CN112553574A - Preparation method of nano manganese oxide powder by PVD (physical vapor deposition) method - Google Patents
Preparation method of nano manganese oxide powder by PVD (physical vapor deposition) method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005240 physical vapour deposition Methods 0.000 title description 12
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 title description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 61
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 59
- 239000011572 manganese Substances 0.000 claims abstract description 59
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 46
- 239000002923 metal particle Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011049 filling Methods 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 238000010891 electric arc Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000011010 flushing procedure Methods 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
The invention discloses a preparation method of nanometer manganese oxide powder by a PVD method, relating to the technical field of nanometer powder preparation, and the key points of the technical scheme comprise the following steps: step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor; step 2, filling nitrogen into the reactor, and controlling the pressure in the reactor to be 70-100 kPa; step 3, igniting and arcing to enable the electric arc to be burnt between the plasma gun and the manganese metal particles, controlling the current of the plasma gun to be 500-600A and the temperature to be more than 1500 ℃, and continuing the step 4 after the manganese metal particles are completely melted; step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be more than 600A; and 5, gradually evaporating the metal manganese particles into manganese particles, introducing the manganese particles into a condenser, and introducing nitrogen-oxygen mixed gas into the condenser to react the evaporated manganese particles with oxygen to form MnO2Powder; step 6, collecting formed MnO by a collector connected with a condenser2And (3) powder. The invention has a displayThe effect of reducing the production difficulty and cost is remarkable.
Description
Technical Field
The invention relates to the technical field of nano powder preparation, in particular to a preparation method of nano manganese oxide powder by a PVD method.
Background
With the development of times and science and technology, people have more deep understanding on the energy storage mechanism of the super capacitor, and the super capacitor is found to have higher power density compared with a lithium ion battery, and has the advantages of high charging and discharging speed, long cycle stability and high specific capacitance, so that the super capacitor becomes a research hotspot of a new energy storage device, and the super capacitor can be roughly divided into a double electric layer capacitor and a pseudo capacitor according to the energy storage mechanism.
To date, transition metal oxide pseudocapacitors have gained much commercial interest because they have higher capacitance values than double layer capacitors, and transition metal oxides such as Mno2，Co3o4Nio, and VOxWhen the compound is used as an electrode material, the redox reaction has the characteristics of high speed, high reversibility and the like, but the current research mainly focuses on simple binary transition metal oxides, probably because a simple method for synthesizing a multi-element metal transition oxide composite material which is particularly effective is lacked. Moreover, the phenomenon of rapid attenuation of capacitance of some binary transition metal oxide nano-grade materials is also a common fault of the materials. Mixed Transition Metal Oxides (MTMO)s) Generally comprising two different metal ions, has received increasing attention due to potential applications in a variety of energy-related fields. Because in MTMOsThe middle paired metal ions have more abundant redox reaction types, and are beneficial to the application of the metal ions in the electrochemical field. In addition, the presence of multiple cations and the controllable stoichiometric/non-stoichiometric composition is MTMOsProvides a larger control space for the physical and chemical properties of the material.
Noble metal oxides such as ruthenium dioxide are successfully applied to electrode materials of supercapacitors due to their excellent electrochemical properties. But its widespread use is limited by expensive cost and toxic properties. Therefore, people are devoted to research and develop other cheap metal oxides, such as nickel oxide, cobalt oxide, manganese oxide and the like, and the manganese oxide is taken as a superior super capacitor electrode material with higher cost performance, wherein the manganese oxide is expected to be a transition metal oxide for replacing ruthenium dioxide due to the advantages of low cost, greenness, no pollution, higher theoretical specific capacitance, wider working potential window and the like. The currently known methods for preparing manganese oxide include the following:
1) thermal decomposition method, 2) liquid-phase coprecipitation method.
The manganese sulfate is prepared by further oxidizing or reducing metal manganese oxide or heating divalent manganese salt in air at 600-800 ℃, but manganese sulfate is not thermally decomposed at 900 ℃. The simplest method is to use manganese nitrate hexahydrate or pure beta-MnO2Heated to constant weight in air at 650 ℃. When manganese nitrate hexahydrate is used as raw material, it is preheated at 190 deg.C to obtain solid (equivalent to beta-MnO)2) The manganese oxide powder was pulverized and then dried by heating at 650 ℃.
With potassium permanganate (KMnO)4) Taking natural graphite powder as a reducing agent as a starting material, and reacting under a hydrothermal condition to generate a manganese dioxide nanowire material precursor; then the manganese oxide powder is prepared by washing and vacuum drying.
However, the two methods for producing manganese oxide powder produce a large amount of waste water and waste liquid in the production process and have the defect of difficult treatment; the manganese oxide powder needs to be heated and dried during preparation, and the problems of complicated production steps, high production cost and inconvenience for large-scale production due to poor powder agglomeration and dispersibility in the drying process need to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of nano manganese oxide powder by a PVD (physical vapor deposition) method, which has the effect of remarkably reducing the production difficulty and cost.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of nanometer manganese oxide powder by a PVD method comprises the following steps:
step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor;
step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be more than 600A;
and 5, gradually evaporating the metal manganese particles into manganese particles, introducing the manganese particles into a condenser, and introducing nitrogen-oxygen mixed gas into the condenser to react the evaporated manganese particles with oxygen to form MnO2Powder;
step 6, collecting formed MnO by a collector connected with a condenser2And (3) powder.
The invention is further configured to: in step 5, the nitrogen-oxygen mixed gas is fed from the tail part of the condenser, cooled and crystallized and nucleated in the condenser of the evaporated manganese particles, and then reacts with oxygen to form MnO2And (3) powder.
The invention is further configured to: the MnO2The diameter of the powder is 10-200 nm.
The invention is further configured to: in step 5, the temperature of the evaporated manganese particles in the condenser is 500-1000 ℃.
The invention is further configured to: in step 6, the manganese oxide collected and formed by the collector is collected by the powder collector after passing through the back flushing device.
The invention is further configured to: the metal manganese particles are blocky metal manganese, and in the graphite pot, the metal manganese particles are used as a negative electrode, and a plasma gun is used as a positive electrode.
In conclusion, the invention has the following beneficial effects:
1. the metal manganese blocks are used as raw materials, the nitrogen is used as protective gas, and the nitrogen is in a fully-closed recycling state, so that no wastewater or waste gas is discharged in the production process, and the safety of the production process is high;
2. by controlling the entering speed of the nitrogen-oxygen mixed gas, the MnO is further controlled2The growth and cooling speed of the powder are controlled, and finally the formed MnO is controlled2The particle size of the powder;
3. MnO to be obtained2The powder has regular spherical appearance, uniform particle size, large specific surface area, good dispersibility, large specific capacity, multiple cycle times and high purity.
Drawings
Fig. 1 is a schematic structural diagram of a PVD-process nano manganese oxide powder preparation apparatus according to this embodiment.
Description of reference numerals: 1. a graphite pot; 2. a reactor; 3. a condenser; 4. a collector; 5. a powder collector.
Detailed Description
In order to make the technical solution and advantages of the present invention more clear, the present invention will be further described in detail with reference to the accompanying drawings.
As shown in fig. 1, a PVD-process apparatus for preparing nano manganese oxide powder comprises a reactor 2, a condenser 3 and a collector 4. A graphite pot 1 and a plasma gun are provided in the reactor 2. The graphite pot 1 is used for placing the manganese metal particles, and the plasma gun is used for heating the manganese metal particles in the graphite pot. Meanwhile, nitrogen is filled in the reactor 2, so that the nitrogen is used as protective gas to avoid oxidation reaction of the manganese metal particles in the reactor 2; the manganese metal particles form manganese particles after evaporation and enter the condenser 3 for condensation, nitrogen-oxygen mixed gas is introduced into one end of the condenser 3 connected with the collector 4, and then the manganese particles moving from the condenser 3 to the collector 4 react with oxygen to form MnO2And (3) powder. It should be mentioned that a powder collector 5 is arranged at the bottom of the collector 4, and MnO is arranged in the collector2The powder enters the powder collector 5 to be collected after passing through a back-blowing device at the mouth of the powder collector 5.
A preparation method of nanometer manganese oxide powder by a PVD method comprises the following steps:
step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor;
step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be more than 600A;
step 6, collecting formed MnO by a collector connected with a condenser2Powder;
step 7, MnO in collector2The powder is collected by a powder collector after passing through a back flushing device.
In step 5, the nitrogen-oxygen mixture gas is fed from the tail of the condenser, so that the evaporated manganese particles are cooled in the condenser, crystallized and nucleated, and then react with oxygen to form MnO2Powder of MnO2The diameter of the powder is 10-200 nm. Meanwhile, the manganese metal particles are blocky manganese metal, and in the graphite pot, the manganese metal particles are used as a negative electrode, and the plasma gun is used as a positive electrode.
Example one
A preparation method of nanometer manganese oxide powder by a PVD method comprises the following steps:
step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor;
step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be 620A;
step 6, collecting formed MnO by a collector connected with a condenser2Powder;
step 7, MnO in collector2The powder is collected by a powder collector after passing through a back flushing device.
In step 5, the nitrogen-oxygen mixture gas is fed from the tail of the condenser, so that the evaporated manganese particles are cooled in the condenser, crystallized and nucleated, and then react with oxygen to form MnO2Powder of MnO2The diameter of the powder was 36 nm. Meanwhile, the manganese metal particles are blocky manganese metal, and in the graphite pot, the manganese metal particles are used as a negative electrode, and the plasma gun is used as a positive electrode.
Example two
A preparation method of nanometer manganese oxide powder by a PVD method comprises the following steps:
step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor;
step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be 650A;
step 6, collecting formed MnO by a collector connected with a condenser2Powder;
step 7, MnO in collector2The powder is collected by a powder collector after passing through a back flushing device.
In step 5, the nitrogen-oxygen mixture gas is fed from the tail of the condenser, so that the evaporated manganese particles are cooled in the condenser, crystallized and nucleated, and then react with oxygen to form MnO2Powder of MnO2The diameter of the powder was 132 nm. Meanwhile, the manganese metal particles are blocky manganese metal, and in the graphite pot, the manganese metal particles are used as a negative electrode, and the plasma gun is used as a positive electrode.
EXAMPLE III
A preparation method of nanometer manganese oxide powder by a PVD method comprises the following steps:
step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor;
step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be 750A;
step 6, collecting formed MnO by a collector connected with a condenser2Powder;
step 7, MnO in collector2The powder is collected by a powder collector after passing through a back flushing device.
In step 5, the nitrogen-oxygen mixture gas is fed from the tail of the condenser, so that the evaporated manganese particles are cooled in the condenser, crystallized and nucleated, and then react with oxygen to form MnO2Powder of MnO2The diameter of the powder was 186 nm. Meanwhile, the manganese metal particles are blocky manganese metal, and in the graphite pot, the manganese metal particles are used as a negative electrode, and the plasma gun is used as a positive electrode.
Comparative example 1
Comparative example one preparation of MnO by liquid Co-precipitation2And (3) powder.
Comparative example No. two
Comparative example II preparation of MnO by thermal decomposition2And (3) powder.
The test results were as follows:
table one test result table
| BET(m2/g) | Specific capacity F/G | Number of charging cycles | |
| Example one | 207 | 239.1 | 1350 |
| Example two | 202 | 232.8 | 1300 |
| EXAMPLE III | 200 | 235.6 | 1300 |
| Comparative example 1 | 160.7 | 203.4 | 1000 |
| Comparative example No. two | 180 | 166 | 950 |
In summary, MnO obtained by the preparation method of the present application2The powder has the effects of increasing the specific surface area by more than 35 percent, increasing the specific capacity by more than 10 percent and increasing the charging cycle times by more than 30 percent. Meanwhile, the metal manganese blocks are used as raw materials, the nitrogen is used as protective gas, and the nitrogen is in a fully-closed recycling state, so that no wastewater or waste gas is discharged in the production process, and the safety of the production process is high; and MnO is controlled by controlling the entering speed of the nitrogen-oxygen mixed gas2The growth and cooling speed of the powder are controlled, and finally the formed MnO is controlled2The particle size of the powder. Thus, MnO was obtained2The powder has regular spherical appearance, and has the effects of uniform particle size, large specific surface area, good dispersibility, large specific capacity, multiple cycle times and high purity.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiment, but all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the present invention may occur to those skilled in the art without departing from the principle of the present invention, and such modifications and embellishments should also be considered as within the scope of the present invention.
Claims (6)
1. A preparation method of nanometer manganese oxide powder by a PVD method is characterized by comprising the following steps:
step 1, screening metal manganese particles, and filling the metal manganese particles into a graphite pot of a reactor;
step 2, filling nitrogen into the reactor, and controlling the pressure in the reactor to be 70-100 kPa;
step 3, igniting and arcing to enable the electric arc to be burnt between the plasma gun and the manganese metal particles, controlling the current of the plasma gun to be 500-600A and the temperature to be more than 1500 ℃, and continuing the step 4 after the manganese metal particles are completely melted;
step 4, increasing the current of the plasma gun, and controlling the current of the plasma gun to be more than 600A;
step 5, gradually evaporating the metal manganese particles into manganese particles, feeding the manganese particles into a condenser, and meanwhile, feeding the manganese particles into the condenserIntroducing mixed nitrogen-oxygen gas to react the evaporated manganese particles with oxygen to form MnO2Powder;
step 6, collecting formed MnO by a collector connected with a condenser2And (3) powder.
2. The PVD method for preparing nanometer manganese oxide powder according to claim 1, characterized in that: in step 5, the nitrogen-oxygen mixed gas is fed from the tail part of the condenser, cooled and crystallized and nucleated in the condenser of the evaporated manganese particles, and then reacts with oxygen to form MnO2And (3) powder.
3. The PVD method for preparing nanometer manganese oxide powder according to claim 2, characterized in that: the MnO2The diameter of the powder is 10-200 nm.
4. The PVD method for preparing nanometer manganese oxide powder according to claim 1, characterized in that: in step 5, the temperature of the evaporated manganese particles in the condenser is 500-1000 ℃.
5. The PVD method for preparing nanometer manganese oxide powder according to claim 1, characterized in that: in step 6, the manganese oxide collected and formed by the collector is collected by the powder collector after passing through the back flushing device.
6. The PVD method for preparing nanometer manganese oxide powder according to claim 1, characterized in that: the metal manganese particles are blocky metal manganese, and in the graphite pot, the metal manganese particles are used as a negative electrode, and a plasma gun is used as a positive electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4365137A1 (en) * | 2022-11-02 | 2024-05-08 | Basf Se | Process for making an oxide of manganese |
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| CN102950290A (en) * | 2012-10-15 | 2013-03-06 | 宁波广博纳米新材料股份有限公司 | Method for producing nanoscale nickel-manganese alloy powder |
| CN109648093A (en) * | 2018-12-18 | 2019-04-19 | 江苏博迁新材料股份有限公司 | A kind of superfine metal nickel powder surface treatment method |
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| JPH07247122A (en) * | 1994-03-10 | 1995-09-26 | Japan Metals & Chem Co Ltd | Activated manganese dioxide and method for producing the same |
| KR20070066545A (en) * | 2005-12-22 | 2007-06-27 | 주식회사 포스코 | Method of making nano mpp powder using rf plasma combustion |
| CN102950289A (en) * | 2012-10-15 | 2013-03-06 | 宁波广博纳米新材料股份有限公司 | Method for producing nanoscale copper-manganese alloy powder |
| CN102950290A (en) * | 2012-10-15 | 2013-03-06 | 宁波广博纳米新材料股份有限公司 | Method for producing nanoscale nickel-manganese alloy powder |
| CN109648093A (en) * | 2018-12-18 | 2019-04-19 | 江苏博迁新材料股份有限公司 | A kind of superfine metal nickel powder surface treatment method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4365137A1 (en) * | 2022-11-02 | 2024-05-08 | Basf Se | Process for making an oxide of manganese |
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Application publication date: 20210326 |