CN107459063B - A kind of manganese molybdate micro Nano material and its preparation method and application - Google Patents

A kind of manganese molybdate micro Nano material and its preparation method and application Download PDF

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CN107459063B
CN107459063B CN201710614329.0A CN201710614329A CN107459063B CN 107459063 B CN107459063 B CN 107459063B CN 201710614329 A CN201710614329 A CN 201710614329A CN 107459063 B CN107459063 B CN 107459063B
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manganese
micro nano
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nano material
mixed solution
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CN107459063A (en
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张利锋
神克超
贺文杰
刘毅
郭守武
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Beijing Yongbo Technology Co ltd
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Shaanxi University of Science and Technology
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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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a kind of manganese molybdate micro Nano materials and its preparation method and application, specific step is as follows: after ten minutes by the stirring of the ethyl alcohol or ethylene glycol solution of four water acetic acid manganese and Sodium Molybdate Dihydrate, it moves in reaction kettle, sealing, it is reacted 3~6 hours under the conditions of 120~180 DEG C of temperature, it collects product and calcines a few hours under air or argon atmosphere, obtain the manganese molybdate micro Nano material of different-shape.The preparation method is easy to operate, reaction condition is general, it is at low cost, it can be directly used for industrial-scale production, the manganese molybdate micro Nano material pattern of preparation is special, crystallinity is preferable, there is excellent electro-chemical activity as lithium ion battery electrode material, provide theoretical basis and practical experience for the controllable preparation and its electrochemical applications of such material.

Description

A kind of manganese molybdate micro Nano material and its preparation method and application
[technical field]
The invention belongs to inorganic micro Nano material preparation field, it is related to a kind of manganese molybdate micro Nano material and preparation method thereof And application.
[background technique]
Recently as the rapid development of science and technology, people increase the demand of the energy year by year, conventional fossil energy by It is increasingly exhausted in immoderate use, while with serious environmental problem, therefore sight is turned to novel green energy by people Source.Lithium ion battery has been widely used in portable electronic product, electric vehicle, boat as a kind of efficient green energy The fields such as empty space flight and defence equipment.Negative electrode material is the important component of lithium battery, determines the performance of lithium battery.Quotient For the negative electrode material of industry mostly based on graphite, the theoretical specific capacity of graphite is relatively low, it is difficult to meet market to high-capacity battery Demand, therefore force people develop height ratio capacity electrode material.
Molybdate (MMoO4) it is bimetallic oxygen hydrochlorate, theoretical specific capacity with higher and good chemical property, quilt It is considered ideal lithium cell negative pole material.Manganese molybdate is widely studied in recent years as the Typical Representative of molybdate.As in State patent CN201110347430.7 discloses the preparation method that nanometer sheet is assembled into the molybdic acid manganese material of micron bar structure；China Patent CN201110048928.3 discloses the preparation method of manganese molybdate cobalt molybdate hierarchical heterostructure line；Chinese patent CN20110347506.6 discloses the preparation method of manganese molybdate nanospheres regular in shape；Chinese patent CN201210012024.X Disclose the preparation method of manganese molybdate microcrystal.
Above-mentioned preparation method step complexity, high production cost, uses a large amount of surfactant dirty at severe reaction conditions Contaminate environment.The present invention provides a kind of method of controllable preparation manganese molybdate micro-nano electrode material, this method simple processes, environment It is friendly, raw materials used be easy to get, production cost is low, is easy to the advantages that being mass produced.By adjusting experiment parameter, can prepare The manganese molybdate micro nano structure of different-shape.
[summary of the invention]
It is an object of the invention to solve above-mentioned the problems of the prior art, provide a kind of manganese molybdate micro Nano material and its Preparation method and application can synthesize the molybdic acid of specific morphology by adjusting experiment parameter using solvent heat-calcining method Manganese.This method simple process, it is environmental-friendly, raw materials used be easy to get, production cost is low, is easy to be mass produced.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of preparation method of manganese molybdate micro Nano material, comprising the following steps:
1) four water acetic acid manganese are dissolved in ethyl alcohol or ethylene glycol under stiring, obtain mixed solution A；
2) Sodium Molybdate Dihydrate is dissolved in ethyl alcohol or ethylene glycol under stiring, obtains mixed solution B；
3) it is 1:(1~2 according to volume ratio by mixed solution A and mixed solution B) after mixing 15 minutes, move to reaction In kettle, sealing；120~180 DEG C at a temperature of sufficiently react, then filtered, washed, is dry；
4) temperature lower calcination by the product of step 3) at 400~700 DEG C obtains the molybdenum of different-shape after being cooled to room temperature Sour manganese micro Nano material.
A further improvement of the present invention lies in that:
In step 1), the concentration of four water acetic acid manganese is 0.05~1 mol/L.
In step 2), the concentration of Sodium Molybdate Dihydrate is 0.05~1 mol/L.
In step 3), the reaction time is 3~6 hours.
In step 4), calcination time is 3~6 hours.
A kind of manganese molybdate micro Nano material, the specific discharge capacity of prepared manganese molybdate micro Nano material are 942.2mAh g-1, charge specific capacity is 710.9mAh g-1。
Application of the manganese molybdate micro Nano material as electrode material.
Compared with prior art, the invention has the following advantages:
The present invention has synthesized purity is high using conventional manganese salt, molybdate as raw material, by solvent heat and calcining two-step method, ties Brilliant degree is high, morphology controllable manganese molybdate micro nano structure, the preparation method is simple to operation, it is repeatable it is strong, at low cost, be easy to Industrialized production.Fig. 3 is charging and discharging curve of the prepared manganese molybdate at 0.1mA/g, specific discharge capacity and charging specific volume Amount is respectively 942.2mAh g-1, 710.9mAh g-1, illustrate that prepared manganese molybdate has preferable electro-chemical activity.
[Detailed description of the invention]
Fig. 1 is the scanning electron microscope (SEM) photograph of prepared manganese molybdate；
Fig. 2 is the XRD diagram of prepared manganese molybdate；
Fig. 3 is the charging and discharging curve of prepared manganese molybdate.
[specific embodiment]
The method that controllable preparation manganese molybdate micro-nano electrode material is further described with reference to the accompanying drawings and examples, The microstructure and performance of product:
Embodiment 1:
Four water acetic acid manganese are dissolved in ethyl alcohol under agitation and are configured to 0.05 mol/L, are denoted as mixed solution A；
Sodium Molybdate Dihydrate is dissolved in ethyl alcohol under agitation and is configured to 0.05 mol/L, is denoted as mixed solution B；
Mixed solution A and mixed solution B (volume ratio 1:0.5) are mixed after ten minutes, moved in reaction kettle, it is close Envelope, 140 DEG C thermotonus 3 hours, then filtered, washed, dry；
The product of step 3) is calcined 5 hours under certain 400 DEG C of argon gas, the molybdenum of different-shape is obtained after being cooled to room temperature Sour manganese micro Nano material.
Embodiment 2:
1) four water acetic acid manganese are dissolved in ethyl alcohol under agitation and are configured to 0.2 mol/L, are denoted as mixed solution A；
2) Sodium Molybdate Dihydrate is dissolved in ethyl alcohol under agitation and is configured to 0.05 mol/L, is denoted as mixed solution B；
3) mixed solution A and mixed solution B (volume ratio 1:1) are mixed after ten minutes, are moved in reaction kettle, it is close Envelope reacts a few hours in certain temperature, is then filtered, washed, is dry；
4) product of step 3) is calcined 6 hours under certain 500 DEG C of argon gas, obtains different-shape after being cooled to room temperature Manganese molybdate micro Nano material.
Embodiment 3:
1) four water acetic acid manganese are dissolved in ethylene glycol under agitation and are configured to 0.2 mol/L, are denoted as mixed solution A；
2) Sodium Molybdate Dihydrate is dissolved in ethylene glycol under agitation and is configured to 0.05 mol/L, is denoted as mixed solution B；
3) mixed solution A and mixed solution B (volume ratio 1:1) are mixed after ten minutes, are moved in reaction kettle, it is close Envelope reacts a few hours in certain temperature, is then filtered, washed, is dry；
4) product of step 3) is calcined 6 hours under certain 500 DEG C of argon gas, obtains different-shape after being cooled to room temperature Manganese molybdate micro Nano material.
Embodiment 4:
1) four water acetic acid manganese are dissolved in ethylene glycol under agitation and are configured to 0.2 mol/L, are denoted as mixed solution A；
2) Sodium Molybdate Dihydrate is dissolved in ethylene glycol under agitation and is configured to 0.05 mol/L, is denoted as mixed solution B；
3) mixed solution A and mixed solution B (volume ratio 1:1) are mixed after ten minutes, are moved in reaction kettle, it is close Envelope reacts a few hours in certain temperature, is then filtered, washed, is dry；
4) product of step 3) is calcined 4 hours under certain 600 DEG C of air, obtains different-shape after being cooled to room temperature Manganese molybdate micro Nano material.
Embodiment 5:
1) four water acetic acid manganese are dissolved in ethylene glycol under agitation and are configured to 0.8 mol/L, are denoted as mixed solution A；
2) Sodium Molybdate Dihydrate is dissolved in ethyl alcohol under agitation and is configured to 0.8 mol/L, is denoted as mixed solution B；
3) mixed solution A and mixed solution B (volume ratio 1:1.5) are mixed after ten minutes, are moved in reaction kettle, Sealing reacts a few hours in certain temperature, is then filtered, washed, is dry；
4) product of step 3) is calcined 6 hours under certain 700 DEG C of argon gas, obtains different-shape after being cooled to room temperature Manganese molybdate micro Nano material.
Fig. 1 is the scanning electron microscope diagram of manganese molybdate prepared by the present embodiment, and product is in silk cocoon shape, mainly small by nanometer Particle and Filamentous manganese molybdate composition.Fig. 2 is the XRD diagram of prepared manganese molybdate.Fig. 3 is prepared manganese molybdate at 0.1mA/g Charging and discharging curve, specific discharge capacity and charge specific capacity are respectively 942.2mAh g-1, 710.9mAh g-1, illustrate made Standby manganese molybdate has preferable electro-chemical activity.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention Protection scope within.

Claims (1)

1. a kind of manganese molybdate micro Nano material, is prepared as follows:
1) the four water acetic acid manganese that concentration is 0.05~1 mol/L are dissolved in ethyl alcohol or ethylene glycol under stiring, obtain mixed solution A；
2) Sodium Molybdate Dihydrate that concentration is 0.05~1 mol/L is dissolved in ethyl alcohol or ethylene glycol under stiring, obtains mixed solution B；
3) it is 1:(1~2 according to volume ratio by mixed solution A and mixed solution B) after mixing 15 minutes, move to reaction kettle In, sealing；120~180 DEG C at a temperature of sufficiently react, the reaction time be 3 hours, then filtered, washed, dry；
4) temperature lower calcination by the product of step 3) at 400~700 DEG C, calcination time are 4~6 hours, after being cooled to room temperature Obtain manganese molybdate micro Nano material；
It is characterized in that, prepared manganese molybdate micro Nano material is in silk cocoon shape, mainly by nanometer little particle and Filamentous manganese molybdate Composition, specific discharge capacity are 942.2mAh g-1, charge specific capacity is 710.9mAh g-1。
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CN108251862A (en) * 2018-01-31 2018-07-06 中国科学院合肥物质科学研究院 A kind of manganese molybdate nanometer sheet material and preparation method and application
CN110137473B (en) * 2019-05-22 2021-08-27 安徽师范大学 Composite material for growing nickel cobaltate nanowire array on micron disk, preparation method and application thereof
CN113880142B (en) * 2021-11-01 2023-03-24 陕西科技大学 MnMoO 4 Micro-nano material and preparation method thereof
CN115621435A (en) * 2022-09-22 2023-01-17 厦门大学 Lithium-sulfur battery positive host material based on manganese sulfide-molybdenum disulfide heterojunction and preparation method and application thereof

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