CN117361630A - Preparation method and application of nano manganese metastanniate material - Google Patents
Preparation method and application of nano manganese metastanniate material Download PDFInfo
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- CN117361630A CN117361630A CN202311381011.4A CN202311381011A CN117361630A CN 117361630 A CN117361630 A CN 117361630A CN 202311381011 A CN202311381011 A CN 202311381011A CN 117361630 A CN117361630 A CN 117361630A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 34
- 239000011572 manganese Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007790 solid phase Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 229910017034 MnSn Inorganic materials 0.000 description 25
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000012535 impurity Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- YGVVXDZBQRDGIV-UHFFFAOYSA-N dioxido(oxo)tin;manganese(2+) Chemical compound [Mn+2].[O-][Sn]([O-])=O YGVVXDZBQRDGIV-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of battery electrode materials, in particular to a preparation method and application of a nano manganese metastanniate material. The preparation method comprises the following steps: dissolving manganese salt and tin salt in deionized water to obtain a precursor solution; adding an ammonia mineralizer into the precursor solution under the condition of stirring until the pH value of the solution is 10-11 to obtain a mixed solution; after the mixed solution is subjected to hydrothermal reaction, cooling to room temperature, and carrying out solid-liquid separation to obtain a product; calcining the product in nitrogen to obtain the nano manganese metastanniate material. The preparation method has low energy consumption, the obtained product is not easy to agglomerate, has small particle size and uniform distribution, has regular cube morphology, can be used for preparing lithium ion anode materials, and has good cycle performance.
Description
Technical Field
The invention relates to the technical field of battery electrode materials, in particular to a preparation method and application of a nano manganese metastanniate material.
Background
Manganese metastanniate (MnSnO) 3 ) Is a typical transition metal bi-metal oxide. Has the characteristics of low toxicity, low resistance, transparency, relatively good conductivity and the like, and is widely applied to the fields of super capacitance, batteries, catalysis, chemical sensing, electro-catalysis and the like.
Currently, with respect to MnSnO 3 The research report of the preparation method is less, and common preparation methods are a coprecipitation method and a high temperature solid phase reaction method. As disclosed in the prior art, a carbon-coated manganese stannate material having a mesoporous structure as a negative electrode material, wherein MnSnO 3 The preparation method of (2) comprises the following steps: dropwise adding a tin source solution into a manganese source solution, and preparing a precursor material by adopting a solution precipitation method; calcining the precursor material in inert atmosphere to obtain MnSnO 3 A nanoparticle mass. However, the coprecipitation method is easy to cause particle agglomeration, is suitable for preparing substances with low requirements on particle size and morphology, but has uneven particle size distribution and poor morphology of MnSnO 3 In practical application, the performance is limited due to the problems of unstable performance and the like. The high-temperature solid-phase reaction method prepares the target product through chemical reaction between solid substances at high temperature (1000-1500 ℃), and has the problems of high energy consumption, insufficient fineness of powder, easy impurity mixing and the like.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a nano manganese metastanniate material. The preparation method has low energy consumption, the obtained product is not easy to agglomerate, has small particle size and uniform distribution, has regular cube morphology, can be used for preparing lithium ion anode materials, and has good cycle performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a nano manganese metastanniate material, comprising the steps of:
dissolving manganese salt and tin salt in deionized water to obtain a precursor solution;
step two, adding an ammonia mineralizer into the precursor solution under the condition of stirring until the pH value of the solution is 10-11, so as to obtain a mixed solution;
thirdly, performing solid-liquid separation after the hydrothermal reaction of the mixed solution to obtain an intermediate product;
and step four, calcining the intermediate product in nitrogen to obtain the nano manganese metastanniate material.
Compared with the coprecipitation method and the high temperature solid phase method in the prior art, the method adopted by the invention does not need reaction conditions with overhigh temperature, and has low energy consumption; the intermediate product obtained in the third step is MnSn (OH) 6 The precursor, the crystal grain is smaller, the MnSn (OH) 6 The precursor can be further refined into grains after being calcined, and the nano MnSnO with special structure (cube structure), difficult agglomeration, 50-70 nm particle size and uniform particle size distribution is obtained 3 A material. The method avoids the problems that the coprecipitation method in the prior art is easy to cause particle agglomeration, uneven in product particle size distribution and poor in appearance, and the high-temperature solid phase reaction method is high in energy consumption.
In the preparation method, step two, ammonia water mineralizer is added into the precursor solution until the pH value of the solution is between 10 and 11, which is beneficial to improving the obtained MnSnO 3 Purity of the material. When the pH value of the solution is less than 9, the tin salt is easy to hydrolyze, so that the product contains tin oxide impurities; when the pH of the solution is more than 11, manganese oxide is easy to preferentially generate, and the product contains manganese oxide impurities.
Preferably, the manganese salt is MnC 4 H 6 O 4 ·4H 2 O, tin salt is SnCl 4 ·5H 2 O。
Preferably, the MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is (1.5-2): 1.
The above-mentioned moleMnC of molar ratio 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 O is favorable for the full reaction of reactants, and finally the nano MnSnO with pure components is obtained 3 A material.
Preferably, the stirring speed is 500-1000 r/min.
Preferably, the temperature of the hydrothermal reaction is 120-150 ℃, and the reaction time is more than or equal to 12 hours.
The hydrothermal reaction time is not less than 12 hours, which is favorable for the full reaction of reactants, and the reactants possibly cannot react completely when the hydrothermal reaction time is less than 12 hours, and the nano MnSnO is obtained after roasting 3 The material may contain impurities. Further preferably, the reaction time is 12 to 15 hours, and the reaction can be ensured to be complete within the reaction time without excessively prolonging the reaction time so as to avoid wasting energy consumption.
Preferably, the solid-liquid separation includes: cooling to room temperature, centrifuging at 2000-3000rpm for 3-6min, taking solid phase, washing with deionized water for at least 10 times, and drying to obtain the product. The operation method of solid-liquid separation can clean impurity ions such as chloride ions in the product, and is finally beneficial to obtaining nano MnSnO with pure components and cubic structure 3 A material.
Preferably, the calcining comprises: heating to 400-600 ℃ at a heating rate of less than or equal to 5 ℃/min, and calcining for 1-4 h.
The invention increases the temperature slowly at the speed of less than or equal to 5 ℃/min, which is beneficial to the more thorough calcination of the product. When the temperature rising rate is too fast (more than 5 ℃/min), equipment is burst, and the furnace body is damaged.
When the calcination time is less than 1h, the reactant is insufficiently calcined, so that manganese oxide or tin oxide impurities are generated after calcination; when the calcination time is > 4 hours, stannate impurities may be formed.
In a second aspect, the invention also provides a nano manganese metastanniate material prepared by the preparation method.
In a third aspect, the application of the nano manganese metastanniate material in preparation of a lithium ion battery anode material is provided.
The first-cycle charge-discharge specific capacity of the lithium ion battery anode material prepared by the nano manganese metastanniate material with the cubic structure is 549mAh/g and 1027mAh/g respectively, the coulomb efficiency is 53%, the discharge specific capacity still has 291mAh/g after 50 cycles, and the stable coulomb efficiency is maintained to be more than 98%, so that the lithium ion battery anode material has good reversible capacity and cycle stability.
Drawings
FIG. 1 shows nano MnSnO of example 1 of the present invention 3 Scanning electron microscope images of materials;
FIG. 2 shows nano MnSnO of example 1 of the present invention 3 An X-ray diffraction pattern of the material;
FIG. 3 shows MnSn (OH) in examples 1, 2 and 1 of the present invention 6 An X-ray diffraction pattern of the precursor;
FIG. 4 shows MnSn (OH) in examples 1 and 3 of the present invention 6 An X-ray diffraction pattern of the precursor;
FIG. 5 shows MnSn (OH) in examples 1, 4 and 2 of the present invention 6 An X-ray diffraction pattern of the precursor;
FIG. 6 shows MnSn (OH) in examples 1, 5 and 3 of the present invention 6 An X-ray diffraction pattern of the precursor;
fig. 7 is a constant current charge-discharge cycle performance curve of the battery 1 assembled as the negative electrode material of the lithium ion battery of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides a preparation method of a nano manganese metastanniate material; the method comprises the following steps:
step one, accurately weighing 91.9mg of MnC respectively 4 H 6 O 4 ·4H 2 O and 87.5mg of SnCl 4 ·5H 2 O was added to 50mL of deionized water and stirred at 1000r/minDissolving to obtain a precursor solution, wherein MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is 1.5:1;
dropwise adding an ammonia mineralizer into the precursor solution under the condition of continuous stirring until the pH value of the solution reaches 10, so as to obtain a mixed solution;
transferring the mixed solution into a 100ml high-pressure reaction kettle, performing hydrothermal reaction at 150 ℃ for 15 hours, cooling to room temperature, centrifuging at 3000rpm for 3 minutes, taking a solid phase, washing with deionized water for 10 times, and drying at 80 ℃ to obtain a product (MnSn (OH) 6 A precursor;
and fourthly, heating the product to 400 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and calcining for 2 hours to obtain the nano manganese metastanniate material.
FIG. 1 shows nano MnSnO of example 1 of the present invention 3 Scanning electron microscope images of materials;
from FIG. 1, it can be seen that nano MnSnO 3 The particles have a cubic structure, the particle size is 50-70 nm, the particle size is uniform and dispersed uniformly, and the phenomenon of particle agglomeration does not exist.
FIG. 2 shows nano MnSnO of example 1 of the present invention 3 An X-ray diffraction pattern of the material;
as shown in FIG. 2, nano MnSnO prepared in example 1 3 The material product is pure and contains no impurity.
Example 2
The embodiment of the invention provides a preparation method of a nano manganese metastanniate material; the method comprises the following steps:
step one, accurately weighing 122.5mg of MnC respectively 4 H 6 O 4 ·4H 2 O and 87.5mg SnCl 4 ·5H 2 O is added into 50mL of deionized water and stirred and dissolved at 800r/min to obtain precursor solution, wherein MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is 2:1;
dropwise adding an ammonia mineralizer into the precursor solution under the condition of continuous stirring until the pH value of the solution reaches 10, so as to obtain a mixed solution;
transferring the mixed solution into a 100ml high-pressure reaction kettle, performing hydrothermal reaction at 150 ℃ for 15 hours, cooling to room temperature, centrifuging at 2500rpm for 4 minutes, taking a solid phase, washing the solid phase with deionized water for at least 10 times, and drying at 80 ℃ to obtain a product (MnSn (OH) 6 A precursor;
and fourthly, heating the product to 400 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere, and calcining for 2 hours to obtain the nano manganese metastanniate material.
Example 3
The embodiment of the invention provides a preparation method of a nano manganese metastanniate material; the method comprises the following steps:
step one, accurately weighing 91.9mg of MnC respectively 4 H 6 O 4 ·4H 2 O and 87.5mg of SnCl 4 ·5H 2 O is added into 50mL of deionized water and stirred and dissolved at 1000r/min to obtain precursor solution, wherein MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is 1.5:1;
dropwise adding an ammonia mineralizer into the precursor solution under the condition of continuous stirring until the pH value of the solution reaches 10, so as to obtain a mixed solution;
transferring the mixed solution into a 100ml high-pressure reaction kettle, performing hydrothermal reaction at 120 ℃ for 15 hours, cooling to room temperature, centrifuging at 3000rpm for 3 minutes, taking a solid phase, washing the solid phase with deionized water for at least 10 times, and drying at 80 ℃ to obtain a product (MnSn (OH) 6 A precursor;
and fourthly, heating the product to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and calcining for 2 hours to obtain the nano manganese metastanniate material.
Example 4
The embodiment of the invention provides a preparation method of a nano manganese metastanniate material; the method comprises the following steps:
step one, accurately weighing 91.9mg of MnC respectively 4 H 6 O 4 ·4H 2 O and 87.5mg of SnCl 4 ·5H 2 O50 mL of deionized water was addedDissolving in water under stirring at 1000r/min to obtain precursor solution, wherein MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is 1.5:1;
dropwise adding an ammonia mineralizer into the precursor solution under the condition of continuous stirring until the pH value of the solution reaches 11 to obtain a mixed solution;
transferring the mixed solution into a 100ml high-pressure reaction kettle, performing hydrothermal reaction at 150 ℃ for 15 hours, cooling to room temperature, centrifuging at 3000rpm for 3 minutes, taking a solid phase, washing the solid phase with deionized water for at least 10 times, and drying at 80 ℃ to obtain a product (MnSn (OH) 6 A precursor;
and fourthly, heating the product to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and calcining for 2 hours to obtain the nano manganese metastanniate material.
Example 5
The embodiment of the invention provides a preparation method of a nano manganese metastanniate material, which comprises the following steps:
step one, accurately weighing 91.9mg of MnC respectively 4 H 6 O 4 ·4H 2 O and 87.5mg of SnCl 4 ·5H 2 O is added into 50mL of deionized water and stirred and dissolved at 1000r/min to obtain precursor solution, wherein MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is 1.5:1;
dropwise adding an ammonia mineralizer into the precursor solution under the condition of continuous stirring until the pH value of the solution reaches 10, so as to obtain a mixed solution;
transferring the mixed solution into a 100ml high-pressure reaction kettle, performing hydrothermal reaction at 150 ℃ for 12 hours, cooling to room temperature, centrifuging at 3000rpm for 3 minutes, taking a solid phase, washing the solid phase with deionized water for at least 10 times, and drying at 80 ℃ to obtain a product (MnSn (OH) 6 A precursor;
and fourthly, heating the product to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and calcining for 2 hours to obtain the nano manganese metastanniate material.
Comparative example 1
The differences from example 1 are: mnC (MnC) 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O was 1:1, the remainder being the same as in example 1.
Comparative example 2
The differences from example 1 are: the pH was adjusted to 9, and the rest was the same as in example 1.
Comparative example 3
The differences from example 1 are: the hydrothermal reaction time was 9h, and the rest was the same as in example 1.
Verification example 1
1. The products prepared before high temperature calcination of examples 1-2 and comparative example 1: mnSn (OH) 6 The precursor was subjected to X-ray diffraction analysis, and the results are shown in fig. 3.
FIG. 3 shows MnSn (OH) in examples 1, 2 and 1 of the present invention 6 An X-ray diffraction pattern of the precursor;
as can be seen from FIG. 3, the products of examples 1 and 2 are both MnSn (OH) having a pure composition 6 The main product of comparative example 1 is MnSn (OH) 6 But impurities are present.
2. MnSn (OH) before high temperature section firing prepared in example 1 and example 3 at different hydrothermal reaction temperatures 6 The precursor was subjected to X-ray diffraction analysis, and the results are shown in fig. 4.
FIG. 4 shows MnSn (OH) in examples 1 and 3 of the present invention 6 An X-ray diffraction pattern of the precursor; as can be seen from FIG. 4, the products of examples 1 and 3 before high temperature calcination, which were prepared at different hydrothermal reaction temperatures, were MnSn (OH) 6 。
3. The high temperature calcined MnSn (OH) 6 precursors prepared at different pH of example 1, example 4 and comparative example 2 were subjected to X-ray diffraction analysis, and the results are shown in fig. 5.
FIG. 5 shows MnSn (OH) in examples 1, 4 and 2 of the present invention 6 An X-ray diffraction pattern of the precursor; as can be seen from FIG. 5, the products of examples 1 and 4 are MnSn (OH) 6 The main product of comparative example 2 is MnSn (OH) 6 But impurities are present.
4. The high temperature pre-calcined MnSn (OH) 6 precursors prepared at different hydrothermal reaction times for example 1, example 5 and comparative example 3 were subjected to X-ray diffraction analysis, and the results are shown in fig. 6.
FIG. 6 shows MnSn (OH) in examples 1, 5 and 3 of the present invention 6 An X-ray diffraction pattern of the precursor; as can be seen from FIG. 6, the products of examples 1 and 5 are MnSn (OH) 6 The main product of comparative example 3 is MnSn (OH) 6 But impurities are present.
Application example 1
The invention also provides an application of the nano manganese metastanniate material with the cube structure obtained by the preparation method in the preparation of the lithium ion battery anode material, which comprises the following specific steps:
nano MnSnO prepared in example 1 3 Grinding the material in an agate mortar for 30min, and grinding the ground nano MnSnO according to the mass ratio of 7:2:1 3 Mixing the material, the conductive agent acetylene black and the binder PVDF, vacuum drying at 80 ℃ overnight, preparing pasty slurry, coating the pasty slurry on foam nickel, vacuum drying overnight, tabletting and obtaining the lithium ion battery negative plate.
MnSnO obtained in example 1 3 The nano cube material is prepared into a lithium ion battery negative plate which is marked as a lithium ion battery negative plate 1.
And assembling the lithium ion battery negative electrode sheet 1, the positive electrode sheet and the lithium sheet in a glove box filled with argon to obtain the CR2032 button battery 1. The electrolyte used was LiPF 6 As solutes, a separator Celgard 2400 was used with a volume ratio of 1:1:1 of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) as solvents.
The assembled button cell 1 is subjected to performance test, and a cell system is adopted to test the charge and discharge cycle performance of the cell under constant current, wherein the charge and discharge voltage range is 0.01-3.0V. The test results are shown in fig. 7.
Fig. 7 is a constant current charge-discharge cycle performance curve of the battery 1 assembled as the negative electrode material of the lithium ion battery of example 1; as can be seen from fig. 7, the battery 1 has a charge-discharge cycle performance at a constant current of 100mA/g, the first charge-discharge specific capacity is 549mAh/g and 1027mAh/g, respectively, the coulomb efficiency is 53%, after 50 cycles, the discharge specific capacity still has 291mAh/g, and the stable coulomb efficiency is maintained at 98% or more.
Thus, nano MnSnO having a cubic structure prepared in example 1 is illustrated 3 The lithium battery assembled by the materials has higher specific capacity and better circularity.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The preparation method of the nano manganese metastanniate material is characterized by comprising the following steps of:
dissolving manganese salt and tin salt in deionized water to obtain a precursor solution;
step two, adding an ammonia mineralizer into the precursor solution under the condition of stirring until the pH value of the solution is 10-11, so as to obtain a mixed solution;
thirdly, performing solid-liquid separation after the hydrothermal reaction of the mixed solution to obtain an intermediate product;
and step four, calcining the intermediate product in nitrogen to obtain the nano manganese metastanniate material.
2. The method for preparing nano manganese metastanniate material according to claim 1, wherein the manganese salt is MnC 4 H 6 O 4 ·4H 2 O, tin salt is SnCl 4 ·5H 2 O。
3. The method for preparing a nano manganese metastannate material according to claim 2, wherein the MnC 4 H 6 O 4 ·4H 2 O and SnCl 4 ·5H 2 The molar ratio of O is (1.5-2): 1.
4. The method for preparing a nano manganese metastannate material according to claim 1, wherein the stirring rate is 500-1000 r/min.
5. The method for preparing the nano manganese metastannate material according to claim 1, wherein the temperature of the hydrothermal reaction is 120-150 ℃ and the reaction time is more than or equal to 12h.
6. The method for preparing a nano manganese metastannate material according to claim 1, wherein the solid-liquid separation comprises: cooling to room temperature, centrifuging at 2000-3000rpm for 3-6min, taking solid phase, washing with deionized water for at least 10 times, and drying to obtain the product.
7. The method of preparing a nano manganese metastannate material according to claim 1, wherein the calcining comprises: heating to 400-600 ℃ at a heating rate of less than or equal to 5 ℃/min, and calcining for 1-4 h.
8. A nano manganese metastannate material prepared by the method of any one of claims 1 to 7.
9. The use of the nano manganese metastannate material of claim 8 in the preparation of negative electrode materials of lithium ion batteries.
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