CN107910525B - Preparation method of nitrogen-doped manganese carbonate and compound thereof - Google Patents
Preparation method of nitrogen-doped manganese carbonate and compound thereof Download PDFInfo
- Publication number
- CN107910525B CN107910525B CN201711137136.7A CN201711137136A CN107910525B CN 107910525 B CN107910525 B CN 107910525B CN 201711137136 A CN201711137136 A CN 201711137136A CN 107910525 B CN107910525 B CN 107910525B
- Authority
- CN
- China
- Prior art keywords
- manganese carbonate
- manganese
- nitrogen
- temperature
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 82
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 82
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 82
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 82
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 11
- 150000001413 amino acids Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- -1 carbon nanotube compound Chemical class 0.000 claims description 9
- 229940024606 amino acid Drugs 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229960002885 histidine Drugs 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nitrogen-doped manganese carbonate and a preparation method of a compound thereof. The method comprises the following steps: gradually dropwise adding the hydrophilic amino acid aqueous solution into the manganese salt aqueous solution, stirring to form a uniform solution, transferring the solution into a reaction kettle, controlling the temperature to be 2-8 ℃/min, heating to 120-220 ℃, carrying out hydrothermal reaction at a constant temperature, cooling to room temperature along with the furnace temperature, filtering, washing and drying to obtain the nitrogen-doped manganese carbonate. The lithium ion battery electrode assembled by the nitrogen-doped manganese carbonate and the compound thereof is formed by respectively taking the compounds of manganese carbonate, manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nano tube as active materials, assembling a button type lithium ion battery and testing the performance of the button type lithium ion battery in the charging and discharging processes, and the result shows that the assembled lithium ion battery has excellent energy storage performance. The material and the compound thereof can be popularized in the aspects of sodium ions, supercapacitors, industrial catalysis, medicines, coatings and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation and application thereof, and particularly relates to a preparation method of nitrogen-doped manganese carbonate and a compound thereof and application of the nitrogen-doped manganese carbonate and the compound thereof in the aspect of lithium ions.
Background
Manganese carbonate is an important inorganic material, and can be widely applied to the fields of catalysts, medicines, ceramics, coatings, electrochemical energy storage and the like, so that the preparation of manganese carbonate is widely concerned at home and abroad, the current industrial manganese carbonate method is usually prepared by wet beneficiation, and the laboratory manganese carbonate preparation method is usually a hydrothermal method, an electrodeposition method and the like. There are researchers with MnSO4·4H2Preparing porous manganese carbonate microparticles by using O, polyvinylpyrrolidone (PVP), vitamin C, triethylene glycol and sodium bicarbonate as raw materials through a hydrothermal method (Kang, W. P.et al., Nanostructured porous carbonate spheres with capacitive effects on the high quality storage capacity, Nanoscale 2015, 7 (22), 10146-phase 10151.); sodium citrate and MnSO have also been studied4The pH value of the solution is controlled to be 6.7-7.0, and the solution and GO are prepared into a composite material of reduced Graphene/manganese carbonate nanocrystals (Gao, M. W et al., Graphene-coated mesoporous MnCO) by an electrodeposition method3 single crystals synthesized by a dynamic floating electrodeposition method for high performance lithium-ion storage. J Mater Chem A 2015, 3 (27), 14126-14133.）。
With the rapid development of electrochemical energy storage and the continuous expansion of application fields, the demand of the market on electrode materials is continuously increased, and researchers are prompted to continuously research the materials in the aspect of electrode application. In view of the fact that manganese carbonate has high theoretical specific capacity of energy storage and good compatibility with the currently used electrolyte, the material has become one of the best choices of chemical energy storage electrode materials such as lithium ion batteries or super capacitors, and also becomes one of the research hotspots for application in chemical energy storage, and meanwhile, nitrogen can more effectively promote the energy storage performance of manganese carbonate. Zhang Jianxin and the like select a potassium permanganate solution and a carbon source to carry out hydrothermal reaction to prepare a carbon-coated manganese carbonate material for a lithium ion battery cathode material (CN 105826522A, a preparation method of in-situ carbon-coated manganese carbonate for a lithium ion battery cathode); s, Devaraj and the like use potassium permanganate solution and commercial sugar solution as raw materials, and a micro-nano manganese carbonate material is prepared by a hydrothermal method and is used as an electrode material of a super capacitor (S, Devaraj, et al, MnCO)3: a novel electrode material for supercapacitors. J. Mater. Chem. A,2014,2,4276-4281.). Therefore, the method has important research significance and application value for the preparation and performance research of the manganese carbonate preparation material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of nitrogen-doped manganese carbonate and a compound thereof.
In order to realize the purpose, the technical scheme is as follows:
a preparation method of nitrogen-doped manganese carbonate comprises the following steps:
gradually dropwise adding a hydrophilic amino acid aqueous solution into a manganese salt aqueous solution, stirring to form a uniform solution, transferring the solution into a reaction kettle, controlling the temperature to be 2-8 ℃/min, heating to 120-220 ℃, carrying out a hydrothermal reaction at a constant temperature, cooling to room temperature along with the furnace temperature, filtering, washing and drying to obtain the nitrogen-doped manganese carbonate.
Preferably, in the above method for preparing nitrogen-doped manganese carbonate, the manganese salt is one of potassium permanganate, manganese sulfate and manganese nitrate, or a mixture of any of them.
Preferably, in the preparation method of nitrogen-doped manganese carbonate, the hydrophilic amino acid is one of glycine, L-histidine, leucine and tyrosine, or a mixture of any of them.
Preferably, in the preparation method of nitrogen-doped manganese carbonate, the stirring time is 20-60 minutes, and the stirring is accompanied with ultrasonic treatment; the constant temperature time is 5-20 hours.
Preferably, in the preparation method of the nitrogen-doped manganese carbonate, the drying method is freeze drying or vacuum drying, wherein the freeze drying temperature is-50 to-5 ℃, and the vacuum drying temperature is 50 to 120 ℃.
A manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nanotube composite is prepared by the following method: respectively reacting the obtained nitrogen-doped manganese carbonate serving as a raw material with glucose, graphene and a carbon nano tube again to obtain a manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nano tube compound;
or:
and adding glucose, graphene and carbon nanotubes in the preparation step of the manganese carbonate to realize in-situ preparation of the manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nanotube compound.
Compared with the prior art, the invention has the following effects: the preparation method of the invention prepares the manganese carbonate by one step by taking manganese salt with abundant reserves and low price and amino acid as raw materials. The method disclosed by the invention is simple to operate, low in cost and environment-friendly, can realize one-step preparation and large-batch preparation of the manganese carbonate material, and meanwhile, the manganese carbonate has good electrochemical energy storage capability. And the method can further prepare manganese carbonate/carbon, manganese carbonate/graphene, manganese carbonate/carbon nanotube composite manganese carbonate and other series materials. The lithium ion battery electrode assembled by the nitrogen-doped manganese carbonate and the compound thereof is formed by respectively taking the compounds of manganese carbonate, manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nano tube as active materials, assembling a button type lithium ion battery and testing the performance of the button type lithium ion battery in the charging and discharging processes, and the result shows that the assembled lithium ion battery has excellent energy storage performance. The material and the compound thereof can be popularized in the aspects of sodium ions, supercapacitors, industrial catalysis, medicines, coatings and the like.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of manganese carbonate;
FIG. 2 is a Transmission Electron Micrograph (TEM) of manganese carbonate;
FIG. 3 is an X-ray diffraction pattern (XRD) of manganese carbonate;
FIG. 4 shows that the lithium ion battery using manganese carbonate as electrode material is at 100mAg-1Time-dependent charge and discharge and coulombic efficiency diagrams;
FIG. 5 shows that the lithium ion battery using manganese carbonate as the electrode material is at 500mAg-1Time-dependent charge and discharge and coulombic efficiency diagrams;
FIG. 6 is a Scanning Electron Micrograph (SEM) of manganese carbonate/carbon;
fig. 7 is a Scanning Electron Micrograph (SEM) of manganese carbonate/graphene.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the invention in any way.
Example 1
Completely dissolving 3.16g (g) of potassium permanganate in 25 milliliters (mL) of deionized water to form a potassium permanganate aqueous solution; 0.75 grams (g) of glycine was completely dissolved in 25 milliliters (mL) of deionized water to form an aqueous glycine solution. Then adding the glycine aqueous solution into the potassium permanganate aqueous solution while stirring, stirring for 30 minutes (min) until the glycine aqueous solution is completely mixed and stirred uniformly, and simultaneously carrying out ultrasonic dispersion with the power controlled at 100W. Transferring the uniformly mixed solution into a polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a hydrothermal reaction kettle, and putting the hydrothermal reaction kettle at 180 DEG CKeeping the temperature in the oven for 10 hours (h), naturally cooling along with the temperature of the oven, and taking out. And washing the reaction product with deionized water for many times, carrying out vacuum filtration until the pH value of the filtrate is 7, and then putting the filtrate into a vacuum drying oven at 65 ℃ (DEG C) for heating and drying for 12 hours (h) to obtain the nitrogen-doped manganese carbonate. The manganese carbonate was tested for performance at 100mAg for a battery-1The discharge performance can reach 590 mAh g after 20 circles of testing-1And when the current is increased to 500mAg-1The discharge performance can reach 305 mAh g-1. FIG. 1 is a Scanning Electron Micrograph (SEM) of manganese carbonate; FIG. 2 is a Transmission Electron Micrograph (TEM) of manganese carbonate A; FIG. 3 is an X-ray diffraction pattern (XRD) of manganese carbonate; FIG. 4 shows manganese carbonate at 100mAg-1A charge and discharge performance map of (1); FIG. 5 shows manganese carbonate at 500mAg-1The charge and discharge performance of (1).
Example 2
Completely dissolving 3.16g of potassium permanganate in 25mL of deionized water to form a potassium permanganate aqueous solution; 1.55g of L-histidine, 0.91g of tyrosine and 2g of glucose were completely dissolved in 25mL of deionized water to form a mixed amino acid aqueous solution. Then adding the amino acid aqueous solution into the potassium permanganate aqueous solution while stirring, and stirring for 30min until the mixture is completely mixed and stirred uniformly. And simultaneously carrying out ultrasonic dispersion, and controlling the power to be 100W. Transferring the uniform solution into a polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a 180 ℃ oven, keeping the temperature for 15 hours, naturally cooling along with the temperature of the oven, and taking out the hydrothermal reaction kettle. And washing the reaction product with deionized water for many times, carrying out vacuum filtration until the pH value of the filtrate is 7, and then putting the filtrate into a vacuum drying oven at 65 ℃ for heating and drying for 12 hours to obtain the nitrogen-doped manganese carbonate/carbon composite material (see figure 6). The prepared manganese carbonate assembled battery is tested for performance when the performance is 100mAg-1The discharge performance can reach 610 mAh g after 100 circles of testing-1And when the current is increased to 500mAg-1The discharge performance can reach 345 mAh g-1。
Example 3
Dissolving 1.51g of manganese sulfate and 2.51g of manganese nitrate in 25mL of deionized water to form a manganese sulfate aqueous solution; 0.75g glycine and 1.96g leucine were completely dissolved in 25mL deionized water to form glycineAn aqueous solution. And then adding the mixed amino acid aqueous solution into a manganese sulfate aqueous solution while stirring, and stirring for 30min until the mixture is completely mixed and uniformly stirred. And simultaneously carrying out ultrasonic dispersion, and controlling the power to be 100W. Transferring the uniform solution into a polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a 200 ℃ oven, keeping the temperature for 10 hours, naturally cooling along with the temperature of the oven, and taking out the hydrothermal reaction kettle. And washing the reaction product with deionized water for many times, carrying out vacuum filtration until the pH value of the filtrate is 7, and then putting the filtrate into a vacuum drying oven at 70 ℃ for heating and drying for 10 hours to obtain the nitrogen-doped manganese carbonate powder. Then, the prepared manganese carbonate powder and graphene solution are self-assembled to prepare the nitrogen-doped manganese carbonate/carbon nanotube composite material (see figure 7), and the prepared material is matched with a lithium ion battery to test the performance of the lithium ion battery, when the performance is 100mAg-1The discharge performance can reach 620 mAh g when 100 circles of discharge are tested-1And when the current is increased to 500mAg-1The discharge performance can reach 360 mAh g-1。
Claims (2)
1. The preparation method of the nitrogen-doped manganese carbonate is characterized by comprising the following steps of:
gradually dropwise adding a hydrophilic amino acid aqueous solution into a manganese salt aqueous solution, stirring to form a uniform solution, transferring the solution into a reaction kettle, controlling the temperature to be 2-8 ℃/min, heating to 120-220 ℃, carrying out a hydrothermal reaction at a constant temperature, cooling to room temperature along with the furnace temperature, filtering, washing and drying to obtain nitrogen-doped manganese carbonate;
the manganese salt is one or a mixture of any one of potassium permanganate, manganese sulfate and manganese nitrate;
the hydrophilic amino acid is one or a mixture of any more of glycine, L-histidine, leucine and leucine;
the stirring time is 20-60 minutes, and ultrasonic treatment is carried out simultaneously; the constant temperature time is 5-20 hours;
the drying method is freeze drying or vacuum drying, wherein the freeze drying temperature is-50 to-5 ℃, and the vacuum drying temperature is 50 to 120 ℃.
2. A preparation method of a manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nanotube compound is characterized by comprising the following steps: the method for preparing manganese carbonate of claim 1, wherein glucose, graphene and carbon nanotubes are added in the step of preparing manganese carbonate, so as to prepare manganese carbonate/carbon, manganese carbonate/graphene and manganese carbonate/carbon nanotube complexes in situ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711137136.7A CN107910525B (en) | 2017-11-16 | 2017-11-16 | Preparation method of nitrogen-doped manganese carbonate and compound thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711137136.7A CN107910525B (en) | 2017-11-16 | 2017-11-16 | Preparation method of nitrogen-doped manganese carbonate and compound thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107910525A CN107910525A (en) | 2018-04-13 |
| CN107910525B true CN107910525B (en) | 2021-01-08 |
Family
ID=61845706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711137136.7A Active CN107910525B (en) | 2017-11-16 | 2017-11-16 | Preparation method of nitrogen-doped manganese carbonate and compound thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107910525B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867564B (en) * | 2018-08-28 | 2021-03-26 | 南京理工大学 | Preparation method of surface-porous manganese carbonate cubic/graphene composite material |
| CN110038557B (en) * | 2019-05-20 | 2022-02-11 | 中国科学院海洋研究所 | Electrocatalysis GOx/MnCO3Composite material, preparation and application thereof |
| CN112661189A (en) * | 2020-12-25 | 2021-04-16 | 陕西科技大学 | Manganese carbonate nano material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013527B (en) * | 2009-09-08 | 2012-08-29 | 清华大学深圳研究生院 | Rechargeable zinc ion battery |
| CN102757096B (en) * | 2012-07-09 | 2014-01-08 | 南京理工大学 | Nanometer manganese carbonate/graphene hydrogel complex and preparation method thereof |
| CN104150473A (en) * | 2014-08-04 | 2014-11-19 | 江苏大学 | Chemical preparation method for nitrogen-doped graphene quantum dot |
| CN105826522B (en) * | 2016-05-18 | 2018-02-02 | 山东大学 | A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate |
| CN106947476B (en) * | 2017-04-03 | 2020-06-05 | 桂林理工大学 | Nitrogen-doped fluorescent graphene quantum dot and preparation method thereof |
-
2017
- 2017-11-16 CN CN201711137136.7A patent/CN107910525B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107910525A (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6172818B2 (en) | Method for producing graphene-based LiFePO4 / C composite material | |
| Zhang et al. | Templated formation of porous Mn2O3 octahedra from Mn-MIL-100 for lithium-ion battery anode materials | |
| CN106848236B (en) | A kind of ferrous sulfate sodium/grapheme composite positive electrode material and preparation method thereof for sodium-ion battery | |
| CN109037625B (en) | Composite material of hierarchical porous carbon and cobalt sulfide, and preparation method and application thereof | |
| CN111106335B (en) | Preparation method of lithium ion battery composite negative electrode material | |
| CN111377426B (en) | Preparation method of anhydrous iron phosphate nanoparticles | |
| CN110364372B (en) | Nickel vanadate material for supercapacitor, and preparation method and application thereof | |
| CN107910525B (en) | Preparation method of nitrogen-doped manganese carbonate and compound thereof | |
| CN104332629B (en) | The preparation method of a kind of lithium manganese phosphate hollow nanospheres and product | |
| Pal et al. | Morphology-mediated tailoring of the performance of porous nanostructured Mn 2 O 3 as an anode material | |
| Ghiyasiyan-Arani et al. | Synergic and coupling effect between SnO 2 nanoparticles and hierarchical AlV 3 O 9 microspheres toward emerging electrode materials for lithium-ion battery devices | |
| CN106058249A (en) | Method for preparing carbon coated nano rodlike sodium ferrous phosphate material by solvent thermal | |
| CN104993116B (en) | A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method | |
| CN111384366B (en) | alpha-MnO 2 Carbon/carbon composite electrode material and preparation method and application thereof | |
| CN112357956B (en) | Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof | |
| Wang et al. | Enhanced cyclic performance of Cu2V2O7/reduced Graphene Oxide mesoporous microspheres assembled by nanoparticles as anode for Li-ion battery | |
| Chen et al. | Synthesis of K0. 25V2O5 hierarchical microspheres as a high-rate and long-cycle cathode for lithium metal batteries | |
| CN112768656A (en) | Carbon-coated mesoporous transition metal sulfide negative electrode material and preparation method and application thereof | |
| Zhao et al. | Facile fabrication of hollow CuO nanocubes for enhanced lithium/sodium storage performance | |
| CN103413918A (en) | Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries | |
| CN104085868A (en) | Preparation method of 3D micro/nano-structure spherical active iron phosphate | |
| CN113346055A (en) | Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof | |
| CN111224084B (en) | Lithium iron phosphate/lithium silicate composite material and preparation method and application thereof | |
| CN111916733A (en) | Hollow tetrahedral transition metal sulfide Cu2MoS4Preparation method of lithium battery negative electrode material | |
| CN108275724B (en) | Preparation method of molybdenum trioxide self-assembled nano-particle electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |