CN115084485A - 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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- 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 67
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 67
- 239000011572 manganese Substances 0.000 title claims abstract description 65
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 61
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims description 26
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 12
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 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
- 239000002002 slurry Substances 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
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims 7
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000011160 research 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
- 238000011161 development Methods 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
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 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
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Abstract
The invention discloses a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, wherein a positive electrode material comprises carbon fibers, and a manganese molybdate/manganese oxide nano heterojunction structure is loaded on the surfaces of the carbon fibers; 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 carbon fiber load can improve the problem that the volume change of the manganese oxide is large in the charging and discharging process, and the heterostructure building technology provides an opportunity for solving the problem of low capacity of the manganese oxide. The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material can synergistically exert the advantages of manganese molybdate and manganese oxide, and has high rate capacity and good cycle performance when being applied to a zinc ion battery, 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 as well as a preparation method and application thereof.
Background
With the development of large energy storage systems such as electric cars and smart power grids, the disadvantages of lithium ion batteries are gradually obvious, the lithium resource reserves are limited, so that the cost is higher, the application of the lithium ion batteries in the large energy storage systems is limited, and the increasing energy requirements of people cannot be met, and zinc ion batteries are gradually an ideal substitute for the lithium ion batteries due to the characteristics of low cost, rich reserves and wide distribution.
The manganese oxide can be used as the anode material of the zinc ion battery due to the characteristics of higher theoretical capacity, small polarization voltage and moderate working voltage. However, the manganese oxide has large volume change and low capacity in the charging and discharging processes.
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 large volume change and low capacity of manganese oxide in the charge and discharge processes.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, wherein basic units of a 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.
Preferably, the basic unit size of the manganese molybdate/manganese oxide heterojunction is 10-500 nm.
Preferably, the mass fraction of manganese oxide is 50-80%, and the mass fraction of 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, mixing KMnO 4 Dissolving the precursor solution and ammonium oxalate in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A and carbon fibers 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 the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
Preferably, in step S1, KMnO 4 And the ammonium oxalate concentration is 0.02-0.03M and 0.001M respectively; in step S3, the concentration of sodium molybdate is 0.01-5M.
Preferably, in step S2, the hydrothermal reaction temperature is 120 to 200 ℃ and the reaction time is 0.5 h.
Preferably, in step S3, the ratio of the sodium molybdate, the polyethylene glycol and the deionized water is (0.12-0.48) g: 0.16 g: 30 mL.
Preferably, in step S4, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 24 h.
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 weight ratio of 7: 2:1 into 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 a 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, wherein a positive electrode material comprises carbon fibers, and manganese molybdate/manganese oxide nano heterojunction is loaded on the surfaces of the carbon fibers; 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 carbon fiber load can improve the problem that the volume change of the manganese oxide is large in the charging and discharging process, and the heterostructure building technology provides an opportunity for solving the problem of low capacity of the manganese oxide. The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material can synergistically exert the advantages of manganese molybdate and manganese oxide, so that the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material is high in multiplying power capacity and good in cycle performance.
Furthermore, 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 improved.
The invention also discloses a preparation method of the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, which is implemented by KMnO 4 Carrying out hydrothermal reaction on ammonium oxalate and carbon fiber to obtain carbon fiber loaded manganese oxide; and further carrying out hydrothermal reaction on the sodium molybdate, the 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 energy storage.
The carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material disclosed by the invention is applied to a zinc ion battery anode material, and manganese molybdate can effectively relieve manganese oxide dissolution, 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 the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Moreover, 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 relates to a method for preparing a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material, which comprises the following steps of:
s1, mixing KMnO 4 Dissolving the precursor solution and ammonium oxalate in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fibers into a reaction kettle, and carrying out 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 carrying out hydrothermal preparation to obtain a carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material;
specifically, in step S1, KMnO 4 And the concentration of ammonium oxalate is 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, mixing 30mM KMnO 4 Dissolving 1mM ammonium oxalate in 30mL deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fibers into a reaction kettle, and reacting at 120 ℃ for 0.5h 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:
a button cell is adopted to research the electrochemical performance of the anode material, and the formula of the electrode plate is as follows: PVDF: acetylene black ═ 7: 2: preparing the mixture into slurry according to the proportion of 1, uniformly coating the slurry on a stainless steel foil, drying the stainless steel foil in a vacuum drying oven at the temperature of 80 ℃ for 12 hours, and punching to obtain the pole piece for the experimental battery. The metal zinc foil is used as a counter electrode, and the electrolyte is 1.0M ZnSO 4 And 0.1M MnSO 4 The diaphragm is a Watman GF/A glass fiber diaphragm, and the button cell is assembled in the 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 500 mA/g.
Example 2
S1, 20mM KMnO 4 And 1mM ammonium oxalate inUniformly stirring the mixture in 30mL of deionized water to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fiber into a reaction kettle, and reacting at 160 ℃ for 0.5h 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:
a button cell is adopted to research the electrochemical performance of the anode material, and the formula of the electrode plate is as follows: PVDF: acetylene black ═ 7: 2: preparing the mixture into slurry according to the proportion of 1, uniformly coating the slurry on a stainless steel foil, drying the stainless steel foil in a vacuum drying oven at the temperature of 80 ℃ for 12 hours, and punching to obtain the pole piece for the experimental battery. The metal zinc foil is used as a counter electrode, and the electrolyte is 1.0M ZnSO 4 And 0.1M MnSO 4 The diaphragm is a Watman GF/A glass fiber diaphragm, and the button cell is assembled in the air atmosphere. And (3) carrying out charge-discharge cycle test on the mouth test battery: the charge-discharge cut-off voltage is 0.8-1.8V, and the charge-discharge current is 500 mA/g.
Example 3
S1, mixing 30mM KMnO 4 Dissolving 1mM ammonium oxalate in 30mL deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A and the carbon fiber into a reaction kettle, and reacting at 200 ℃ for 0.5h 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:
a button cell is adopted to research the electrochemical performance of the anode material, and the formula of the electrode slice is as follows: PVDF: acetylene black ═ 7: preparing slurry according to the ratio of 2:1, uniformly coating the slurry on a stainless steel foil, drying the stainless steel foil in a vacuum drying oven at 80 ℃ for 12 hours, and punching to obtain the pole piece for the experimental battery. The metal zinc foil is used as a counter electrode, and the electrolyte is 1.0M ZnSO 4 And 0.1M MnSO 4 The diaphragm is a Watman GF/A glass fiber diaphragm, and the button cell is assembled in the air atmosphere. And (3) carrying out charge-discharge cycle test on the mouth test battery: the charge-discharge cut-off voltage is 0.8-1.8V, and the charge-discharge current is 500 mA/g.
The preparation process is simple and convenient, and the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material is applied to the positive electrode material of the zinc ion battery, and the manganese molybdate can effectively relieve the dissolution of manganese oxide, so that the storage performance of zinc ions is improved, and the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material has certain advantages in the application of the positive electrode material of the zinc ion battery.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material is characterized in that basic units of a 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.
2. The carbon fiber-supported manganese molybdate/manganese oxide nano heterojunction material according to 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 as claimed in claim 1, wherein the mass fraction of manganese oxide is 50-80%, and the mass fraction of manganese molybdate is 20-50%.
4. The preparation method of the carbon fiber-supported manganese molybdate/manganese oxide nano heterojunction material as claimed in claim 1, which is characterized by comprising the following steps:
s1, mixing KMnO 4 Dissolving ammonium oxalate in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A and carbon fibers 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 the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material.
5. The method for preparing the carbon fiber-supported manganese molybdate/manganese oxide nano heterojunction material as claimed in claim 4, wherein in the step S1, KMnO 4 And the ammonium oxalate concentration is 0.02-0.03M and 0.001M respectively; in step S3, the concentration of sodium molybdate is 0.01-5M.
6. The method for preparing the carbon fiber-supported manganese molybdate/manganese oxide nano heterojunction material as claimed in claim 4, wherein in the step S2, the hydrothermal reaction temperature is 120-200 ℃ and the reaction time is 0.5 h.
7. The method for preparing the carbon fiber-supported manganese molybdate/manganese oxide nano heterojunction material as claimed in claim 4, wherein in the step S3, the ratio of the amounts of sodium molybdate, polyethylene glycol and deionized water is (0.12-0.48) g: 0.16 g: 30 mL.
8. The method for preparing the carbon fiber-supported manganese molybdate/manganese oxide nano heterojunction material as claimed in claim 4, wherein in the step S4, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 24 h.
9. The application of the carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material as claimed in any one of claims 1 to 3 in a zinc ion battery.
10. The application of claim 9, wherein the carbon fiber loaded manganese molybdate/manganese oxide nano-heterojunction material, PVDF and acetylene black are mixed in a ratio of 7: 2:1 into 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 a battery.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154701A (en) * | 2011-03-01 | 2011-08-17 | 武汉理工大学 | Method for preparing manganese molybdate/cobalt molybdate hierarchical heterostructure nanowires |
| CN106673065A (en) * | 2016-12-14 | 2017-05-17 | 西北大学 | Inorganic non-metallic material sodium manganese molybdate and preparation method and application thereof |
| CN106887346A (en) * | 2017-03-07 | 2017-06-23 | 信阳师范学院 | The electrostatic spinning preparation method and manganese molybdate porous nanotube of a kind of manganese molybdate porous nanotube |
| CN109560265A (en) * | 2018-11-02 | 2019-04-02 | 中国电力科学研究院有限公司 | A kind of effective method for coating for inhibiting lithium-rich manganese-based anode material oxygen to be lost |
| CN110085447A (en) * | 2019-04-28 | 2019-08-02 | 江苏理工学院 | A kind of Cu-MnO/ carbon nano-fiber composite material and its preparation method and application |
| CN110265649A (en) * | 2019-06-28 | 2019-09-20 | 大连海事大学 | A kind of preparation method of the chargeable water system Zinc ion battery positive electrode of manganese dioxide of metal oxide cladding |
| CN110342579A (en) * | 2019-08-16 | 2019-10-18 | 陕西科技大学 | A kind of manganese molybdate carbon composite nano ball and preparation method thereof |
| US20200330962A1 (en) * | 2019-04-19 | 2020-10-22 | Soochow University | Copper mesh coated with manganese molybdate and application thereof in the separation of oil-water emulsion and degradation of organic pollutants in water |
| CN112624199A (en) * | 2020-12-16 | 2021-04-09 | 扬州大学 | Carbon quantum dot/manganese dioxide nano composite material, preparation method and application thereof |
| CN113725423A (en) * | 2021-09-17 | 2021-11-30 | 陕西科技大学 | MnCO3/MoS2Heterojunction composite material and preparation method and application thereof |
| CN113823788A (en) * | 2021-09-17 | 2021-12-21 | 陕西科技大学 | MnO (MnO)2/MoS2Heterojunction composite material and preparation method and application thereof |
| CN114335482A (en) * | 2021-12-28 | 2022-04-12 | 陕西科技大学 | MnO (MnO)2-metal heterojunction composite material and preparation method and application thereof |
-
2022
- 2022-07-29 CN CN202210912310.5A patent/CN115084485B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154701A (en) * | 2011-03-01 | 2011-08-17 | 武汉理工大学 | Method for preparing manganese molybdate/cobalt molybdate hierarchical heterostructure nanowires |
| CN106673065A (en) * | 2016-12-14 | 2017-05-17 | 西北大学 | Inorganic non-metallic material sodium manganese molybdate and preparation method and application thereof |
| CN106887346A (en) * | 2017-03-07 | 2017-06-23 | 信阳师范学院 | The electrostatic spinning preparation method and manganese molybdate porous nanotube of a kind of manganese molybdate porous nanotube |
| CN109560265A (en) * | 2018-11-02 | 2019-04-02 | 中国电力科学研究院有限公司 | A kind of effective method for coating for inhibiting lithium-rich manganese-based anode material oxygen to be lost |
| US20200330962A1 (en) * | 2019-04-19 | 2020-10-22 | Soochow University | Copper mesh coated with manganese molybdate and application thereof in the separation of oil-water emulsion and degradation of organic pollutants in water |
| CN110085447A (en) * | 2019-04-28 | 2019-08-02 | 江苏理工学院 | A kind of Cu-MnO/ carbon nano-fiber composite material and its preparation method and application |
| CN110265649A (en) * | 2019-06-28 | 2019-09-20 | 大连海事大学 | A kind of preparation method of the chargeable water system Zinc ion battery positive electrode of manganese dioxide of metal oxide cladding |
| CN110342579A (en) * | 2019-08-16 | 2019-10-18 | 陕西科技大学 | A kind of manganese molybdate carbon composite nano ball and preparation method thereof |
| CN112624199A (en) * | 2020-12-16 | 2021-04-09 | 扬州大学 | Carbon quantum dot/manganese dioxide nano composite material, preparation method and application thereof |
| CN113725423A (en) * | 2021-09-17 | 2021-11-30 | 陕西科技大学 | MnCO3/MoS2Heterojunction composite material and preparation method and application thereof |
| CN113823788A (en) * | 2021-09-17 | 2021-12-21 | 陕西科技大学 | MnO (MnO)2/MoS2Heterojunction composite material and preparation method and application thereof |
| CN114335482A (en) * | 2021-12-28 | 2022-04-12 | 陕西科技大学 | MnO (MnO)2-metal heterojunction composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIASHENG XU等: ""Fabrication of hierarchical MnMoO4•H2O@MnO2 core-shell nanosheet arrays on nickel foam as an advanced electrode for asymmetric supercapacitors"" * |
| 王志超;商洪静;郭广志;汤杰;李嵩;王昕宇;孙俊才;: "高稳定性水系锌离子电池正极材料MnO2@MgO的制备与性能" * |
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