CN102437324B - Preparation method of cobalt-manganese composite oxide nanoparticles and cobalt-manganese composite oxide nanoparticles prepared by adopting same - Google Patents
Preparation method of cobalt-manganese composite oxide nanoparticles and cobalt-manganese composite oxide nanoparticles prepared by adopting same Download PDFInfo
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- CN102437324B CN102437324B CN201110412563.8A CN201110412563A CN102437324B CN 102437324 B CN102437324 B CN 102437324B CN 201110412563 A CN201110412563 A CN 201110412563A CN 102437324 B CN102437324 B CN 102437324B
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- cobalt
- composite oxide
- manganese composite
- nano particle
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- 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
Abstract
The invention provides a preparation method of cobalt-manganese composite oxide nanoparticles and the application of the cobalt-manganese composite oxide nanoparticles prepared by adopting the method in a lithium ion battery. The corresponding method comprises the steps that a predetermined amount of manganese acetate and polyvinylpyrrolidone are dissolved in water and an ethanol solution, and a manganese acetate and polyvinylpyrrolidone solution is obtained; under a predetermined temperature condition, a cobalt potassium cyanate solution is dropwise added into the manganese acetate and polyvinylpyrrolidone solution, is magnetically stirred and then stands still for predetermined time, and cobalt cyanic acid radical complex nanoparticles are obtained through centrifugal separation; and the dried cobalt cyanic acid radical complex nanoparticles are calcined in air for predetermined time at a calcination temperature of 400 DEG C, and the cobalt-manganese composite oxide nanoparticles are obtained after the calcination. According to the preparation method, higher temperature and longer reaction time are not needed, the shapes and the structures of the particles are easy to control, the manufacturing process is relatively simple, the requirement for equipment is not high, and large-scale popularization and application can be realized.
Description
Technical field
The invention belongs to nano material preparing technical field, the cobalt manganese composite oxide nano particle that particularly prepared by a kind of preparation method of cobalt manganese composite oxide nano particle and the method.
Background technology
Cobalt manganese composite oxide is a kind of new material with extensive use, because it contains two kinds of different metal ions and has special spinel type crystal structure, therefore at aspects such as magnetics, electronics, catalysis, Conversion of Energy and storages, there is great application prospect.In the prior art, by using sol-gel process to heat, within 24 hours, prepared MnCo at 800 ℃
2o
4material, and this material is when as lithium ion battery negative material, after 50 circulations, still has 450mAh g
-1capacity, shown good performance; In the prior art, can also be by using liquid phase synthesizing method at room temperature to synthesize the CoMn with good electrical catalytic performance
2o
4nanocrystal.In order to prepare in large quantity cobalt manganese composite oxide, need to be a kind of safe, simple, efficient, be easy to control the method for product pattern and size simultaneously.But the method for preparing at present cobalt manganese composite oxide is mainly confined to high temperature solid-state method and sol-gal process, these methods all need higher temperature and longer reaction time, and pattern and the structure of particle are not easy controlled simultaneously.In addition the method for preparing under some room temperatures, the reagent dangerous because needs are used is (as NaBH
4) or complicated preparation technology, be also difficult to obtain spread and commercial application.
Summary of the invention
The invention provides a kind of preparation method of cobalt manganese composite oxide nano particle and cobalt manganese composite oxide nano particle prepared by the method, the problem that is not easy control, complicated process of preparation, is difficult to large-scale promotion application for solving pattern and the structure of temperature that needs that the preparation method of existing cobalt manganese composite oxide exists are higher and longer reaction time, particle.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for cobalt manganese composite oxide nano particle, comprising:
By in the manganese acetate of scheduled volume and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidonesolution solution;
Under predetermined temperature, cobalt potassium cyanate solution is added drop-wise in described cobalt acetate and polyvinylpyrrolidonesolution solution, the standing scheduled time after magnetic agitation, by centrifugation, obtaining cobalt cyanate radical complex nano particle;
Dried described cobalt cyanate radical complex nano particle is calcined the scheduled time in air, and calcining heat is 400 ℃, obtains cobalt manganese composite oxide nano particle after calcining.
A cobalt manganese composite oxide nano particle, described cobalt manganese composite oxide nano particle has loose structure, and particle diameter is 180～220nm, and specific surface is 125～130m
2/ g, pore-size distribution is 5～10nm.
Beneficial effect of the present invention: without higher temperature and longer reaction time, pattern and the structure of particle are easily controlled, and manufacturing process is fairly simple, not high to equipment requirement, can realize large-scale promotion and application.
Accompanying drawing explanation
The preparation method's of the cobalt manganese composite oxide nano particle that Fig. 1 provides for the specific embodiment of the present invention schematic flow sheet;
Fig. 2 is the X-ray diffractogram of cobalt cyanic acid manganese in embodiments of the invention 1;
Fig. 3 is the stereoscan photograph of cobalt cyanic acid manganese in embodiments of the invention 1;
Fig. 4 is the transmission electron microscope photo of cobalt cyanic acid manganese in embodiments of the invention 1;
Fig. 5 is the X-ray diffractogram of cobalt manganese composite oxide nano particle in embodiments of the invention 2;
Fig. 6 is scanning and the transmission electron microscope photo of cobalt manganese composite oxide nano particle in embodiments of the invention 2;
Fig. 7 is the nitrogen adsorption curve of cobalt manganese composite oxide nano particle in embodiments of the invention 2;
Fig. 8 is charge/discharge capacity and the cycle-index curve of test battery in embodiments of the invention 3.
Embodiment
This embodiment provides a kind of preparation method of cobalt manganese composite oxide nano particle and cobalt manganese composite oxide nano particle prepared by the method, and as shown in Figure 1, corresponding preparation method comprises:
Step 1, by the manganese acetate of scheduled volume and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtains manganese acetate and polyvinylpyrrolidonesolution solution;
Step 2, under predetermined temperature, is added drop-wise to cobalt potassium cyanate solution in described cobalt acetate and polyvinylpyrrolidonesolution solution, the standing scheduled time after magnetic agitation, is obtaining cobalt cyanate radical complex nano particle by centrifugation;
Step 3 is calcined dried described cobalt cyanate radical complex nano particle the scheduled time in air, and calcining heat is 400 ℃, obtains cobalt manganese composite oxide nano particle after calcining.
The preparation method's who this embodiment is provided below in conjunction with Figure of description principle and function are introduced.
The uniform cobalt cyanic acid manganese (Mn of embodiment 1. preparation
3[Co (CN)
6]
2) nano particle
Under room temperature environment, with syringe, 10mL is contained to 17mg (0.05mmol) K
3[Co (CN)
6] the aqueous solution be added drop-wise to 20mL and contain 18mg (0.075mmol) cobalt acetate (Co (CH
3cOO)
2) and the solution (5mL water, 15mL ethanol) of the PVP of 0.3g in, after magnetic agitation, static 24 hours, centrifugation obtained cobalt cyanic acid manganese nano particle.
The composition of particle can be determined by X-ray diffraction.As shown in Figure 2, the X-ray diffraction of prepared product in the present embodiment
figure, all diffraction maximums position corresponds respectively to (200) of cobalt cyanic acid cobalt, (220), (400), (420), (422), (440), (600), (620), (640), (642) crystal face, shows that product is the good cobalt cyanic acid manganese of crystallinity.Fig. 3 is ESEM (SEM) photo of product, and as can be seen from the figure cobalt cyanic acid manganese exists with nanoparticle form, and the pattern homogeneous of particle is cube shape, and appearance is smooth smooth, and particle diameter is in 200nm left and right.Fig. 4 is transmission electron microscope (TEM) photo of product, can find out that product particle is solid construction, can clearly recognize the lattice fringe (shown in the medium and small figure of Fig. 4 b) that spacing of lattice is respectively 0.362nm and 0.515nm under high-resolution transmission microscopy.
Embodiment 2. prepares cobalt manganese composite oxide (Co
xmn
3-xo
4) nano particle
30mg cobalt cyanic acid manganese nano particle is placed in crucible, the temperature lower calcinations of 400 ℃ 1 hour, can obtains cobalt manganese composite oxide nano particle.
The chemical composition of particle can be determined by X-ray diffraction.As shown in Figure 5, the X-ray diffraction of products therefrom in the present embodiment
figure, the position of all diffraction maximums all and CoMn
2o
4standard X-ray diffraction pattern coincide, respectively corresponding (101), (112), (103), (211), (220), (321), (224), (400) crystal face, show sample is cobalt manganese composite oxide.Do not find the diffraction maximum of cobalt cyanic acid manganese, illustrate that cobalt cyanic acid manganese is all converted into cobalt manganese composite oxide.ESEM (SEM) and transmission electron microscope (TEM) photo (shown in Fig. 6) by product can be found out.Product, after calcining, still can keep the cubical profile of precursor, and particle diameter, in 200nm left and right, due to the effusion of internal gas in calcination process, has generated fluffy loose structure simultaneously, and the surface of particle becomes uneven.Under high-resolution transmission microscopy, can recognize the lattice fringe that spacing of lattice is 0.49nm, corresponding (011) crystal face of cobalt manganese composite oxide.By the result of nitrogen adsorption (shown in Fig. 7), can learn that product is loose structure, specific surface is 128m
2/ g, and centralized particle diameter is in 5-10nm left and right.
Embodiment 3. application of cobalt manganese composite oxide nano particle in lithium ion battery negative
By the cobalt manganese composite oxide nano particle and the acetylene black that obtain under 400 ℃ of calcining heats, Kynoar (PVDF) is mixed and made into muddy material in mass ratio at 5: 3: 2, material is evenly coated on Copper Foil, after drying, Copper Foil is cut into the circular electric pole piece that diameter is 14mm in the baking oven of 100 ℃.The load of take has the electrode slice of cobaltosic oxide nano cage as anodal, and the circular metal lithium sheet that the diameter of take is 14mm is negative pole, take concentration as 1mol/L lithium hexafluoro phosphate (LiPF
6) ethylene carbonate (EC) and diethyl carbonate (DEC) (mass ratio EC: DEC=1: 1) solution is electrolyte, the circular polypropylene film that the diameter of take is 16mm is barrier film.In the glove box of argon atmosphere protection, be assembled into button cell.Battery test system is Neware BTS-610, and discharging current is 200mA g
-1.As shown in Figure 8, the discharge capacity first of test battery has reached 1400mAh g to test result
-1, having circulated after 40 times, still have 670mAh g
-1discharge capacity.This capacity is far above theoretical capacity (the 372mAh g of existing commercial graphite cathode
-1).
In a word, the present invention is simply efficient, and safety is easily gone, and can produce cobalt manganese composite oxide nano particle in enormous quantities, and resulting particle has the pattern of homogeneous and larger specific surface, can be applied at aspects such as electrochemical energy storage and electro-catalysis.
The technical scheme that this embodiment provides advantage is compared with prior art:
(1) the current frequent adopted method of preparing cobalt manganese composite oxide nano particle is high temperature solid-state method and sol-gal process.High-temperature calcination high temperature solid-state method need to mix different types of slaine with cobalt salt after, sol-gal process also needs prepared gel at high temperature to calcine.These two kinds of methods all need to use HTHP, and are not easy to control the pattern of product, particle diameter and specific surface.Under some room temperatures, prepare the method for cobalt manganese composite oxide nano particle and need to use hazardous agents (as NaBH4) or complicated preparation technology, be not easy to produce in enormous quantities.Compare with these methods, the present invention at room temperature generates cobalt cyanate radical complex nano particle by the precipitation method, because two metal ion species are in same lattice, realize the blend of ion, using it as precursor, can obtain at relatively low temperature lower calcination cobalt manganese composite oxide nano particle.Preparation technology is simply efficient, and safety is easily gone, and synthesis cycle is short, is expected to be promoted with industrialization produce.
(2) the present invention has used surfactant (PVP) to assist synthetic cobalt cyanate radical complex nano particle, makes the pattern of particle controlled, good dispersion, and after calcining, can keep the original pattern of precursor.Cyanogen root (CN in cobalt cyanate radical complex
-) and surfactant meeting and air reaction in calcination process, generate a large amount of gas and overflow from inside particles, the cobalt manganese composite oxide nano particle therefore obtaining is porous, has larger specific area.
(3) the cobalt manganese composite oxide nano particle that the present invention obtains can be used for electrochemical energy storage and electro-catalysis, because it has larger specific area and the structure of porous, very high capacity and good cycle performance when being applied as lithium ion battery negative material, have been shown.
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (1)
1. a preparation method for cobalt manganese composite oxide nano particle, is characterized in that, comprising:
By in the manganese acetate of scheduled volume and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidonesolution solution;
Under predetermined temperature, cobalt potassium cyanate solution is added drop-wise in described manganese acetate and polyvinylpyrrolidonesolution solution, the standing scheduled time after magnetic agitation, then obtain cobalt cyanate radical complex nano particle by centrifugation;
Dried described cobalt cyanate radical complex nano particle is calcined the scheduled time in air, and calcining heat is 400 ℃, obtains cobalt manganese composite oxide nano particle after calcining.
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| CN103746104A (en) * | 2013-12-09 | 2014-04-23 | 中国科学院福建物质结构研究所 | Manganese cobalt oxide self-assembled micro-spheres, and preparation and applications thereof |
| CN103752321B (en) * | 2014-01-02 | 2016-08-17 | 上海大学 | The preparation method of hierarchy bimetallic composite oxide denitrification catalyst |
| CN103943849B (en) * | 2014-05-04 | 2016-05-04 | 汝南县广森电动车科技有限公司 | The preparation method of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery |
| CN104332626B (en) * | 2014-09-09 | 2017-01-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of negative electrode material Mn2CoO4/poly(3,4-ethylenedioxythiophene) |
| CN105388136B (en) * | 2015-11-30 | 2018-05-29 | 中国科学技术大学 | A kind of fluorescence imaging probe and preparation method thereof, purposes |
| CN105742623A (en) * | 2016-04-07 | 2016-07-06 | 华南师范大学 | Nanometer prismatic lithium-rich material and preparation method and application thereof |
| CN106334572A (en) * | 2016-07-28 | 2017-01-18 | 新疆轻工职业技术学院 | Cu/Co@NPC compound used for catalytic reduction of p-nitrophenol |
| CN109319845B (en) * | 2018-09-18 | 2020-01-17 | 山东大学 | Spherical porous lithium manganate and preparation method and application thereof |
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