/PPy composite material as a zinc battery positive electrode material has more excellent rate performance compared with commercial electrolytic manganese dioxide. And when the final current density returns to 0.1A/g, the zinc battery prepared by the material of the invention shows higher discharge specific capacity than the initial specific capacity. This is largely due to its particular morphology and the good conductivity of PPy nanowires.
And testing the charge-discharge long-cycle performance of the prepared zinc ion battery.
And (3) testing the long-cycle performance of the prepared zinc ion battery at room temperature by using a newware battery testing system. The obtained zinc ion battery is clamped on a neware battery tester, and the current density of the first three circles of charge-discharge circulation is set to be 0.05A/g, so that the zinc ion battery is used as the activation process of the battery anode material. And then setting the current density to be 0.2A/g, and circulating for 1000 circles to obtain a charge-discharge long cycle performance map of the prepared zinc ion battery.
As shown in FIG. 5, the results show that MnO in the three-dimensional mesoporous microsphere structure prepared by the method of the present invention2Compared with commercial electrolytic manganese dioxide, the specific capacity of the zinc battery anode material made of the/PPy composite material is higher at the 50 th circle, and the specific capacity of the zinc battery assembled by commercial manganese dioxide serving as the anode material is reduced to 85.3mAh/g along with the charging and discharging, while the specific capacity of the zinc battery made of the composite material serving as the anode material is increased to 361.8 mAh/g. This phenomenon indicates that the MnO of the present invention has a three-dimensional mesoporous microsphere structure2the/PPy composite material has higher cycle stability and conductivity.
The pseudocapacitance property of the prepared zinc ion battery is tested.
The pseudocapacitance properties of the prepared zinc ion battery were tested at room temperature using the CHI660 electrochemical workstation. The obtained zinc ion battery is clamped into a CHI660 electrochemical workstation, and the CV curve of the zinc ion battery is measured by using cyclic voltammetry at different scanning rates and with a voltage window ranging from 1.8V to 0.8V. And simulating the occupation ratio of the pseudocapacitance in the total capacity of the zinc ion battery according to the obtained CV curve. The different scan rates were 0.4, 0.6, 0.8, 1.0mV/s, respectively.
The results show that the contribution ratios of the pseudocapacitance characteristics in the total specific capacity of the zinc ion battery are 46%, 52.6%, 55.6% and 61.4% in sequence at different scan rates (0.4, 0.6, 0.8, 1.0 mV/s). Proves that the invention has a three-dimensional mesoporous microsphere structure MnO2The zinc ion battery with the/PPy composite material as the anode material has good pseudo-capacitance characteristics.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. MnO with three-dimensional mesoporous microsphere structure2The preparation method of the/PPy composite material is characterized by comprising the following steps:
s1: synthesizing a PPy nanowire by using a chemical oxidative polymerization method by using a pyrrole monomer and an ammonium persulfate solution as raw materials and cetyl trimethyl ammonium bromide as a template;
s2: dispersing PPy nano-wires in deionized water, and then adding MnSO4•H2O, obtaining a mixed solution, and forming a PPy nanowire group in the mixed solution by the PPy nanowire;
s3: adding ammonium persulfate solution into the mixed solution under the stirring condition to obtain a mixture, and performing hydrothermal reaction to obtain MnSO4•H2MnO formed by thermal decomposition of O2Interpenetration and synthesis of MnO in PPy nanowire coils2Washing and drying the nano-rods to obtain MnO with a three-dimensional mesoporous microsphere structure2a/PPy composite material.
2. The three-dimensional mesoporous microsphere structure MnO of claim 12The preparation method of the/PPy composite material is characterized by comprising the following steps: in step S1, the molar ratio of pyrrole monomer to ammonium persulfate is 1: 1.2.
3. the preparation method of the three-dimensional mesoporous microsphere structure MnO2/PPy composite material of claim 1, wherein the preparation method comprises the following steps: in step S1, the molar ratio of cetyltrimethylammonium bromide to pyrrole monomer is 1: 4.
4. the three-dimensional mesoporous microsphere structure MnO of claim 12The preparation method of the/PPy composite material is characterized by comprising the following steps: in step S1, the temperature of the chemical oxidative polymerization method is 0-5%oAnd C, the time is 4 hours.
5. The three-dimensional mesoporous microsphere junction according to claim 1Form MnO2The preparation method of the/PPy composite material is characterized by comprising the following steps: in step S2, the amount of PPy nanowires was 0.04g, and the amount of deionized water was 40 ml.
6. The three-dimensional mesoporous microsphere structure MnO of claim 12The preparation method of the/PPy composite material is characterized by comprising the following steps: in step S2, MnSO4•H2The amount of O was 4.6 mmol.
7. The three-dimensional mesoporous microsphere structure MnO of claim 12The preparation method of the/PPy composite material is characterized by comprising the following steps: in step S3, the amount of ammonium persulfate added was 9.2 mmol.
8. The three-dimensional mesoporous microsphere structure MnO of claim 12The preparation method of the/PPy composite material is characterized by comprising the following steps: in step S3, the hydrothermal reaction was carried out at 120 ℃ for 12 hours.
9. A zinc ion battery positive electrode is characterized in that: the material of the positive electrode of the zinc ion battery comprises MnO with a three-dimensional mesoporous microsphere structure prepared by the method of any one of claims 1 to 82a/PPy composite material.
10. A zinc ion battery comprises a zinc ion battery body and is characterized in that: the positive electrode of the zinc-ion battery body is the positive electrode of the zinc-ion battery according to claim 9.
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