CN115084485B - Carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material and preparation method and application thereof - Google Patents
Carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material and preparation method and application thereof Download PDFInfo
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- CN115084485B CN115084485B CN202210912310.5A CN202210912310A CN115084485B CN 115084485 B CN115084485 B CN 115084485B CN 202210912310 A CN202210912310 A CN 202210912310A CN 115084485 B CN115084485 B CN 115084485B
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 164
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000011572 manganese Substances 0.000 title claims abstract description 64
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 60
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 235000015393 sodium molybdate Nutrition 0.000 claims description 13
- 239000011684 sodium molybdate Substances 0.000 claims description 13
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 13
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
Classifications
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, which comprises carbon fibers, wherein the carbon fibers are loaded with manganese molybdate/manganese oxide nano heterojunction structures on the surfaces of the carbon fibers; the basic units of the manganese molybdate/manganese oxide heterojunction are connected with the carbon fiber through C-Mn bonds, and the basic units of the manganese molybdate/manganese oxide heterojunction are bridged with each other. The carbon fiber load can improve the problem of large volume change of the manganese oxide in the charging and discharging process, and the heterostructure construction technology provides a opportunity for solving the problem of low capacity of the manganese oxide. The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material can cooperatively play the advantages of manganese molybdate and manganese oxide, and has high rate capacity and good cycle performance when being applied to zinc ion batteries, so that the storage performance of zinc ions can be improved.
Description
Technical Field
The invention belongs to the technical field of zinc ion battery anode materials, and particularly relates to a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, and a preparation method and application thereof.
Background
With the development of large-scale energy storage systems such as electric cars and smart grids, the disadvantages of the lithium ion battery are gradually obvious, the lithium resource reserve is limited to make the cost higher, the application of the lithium ion battery in the large-scale energy storage system is limited, and the increasing energy demands of people cannot be met, but the zinc ion battery is an ideal substitute for the lithium ion battery due to the characteristics of low cost, abundant reserve and wide distribution.
The manganese oxide has the characteristics of higher theoretical capacity, small polarization voltage and moderate working voltage, and can be used as the positive electrode material of the zinc ion battery. However, the volume of manganese oxide is changed greatly in the charge and discharge process, and the capacity is low.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, and a preparation method and application thereof, so as to solve the problems of larger volume change and low capacity of manganese oxide in the charging and discharging process.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, wherein the basic units of the manganese molybdate/manganese oxide heterojunction are connected with carbon fibers through C-Mn bonds, and the basic units of the manganese molybdate/manganese oxide heterojunction are mutually bridged.
Preferably, the basic unit size of the manganese molybdate/manganese oxide heterojunction is 10 to 500nm.
Preferably, the mass fraction of the manganese oxide is 50% -80%, and the mass fraction of the manganese molybdate is 20% -50%.
The invention also discloses a preparation method of the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, which comprises the following steps:
s1, KMnO 4 And ammonium oxalate are dissolved in deionized water and stirred uniformly to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A and the carbon fiber to obtain carbon fiber loaded manganese oxide;
s3, dissolving sodium molybdate and polyethylene glycol in deionized water, and uniformly stirring to obtain a precursor solution B;
and S4, carrying out hydrothermal reaction on the carbon fiber loaded manganese oxide and the precursor solution B to obtain the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
Preferably, in step S1, KMnO 4 And ammonium oxalate concentrations of 0.02-0.03M and 0.001M, respectively; in the step S3, the concentration of sodium molybdate is 0.01 to 5M.
Preferably, in the step S2, the hydrothermal reaction temperature is 120-200 ℃ and the reaction time is 0.5h.
Preferably, in the step S3, the dosage ratio of sodium molybdate, polyethylene glycol and deionized water is (0.12 to 0.48) g:0.16g:30mL.
Preferably, in step S4, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 24 hours.
The invention also discloses application of the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material in a zinc ion battery.
Preferably, the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, PVDF and acetylene black are mixed according to the ratio of 7:2: mixing the materials according to the mass ratio of 1, preparing slurry, uniformly coating the slurry on a stainless steel foil, drying to obtain a working electrode, and matching the working electrode with a counter electrode metal zinc foil to assemble the battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, which comprises carbon fibers, wherein the carbon fibers are loaded with manganese molybdate/manganese oxide nano heterojunction on the surface of the carbon fibers; the basic units of the manganese molybdate/manganese oxide heterojunction are connected with the carbon fiber through C-Mn bonds, and the basic units of the manganese molybdate/manganese oxide heterojunction are bridged with each other. The carbon fiber load can improve the problem of large volume change of the manganese oxide in the charging and discharging process, and the heterostructure construction technology provides a opportunity for solving the problem of low capacity of the manganese oxide. The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material can cooperatively play the advantages of manganese molybdate and manganese oxide, so that the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material has high rate capacity and good cycle performance.
Further, the basic unit size of the manganese molybdate/manganese oxide heterojunction is 10-500 nm, so that the electrode material is ensured to be fully contacted with the electrolyte, and the capacity performance of the battery is further improved.
The invention also discloses a preparation method of the carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material, which comprises the following steps of KMnO 4 And carrying out hydrothermal reaction on ammonium oxalate and carbon fiber to obtain carbon fiber loaded manganese oxide; and carrying out further hydrothermal reaction on the sodium molybdate and polyethylene glycol and the carbon fiber loaded manganese oxide to obtain the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material. The invention has simple preparation process and low cost, and is suitable for large-scale use of energy storage.
The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material disclosed by the invention has the advantages that the manganese molybdate can effectively relieve the dissolution of manganese oxide in the application of the zinc ion battery anode material, so that the zinc ion storage performance is improved, and the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material has certain advantages in the application of the zinc ion battery anode material.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, which comprises carbon fibers and a manganese molybdate/manganese oxide nano heterojunction structure loaded on the surfaces of the carbon fibers.
The invention discloses a method for preparing a carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material, which comprises the following steps:
s1, KMnO 4 And ammonium oxalate are dissolved in deionized water and stirred uniformly to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fiber into a reaction kettle, and performing hydrothermal preparation to obtain carbon fiber loaded manganese oxide;
s3, dissolving sodium molybdate and polyethylene glycol in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the carbon fiber loaded manganese oxide and the precursor solution B into a reaction kettle, and performing hydrothermal preparation to obtain a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material;
specifically, the steps are as followsIn S1, KMnO 4 And ammonium oxalate concentrations of 0.02-0.03M and 0.001M, respectively;
specifically, in step S3, the concentration of sodium molybdate is 0.01 to 5M.
Example 1
S1, 30mM KMnO 4 And 1mM ammonium oxalate are dissolved in 30mL deionized water and stirred uniformly to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fiber into a reaction kettle, and reacting for 0.5h at 120 ℃ to obtain carbon fiber loaded manganese oxide;
s3, dissolving 0.24g of sodium molybdate and 0.16g of polyethylene glycol in 30mL of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the carbon fiber loaded manganese oxide and the precursor solution B into a reaction kettle, and reacting at 200 ℃ for 24 hours to prepare the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
The electrochemical test method of the obtained carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material comprises the following steps:
the electrochemical performance of the positive electrode material is studied by adopting a button cell, and the formula of the electrode plate comprises the following active substances: PVDF: acetylene black=7: 2:1, uniformly coating the slurry on stainless steel foil, putting the stainless steel foil into a vacuum drying oven, drying at 80 ℃ for 12 hours, and punching to obtain the pole piece for the experimental battery. The metallic zinc foil is used as a counter electrode, and the electrolyte is 1.0M ZnSO 4 And 0.1M MnSO 4 The separator was a Watman GF/A glass fiber separator and assembled into a button cell under an air atmosphere. And (3) carrying out charge-discharge cycle test on the button cell: the charge-discharge cut-off voltage is 0.8-1.8V, and the charge-discharge current is 500mA/g.
Example 2
S1, 20mM KMnO 4 And 1mM ammonium oxalate are dissolved in 30mL deionized water and stirred uniformly to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fiber into a reaction kettle, and reacting for 0.5h at 160 ℃ to obtain carbon fiber loaded manganese oxide;
s3, dissolving 0.48g of sodium molybdate and 0.16g of polyethylene glycol in 30mL of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the carbon fiber loaded manganese oxide and the precursor solution B into a reaction kettle, and reacting at 200 ℃ for 24 hours to prepare the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
The electrochemical test method of the obtained carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material comprises the following steps:
the electrochemical performance of the positive electrode material is studied by adopting a button cell, and the formula of the electrode plate comprises the following active substances: PVDF: acetylene black=7: 2:1, uniformly coating the slurry on stainless steel foil, putting the stainless steel foil into a vacuum drying oven, drying at 80 ℃ for 12 hours, and punching to obtain the pole piece for the experimental battery. The metallic zinc foil is used as a counter electrode, and the electrolyte is 1.0M ZnSO 4 And 0.1M MnSO 4 The separator was a Watman GF/A glass fiber separator and assembled into a button cell under an air atmosphere. The oral test battery was subjected to a charge-discharge cycle test: the charge-discharge cut-off voltage is 0.8-1.8V, and the charge-discharge current is 500mA/g.
Example 3
S1, 30mM KMnO 4 And 1mM ammonium oxalate are dissolved in 30mL deionized water and stirred uniformly to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fiber into a reaction kettle, and reacting for 0.5h at 200 ℃ to obtain carbon fiber loaded manganese oxide;
s3, dissolving 0.12g of sodium molybdate and 0.16g of polyethylene glycol in 30mL of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the carbon fiber loaded manganese oxide and the precursor solution B into a reaction kettle, and reacting at 200 ℃ for 24 hours to prepare the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
The electrochemical test method of the obtained carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material comprises the following steps:
the electrochemical performance of the positive electrode material is studied by adopting a button cell, and the formula of the electrode plate comprises the following active substances: PVDF: acetylene black=7: preparing into slurry according to the ratio of 2:1, uniformly coating the slurry on a stainless steel foil, and placing the stainless steel foil into a vacuum drying oven for 80 ℃ for shootingAnd (3) drying the battery at the temperature of 12 hours, and punching to obtain the pole piece for the experimental battery. The metallic zinc foil is used as a counter electrode, and the electrolyte is 1.0M ZnSO 4 And 0.1M MnSO 4 The separator was a Watman GF/A glass fiber separator and assembled into a button cell under an air atmosphere. The oral test battery was subjected to a charge-discharge cycle test: the charge-discharge cut-off voltage is 0.8-1.8V, and the charge-discharge current is 500mA/g.
The preparation process is simple and convenient, and the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material has certain advantages in the application of the zinc ion battery anode material, and the manganese molybdate can effectively relieve the dissolution of manganese oxide, so that the zinc ion storage performance is improved.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material is characterized in that the basic units of the manganese molybdate/manganese oxide heterojunction are connected with carbon fibers through C-Mn bonds, and the basic units of the manganese molybdate/manganese oxide heterojunction are bridged with each other;
the preparation method of the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material comprises the following steps:
s1, KMnO 4 And ammonium oxalate are dissolved in deionized water and stirred uniformly to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A and the carbon fiber to obtain carbon fiber loaded manganese oxide;
s3, dissolving sodium molybdate and polyethylene glycol in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, carrying out hydrothermal reaction on the carbon fiber loaded manganese oxide and the precursor solution B to obtain a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material;
wherein the sodium molybdate is MnMoO 4 The method comprises the steps of carrying out a first treatment on the surface of the Manganese oxide as MnO 2 。
2. The carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material of claim 1, wherein the basic unit size of the manganese molybdate/manganese oxide heterojunction is 10-500 nm.
3. The carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material of claim 1, wherein the mass fraction of manganese oxide is 50% -80%, and the mass fraction of manganese molybdate is 20% -50%.
4. The carbon fiber supported manganese molybdate/manganese oxide nano-heterojunction material of claim 1, wherein in step S1 KMnO 4 And the concentration of ammonium oxalate is 0.02-0.03M and 0.001M respectively; in the step S3, the concentration of sodium molybdate is 0.01-5M.
5. The carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material of claim 1, wherein in step S2, the hydrothermal reaction temperature is 120-200 ℃ and the reaction time is 0.5h.
6. The carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material according to claim 1, wherein in step S3, the dosage ratio of sodium molybdate, polyethylene glycol and deionized water is (0.12 to 0.48) g:0.16g:30 And (3) mL.
7. The carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material of claim 1, wherein in step S4, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 24h.
8. The application of the carbon fiber supported manganese molybdate/manganese oxide nano heterojunction material in a zinc ion battery according to any one of claims 1-7.
9. The use according to claim 8, wherein the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, PVDF and acetylene black are mixed according to a ratio of 7:2: mixing the materials according to the mass ratio of 1, preparing slurry, uniformly coating the slurry on a stainless steel foil, drying to obtain a working electrode, and matching the working electrode with a counter electrode metal zinc foil to assemble the battery.
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| CN202210912310.5A CN115084485B (en) | 2022-07-29 | 2022-07-29 | Carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material and preparation method and application thereof |
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| CN202210912310.5A CN115084485B (en) | 2022-07-29 | 2022-07-29 | Carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material and preparation method and application thereof |
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| CN115084485A CN115084485A (en) | 2022-09-20 |
| CN115084485B true CN115084485B (en) | 2023-08-18 |
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