CN108046217A - The preparation method of nano composite metal oxide - Google Patents
The preparation method of nano composite metal oxide Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of nano composite metal oxide, including：The nano-metal-oxide of one of major metal component using metal composite oxide is as nano-form, make in the aqueous solution of the water soluble salt for other metal ingredients that nano-form is dispersed in metal composite oxide to obtain mixed dispersion liquid, major metal component refer to its molar content account for the molar content of all metal ingredients ratio be more than 30% metal ingredient；Mixed dispersion liquid is dried to obtain powder mixture by spray drying or vacuum freeze-drying method；Powder mixture is heated so that water soluble salt decomposes the oxide of generation and nano-metal-oxide combines to form nano composite metal oxide.The preparation method of the present invention significantly reduces cost and operation difficulty, and avoids a large amount of uses of organic compound, and avoid that batch mixing is uneven and ball milling impurity introduces and caused by the not pure and mild microstructure of ingredient the problem of being difficult to control.
Description
Technical field
The present invention relates to the preparing technical field of nano material, in particular to a kind of nano composite metal oxide
Preparation method.
Background technology
The existing method for preparing nano composite metal oxide mainly includes two major classes, and one kind is liquid phase method or wet
Chemical method, including coprecipitation, hydro-thermal method, sol-gal process, another kind of is solid phase method.The above method is simply introduced below
It is as follows：
1st, coprecipitation：Compound containing metallic element is dissolved in liquid (deionized water or absolute ethyl alcohol etc., according to
The species of the different definite solvents of the property of compound), it adds in precipitating reagent and stirs, several metal ion species is made proportionally to generate heavy
It forms sediment, after then sediment is washed, calcine, obtains target product.
2nd, hydro-thermal method：A kind of deformation of coprecipitation, precursor liquid is consistent with coprecipitation, will then add precipitating reagent
Mixed solution be put into the reaction kettle of sealing, (be more than 100 DEG C) heating at high temperature is produced using the boiling of water or other solvents
Raw high pressure, so as to generate the precipitation with special appearance.
3rd, sol-gal process：It is similar with coprecipitation, but precipitating reagent is added without in solution, but complexing agent is added in, make
Local segregation does not occur with the reduction of solution for the metal ion profile in solution, and final product component is avoided to become
Change.Heated solution simultaneously stirs, and becomes the gel with certain viscosity, will obtain target product after gel drying and sintering.
4th, solid phase method：By compound (generally oxide) directly mixing, ball milling, drying containing metallic element, and
It is calcined at a temperature of certain, makes different substance interreactions, so as to generate new phase.
From preparing in effect, liquid phase method is better than solid phase method.Most the underlying cause be liquid phase method can in molecule or
Ion level is realized the mixing of Determination of multiple metal elements in product and is uniformly distributed, so as to be able to accurately control the ingredient of product, and
And pattern and the more uniformly distributed nano-particle of grain size can be obtained.
Solid phase method due to be physical layer the i.e. particle of mixing with the mixing of particle with contacting, easily generate ingredient not
It is uniformly distributed, and the substance of container inner wall and abrading-ball surface is inevitably mixed in mechanical milling process, cause product component
It is impure.
Further, since solid-phase ball milling is physical mixed, the rise of phase temperature is resulted in the need for into, high temperature sintering brings particle again
Grow up, inhomogeneities aggravation and surface area reduce etc. microarchitectural deteriorations the problem of.The prior art provides a kind of improved solid phase
Method prepares the metal composite oxide of fluorite structure or perovskite structure, is improved by adding in readily soluble organic matter in ball milling
The dispersing uniformity of solid phase method batch mixing, but the method cannot still control the particle size of product and be distributed and draw without solving ball milling
The problem of entering impurity.
But, economically consider, solid phase method is significantly better than liquid phase method, and solid phase method flow is simple, of low cost, is easy to
Amplification.In contrast, liquid phase method has many restrictions in the control of reaction condition and the aspect of selecting of presoma.
By taking the synthesis of the metal composite oxide containing niobium as an example, the precipitation method or compound of the hydro-thermal method synthesis containing niobium are most-often used
Persursor material for ethyl alcohol niobium, target product is obtained by co-precipitation or high temperature and pressure in organic solution system
(SrTixNb1-xO3, SrxBa1-xNb2O6, LiNbO3, SrBi2Nb2O9Deng).
The major defect of this method be as presoma ethyl alcohol niobium price it is very expensive and equal to oxygen and moisture
Extreme sensitivity is very easy to decompose.Therefore in process for preparation, in order to strictly ensure anhydrous and oxygen free condition, it is necessary to non-
The preservation of Chang little Xin, while anhydrous, anaerobic operation is carried out in glove box.
In addition, it is not chemically reacted even if the storage of prepared precursor solution is also required to be used to ensure that as early as possible.To the greatest extent
Pipe can improve the stability (as used ethylene glycol or methyl ether equal solvent) of presoma by some corrective measures, but not from
It fundamentally solves the problems, such as this, also significantly limits the commercial applications of similar precursor system.
Columbium pentachloride is dissolved in the niobium pentoxide of hydrofluoric acid and can also be used by the presoma as niobium, although opposite alcohol
Salt, the price of halogen salt is relatively inexpensive, and stability also has improvement, still, can not due to containing halogen in precursor liquid
Halogen residual is had in the final material avoided, the relevant property of material may be deteriorated.
Even if without using expensive organic precursors, hydro-thermal method prepare metal composite oxide still need to rely on it is high-temperature and high-presure resistent
Hydrothermal reaction kettle, for large-scale production, equipment investment is big and Operation and Maintenance difficulty is high.
In addition, composition metal oxide nano particle is prepared using sol-gal process, it is necessary to largely add citric acid, sweet ammonia
The organic substances such as acid are as complexing agent (bibliography J.Phys.Chem.C 112 (2008) 14064-14074；Ceramics
International 37 (2011) 951-955), so as to cause substantial amounts of dirty during the increase of cost of material and subsequent calcination
Contaminate object discharge.
All in all, the production method of nano composite metal oxide mainly leaves problems at present：
1. though solid phase method is simple cheap, it can not realize the accurate control to product composition and micro-structure.
2. though wet chemistry method can obtain purity and the good product of micro-structure, Preparation equipment or technological process are complicated, also
Expensive organic precursors or substantial amounts of organic complexing agent need to be used.
The content of the invention
In view of the above problems, the present invention provides a kind of preparation methods of new nano composite metal oxide.
An embodiment of the invention provides a kind of preparation method of nano composite metal oxide, including：
The nano-metal-oxide of one of major metal component using the metal composite oxide makes as nano-form
The nano-form is dispersed in the aqueous solution of the water soluble salt of other metal ingredients in the metal composite oxide
To obtain mixed dispersion liquid, the major metal component refers to that its molar content accounts for the ratio of the molar content of all metal ingredients
Metal ingredient more than 30%；
The mixed dispersion liquid is dried to obtain powder mixture by spray drying or vacuum freeze-drying method；
The powder mixture is heated so that the oxide that the water soluble salt decomposes generation is received with described
Rice metal oxide combines to form the nano composite metal oxide.
In the preparation method of above-mentioned nano composite metal oxide, the nano-form further include it is at least one other
The nano-metal-oxide of metal ingredient.
In the preparation method of above-mentioned nano composite metal oxide, the form of the nano-form is nano particle,
One or more in nanotube, nanometer rods and nano-hollow ball.
In the preparation method of above-mentioned nano composite metal oxide, the water soluble salt is nitrate, acetate, carbon
One or more in hydrochlorate, sulfate and oxalates.
In the preparation method of above-mentioned nano composite metal oxide, the metal composite oxide for fluorite structure,
Perovskite structure, spinel structure, layered rock salt structure etc..
In the preparation method of above-mentioned nano composite metal oxide, the metal composite oxide is SrxTi(1-y)
ByO3±δ, wherein B is one or both of Nb, Ta, Co, Ni, Fe；X=0.9-1, y=0-0.9, δ represent what is generated by doping
Oxygen nonstoichiometry.
In the preparation method of above-mentioned nano composite metal oxide, the metal composite oxide is AxCe(1-x)
O2±δ, wherein A is one or both of for Gd, Sm, Pr, Nd, La, and 0<X≤0.6, δ represent the non-chemical meter of oxygen generated by doping
Magnitude.
In the preparation method of above-mentioned nano composite metal oxide, the metal composite oxide is AxZr(1-x)
O2±δ, wherein A is one or both of for Y, Sc, Ce, and 0<X≤0.4, δ represent the oxygen nonstoichiometry generated by doping.
In the preparation method of above-mentioned nano composite metal oxide, the metal composite oxide is LiAO2±δ,
Middle A is one or more of Ni, Mn, Co, Al, Ti.
In the preparation method of above-mentioned nano composite metal oxide, the grain size of the nano composite metal oxide is
5-1000nm。
In the preparation method of above-mentioned nano composite metal oxide, the mixed dispersion liquid is passing through spray dryer
When being spray-dried, inlet air flow is arranged to 150-180 DEG C, throughput 120-200L/min, residence time 1-4s.
Nano composite metal oxide is synthesized using the method for the present invention, not only operating process is simple, but also in normal pressure and water
It can be carried out in phase, compared to existing liquid phase method, the method for the present invention is loose for preparation condition requirement, can significantly reduce equipment
Cost and operation difficulty, it is often more important that inventive process avoids metal-organic precursor body costly and a large amount of networks
The use of the organic compounds such as mixture so as to greatly reduce pollutant emission and the production cost in subsequent preparation process, belongs to
In green synthesis techniques.
In addition, compared to solid phase method, the method for the present invention is passed through by the homodisperse accurate control product component of molecular level
Original template accurately controls particle size and pattern, avoid that solid phase method batch mixing is uneven and ball milling impurity introduces and caused by ingredient
The problem of not pure and mild microstructure is difficult to control.
Description of the drawings
In order to illustrate more clearly of technical scheme, letter will be made to attached drawing needed in the embodiment below
It singly introduces, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as to the present invention
The restriction of protection domain.
Fig. 1 is the SrTiO obtained according to the embodiment 1 of the preparation method of the nano composite metal oxide of the present invention3±δPowder
The XRD diagram of body.
Fig. 2 is the SrTiO obtained according to the embodiment 1 of the preparation method of the nano composite metal oxide of the present invention3±δPowder
The SEM photograph of body.
Fig. 3 is to be obtained according to the embodiment 2 of the preparation method of the nano composite metal oxide of the present invention
Sr0.95Ti0.9Nb0.1O3±δThe XRD diagram of powder.
Fig. 4 is to be obtained according to the embodiment 2 of the preparation method of the nano composite metal oxide of the present invention
Sr0.95Ti0.9Nb0.1O3±δThe SEM photograph of powder.
Fig. 5 is to be obtained according to the embodiment 3 of the preparation method of the nano composite metal oxide of the present invention
Sc0.18Y0.02Zr0.80O2±δThe XRD diagram of powder.
Fig. 6 is to be obtained according to the embodiment 3 of the preparation method of the nano composite metal oxide of the present invention
Sc0.18Y0.02Zr0.80O2±δThe SEM photograph of powder.
Fig. 7 is to be obtained according to the embodiment 4 of the preparation method of the nano composite metal oxide of the present invention
Gd0.1Ce0.9O2±δThe XRD diagram of powder at different temperatures.
Fig. 8 is to be obtained according to the embodiment 4 of the preparation method of the nano composite metal oxide of the present invention
Gd0.1Ce0.9O2±δThe SEM photograph of powder.
Fig. 9 is to be obtained according to the embodiment 5 of the preparation method of the nano composite metal oxide of the present invention
LiNi0.65Co0.25Mn0.1O2±δThe XRD diagram of ternary material.
Figure 10 is to be obtained according to the embodiment 6 of the preparation method of the nano composite metal oxide of the present invention
LiNi0.333Co0.333Mn0.333O2±δThe XRD diagram of ternary material.
Specific embodiment
Below in conjunction with attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Ground describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is right below
The detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit the scope of claimed invention, but
It is merely representative of the selected embodiment of the present invention.Based on the embodiment of the present invention, those skilled in the art are not making creativeness
All other embodiments obtained on the premise of work, belong to the scope of protection of the invention.
An embodiment of the invention provides a kind of preparation method of nano composite metal oxide, including：By described in
The nano-metal-oxide of one of the major metal component of metal composite oxide makes the nano-form equal as nano-form
It is scattered to obtain mixing in the aqueous solution of the water soluble salt of even other metal ingredients being scattered in the metal composite oxide
Liquid, the major metal component refer to that its molar content accounts for metal of the ratio more than 30% of the molar content of all metal ingredients
Ingredient；The mixed dispersion liquid is dried to obtain powder mixture by spray drying or vacuum drying method；By described in
Powder mixture is heated so that the water soluble salt decomposes the oxide of generation and the nano-metal-oxide knot
Conjunction forms the nano composite metal oxide.
The present invention program is using the nano-oxide of main metal element as template, the soluble-salt that adds in aqueous solution
(such as inorganic salts) by stirring and rapid draing, are evenly distributed on the surface of nano-form particle, after high temperature sintering, metal
Salt decomposes generation metal oxide and is simultaneously reacted with templated metal oxide, and generation is similar with template microstructure nano combined
Metal oxide target product.
There are many during major metal component, the nano composite metal oxide as nano-form can be used relatively inexpensive
The nano-oxide for the major metal component being easy to get.Nano-form is dispersed in the water of the water soluble salt of other metal ions
In solution, the methods of then passing through spray drying rapid draing obtains molecular level and uniformly disperses Determination of multiple metal elements/nanogold
Belong to hopcalite, be thermally treated resulting in the nano-powder product of metal composite oxide afterwards.
The mixed dispersion liquid can be such as suspension or solution.It can be added in the mixed dispersion liquid a small amount of
Surfactant.The surfactant is preferably that (polyethylene oxide-polypropylene oxide-polyethylene oxide three is embedding by such as P123
Section copolymer), PVP (polyvinylpyrrolidone), Triton-100 (Triton X-100) and PEG (polyethylene glycol)
One or more in 400-2000.
A small amount of complexing agent can be added in the mixed dispersion liquid, complexing agent rubs with solvable presoma metal ion
You are than being less than 50%, preferably smaller than 30%, for forming more stable solution with complexing of metal ion.The complexing agent can be
Such as the complexing agents such as citric acid, EDTA.
The form of nano-form can be one kind or more in nano particle, nanotube, nanometer rods and nano-hollow ball etc.
Kind.Metal oxide nano template used includes nano particle, nanotube, nanometer rods, nano-hollow ball of different-shape etc.
When, the grain size and microscopic appearance of product are controlled by nano-form.
Above-mentioned water soluble salt can be the one or more in nitrate, acetate, carbonate, sulfate and oxalates.
It is preferable to use the inorganic salts such as nitrate, carbonate and sulfate.
It is brilliant that the preparation method of the nano composite metal oxide of the present invention can prepare fluorite structure, perovskite structure, point
Stone, the isostructural metal composite oxide of stratiform rock salt.
The metal composite oxide is preferably SrxTi(1-y)ByO3±δ, wherein B be Nb, Ta, Co, Ni, Fe in one kind or
Two kinds；X=0.9-1, y=0-0.9, δ represent the oxygen nonstoichiometry generated by doping.δ is former for Lacking oxygen or gap digit oxygen
Quantum count, factor value very little and all closely related with doping, temperature, atmosphere are usually replaced with δ.The numerical value of x is smaller than 1, table
Omission can artificially be caused in the site where Sr by showing, typically to the precipitation for preventing Sr and in order to which more Lacking oxygens generate.
The metal composite oxide is also preferably AxCe(1-x)O2±δ, wherein A be Gd, Sm, Pr, Nd, La in one kind or
Two kinds, 0<X≤0.6 is, for example, that 0.1,0.2,0.3,0.4 or 0.5, δ represent the oxygen nonstoichiometry generated by doping.
The metal composite oxide is also preferably AxZr(1-x)O2±δ, wherein A is one or both of for Y, Sc, Ce, and 0<x
≤ 0.4, it is, for example, that 0.1,0.2 or 0.3, δ represent the oxygen nonstoichiometry generated by doping.
The metal composite oxide is also preferably LiAO2±δ, wherein A is one or more of Ni, Mn, Co, Al, Ti.
In the preparation method of above-mentioned nano composite metal oxide, the grain size of the nano composite metal oxide can
Think 5-1000nm, be, for example, 10,50,100,300,600 or 900nm, be preferred for 5-300nm.
In the preparation method of above-mentioned nano composite metal oxide, the mixed dispersion liquid is passing through spray dryer
When being spray-dried, inlet air flow is arranged to 150-180 DEG C, such as 160 or 170 DEG C, throughput 120-200L/min, example
Such as 130,140,150,160,170,180 or 190L/min, residence time 1-4s, such as 2s or 3s.
In the preparation method of above-mentioned nano composite metal oxide, passing through spray drying or vacuum freeze drying side
After method dry mixed dispersion liquid, first powder can be dried in an oven, such as the drying at 90-250 DEG C.It can dry in an oven
Such as 2-10 it is small when.Drying in baking oven can be divided into multiple stages and be dried, for example, can (example in the first stage successively
Such as 90-150 DEG C) and the second thermophase (such as 110-250 DEG C) drying.
Then high-temperature calcination is carried out, uses such as Muffle furnace and tube furnace etc..High-temperature calcination can also be divided into multiple stages,
For example, can successively in the first stage (such as 300-600 DEG C) and second stage (such as 600-1300 DEG C, such as 600,700,
800th, 900,1000,1100 or 1300 DEG C) calcining.It can be small in target temperature heat preservation 0.5-6 respectively in the first and second stages
When, when preferably 1-3 is small.Progressively heating mode can be used in temperature rise period in high-temperature calcination, such as the 60-200 that heats up per hour
℃.In high-temperature calcination second stage inert gas (such as nitrogen) can first be used to purge, then with the gaseous mixture of hydrogen-inert gas
Body (such as hydrogen nitrogen mixed gas containing 9% hydrogen).
The preparation method of the nano composite metal oxide of the present invention can be used for electrode material and electrolyte and its
His composite metal oxide material etc..
Illustrate the preparation method of the nano composite metal oxide of the present invention with specific embodiment below, certainly, this
The protection domain of invention is not limited to these embodiments.
Embodiment 1
SrTiO3±δPreparation
1. weigh TiO of the grain size in 15 rans of 0.2mol2Particle is simultaneously positioned in beaker, add in 100mL go from
It is stirred after sub- water, forms suspension, be set as A；
2. according to the molar ratio 1 of Sr and Ti:1 weighs 0.2mol Sr (NO3)2, add in 800mL deionized water dissolvings, setting
For B；
3. B is poured slowly into A, it is uniformly mixed；Add in a small amount of surfactant (P123, PVP, Triton-
100 or PEG400-2000), form stable suspension.
It is spray-dried 4. the suspension of step 3 is transferred in spray dryer, inlet air flow temperature is set to 150-
180 DEG C, throughput 120-200L/min, residence time 1-4s；
It after when 5. 120 DEG C of dryings 2 are small in air dry oven by powder, take out powder and pours into crucible, crucible is put
In Muffle furnace, when being warming up to 350 DEG C and small heat preservation 1 with the heating rate of 1 DEG C/min, crucible is placed in tube furnace after cooling
Between, nitrogen is passed through after sealing as purge gass, the gaseous mixture of 9% hydrogen-nitrogen is changed to after a period of time, and with 1 DEG C/min's
Heating rate is warming up to 600-800 DEG C, and keep the temperature 2 it is small when, be so attached to TiO2Sr (the NO of particle surface3)2Decompose generation
SrO, and and TiO2It is combined with each other, SrTiO of the generation with perovskite structure3±δProduct.
The ingredient and crystal structure of product can measure to determine that Fig. 1 gives products therefrom by X-ray diffraction (XRD)
XRD datagrams, after being compared with standard database determine product for essentially perovskite structure SrTiO3±δ, contain only
Trace Ti O2Phase.The microscopic appearance of powder can be observed by the electronic scanner microscope (SEM) of high-amplification-factor.Fig. 2 gives
Gained SrTiO is gone out3±δThe SEM photograph of powder, as can be seen from the figure SrTiO3±δDiameter of particle at 15-20 nanometers, substantially with
Template TiO2Unanimously, and distribution is visibly homogeneous.
Embodiment 2
Sr0.95Ti0.9Nb0.1O3±δPreparation
1. weigh TiO of the grain size of 0.18mol at 60 nanometers2Particle is simultaneously positioned in beaker, adds in 700mL deionized waters
After stir, formed suspension, be set as A；
2. weigh 0.19mol Sr (NO according to ion molar ratio3)2800mL deionized water dissolvings are added in, are set as B；By B
It is poured slowly into A, is uniformly mixed, form solution C；
3. weigh 0.02mol C4H4NNbO9, add in C, it is quick to stir, add in a small amount of surfactant (P123,
PVP, Triton-100 or PEG400-2000), form stable suspension.
4. the suspension of step 3 is shifted vacuum freeze drier, in -10 to -50 DEG C of quick freezes into solid-state, Ran Hou
Vacuum 1.3 is excluded for gaseous state to moisture being made directly to distil under 13Pa.
5. powder is placed in Muffle furnace, when being warming up to 350 DEG C and small heat preservation 1 with the heating rate of 1 DEG C/min, after cooling
Crucible is placed among tube furnace, nitrogen is passed through after sealing as purge gass, the mixed of 9% hydrogen-nitrogen is changed to after a period of time
Close gas, and 600-1000 DEG C be warming up to the heating rate of 1 DEG C/min, and keep the temperature 2 it is small when, be so attached to TiO2Particle surface
Sr (NO3)2Decompose generation SrO, C4H4NNbO9Decompose generation Nb2O5, and and TiO2It is combined with each other, generation has perovskite structure
Sr0.95Ti0.9Nb0.1O3±δProduct.
The ingredient and crystal structure of product can measure to determine that Fig. 3 gives products therefrom by X-ray diffraction (XRD)
XRD datagrams, after being compared with standard database determine product be perovskite structure Sr0.95Ti0.9Nb0.1O3±δ.Powder
Microscopic appearance can be observed by the electronic scanner microscope (SEM) of high-amplification-factor.Fig. 4 gives gained
Sr0.95Ti0.9Nb0.1O3±δThe SEM photograph of powder, as can be seen from Figure 4 Sr0.95Ti0.9Nb0.1O3±δDiameter of particle is about 60-
70 nanometers, substantially with template TiO2Unanimously, and distribution is visibly homogeneous.
Embodiment 3
Prepare Sc0.18Y0.02Zr0.80O2±δNano-powder
1. according to Sc0.18Y0.02Zr0.80O2±δStoichiometric ratio add in scandium nitrate, the yttrium nitrate of corresponding metering, add in one
In the deionized water for determining dosage, it is completely dissolved；
2. according to Sc0.18Y0.02Zr0.80O2±δStoichiometric ratio, add in the ZrO of corresponding measurement2(grain size is nano-particle
40-50nm) to step 1 scandium nitrate and yttrium nitrate aqueous solution in, be sufficiently stirred；Add in a small amount of surfactant (P123,
PVP, Triton-100 or PEG400-2000), form stable suspension.
3. the suspension of step 2 is transferred in spray dryer, inlet air flow temperature is set to 120-150 DEG C, throughput
120-150L/min, residence time 1-4s；
4. the powder that step 3 is dried is put into baking oven, when 120 DEG C of dryings 4 are small, then when 200 DEG C of dryings 4 are small；
5. by the powder of step 4 be put into Muffle furnace with 60 DEG C per hour be warming up to 350 DEG C stop 2 it is small when, then with every
Hours 60 DEG C be warming up to 800-900 DEG C of heat preservation 2 it is small when, Temperature fall after being cooled to 400 DEG C with 100 DEG C per hour is had
The product of perovskite structure.
The ingredient and crystal structure of product can measure to determine that Fig. 5 gives products therefrom by X-ray diffraction (XRD)
XRD datagrams, after being compared with standard database determine product be perovskite structure Sc0.18Y0.02Zr0.80O2±δ.Powder
Microscopic appearance can be observed by the electronic scanner microscope (SEM) of high-amplification-factor.Fig. 6 gives gained
Sc0.18Y0.02Zr0.80O2±δThe SEM photograph of powder, as can be seen from the figure diameter of particle is about 40-50 nanometers, substantially and template
ZrO2Unanimously, and distribution is visibly homogeneous.
Embodiment 4
Prepare Gd0.1Ce0.9O2±δNano-powder
1. according to Gd0.1Ce0.9O2±δStoichiometric ratio add in the gadolinium of corresponding metering, add in doses go from
In sub- water, it is completely dissolved；
2. according to Gd0.1Ce0.9O2±δStoichiometric ratio, add in the CeO of corresponding measurement2(average grain diameter is about nano-particle
30nm) into the gadolinium aqueous solution of step 1, it is sufficiently stirred.A small amount of citric acid or EDTA are added in, with solvable presoma metal
The molar ratio 0-50% of ion, with complexing of metal ion to form stablizing solution.
3. the mixed solution of step 2 is transferred in spray dryer, inlet air flow temperature is set to 150 DEG C, throughput
200L/min, residence time 1-4s；
4. the powder that step 3 is dried is put into baking oven, when 120 DEG C of dryings 4 are small, then when 200 DEG C of dryings 4 are small；
5. by the powder of step 4 be put into Muffle furnace with 60 DEG C per hour be warming up to 350 DEG C stop 2 it is small when, then with every
Hours 60 DEG C be warming up to 600-1000 DEG C of heat preservation 2 it is small when, Temperature fall after being cooled to 400 DEG C with 100 DEG C per hour.
The crystal structure of gained powder is determined using XRD, the results are shown in Figure 7, and gained powder is in 600 DEG C of heat treatment
Single cubic fluorite structure is generated, is formed as Gd0.1Ce0.9O2±δ, the heat treatment through 800 DEG C or 1300 DEG C, phase structure stabilization nothing
Variation.SEM researchs find the Gd of 600 DEG C of heat treatment (referring to Fig. 8)0.1Ce0.9O2±δDiameter of particle is in 30-40 rans, with mould
Plate is basically identical, and is uniformly dispersed.
Embodiment 5
Prepare LiNi0.65Co0.25Mn0.1O2±δ(NCM) ternary lithium electricity nano-powder
1. the NiO powders that 0.065 mole of grain size is about 1 micron are added in 100-200 milliliters according to stoichiometric ratio
In ionized water, it is sufficiently stirred.
2. add in 0.025 mole of Co (NO3)2, 0.1 mole of C2H3O2Li, 0.01 mole of Mn (NO3)2Add in 100-
It is quick to stir in 200 ml deionized waters, and mixed with the NiO suspension in step 1, it stirs evenly, adds in a small amount of surface
Activating agent (P123, PVP, Triton-100, PEG400-2000 etc.), forms stable suspension.
3. the suspension in step 2 is transferred in spray dryer, inlet air flow temperature is set to 150-200 DEG C, air-flow
Measure 200L/min, residence time 1-4s；
4. the powder that step 3 is dried is put into baking oven, when 120 DEG C of dryings 4 are small, then 2- is sintered at 600-1000 DEG C
4 it is small when, obtain ternary composite electrode material.The ingredient and crystal structure of product can be measured by X-ray diffraction (XRD) come really
Fixed, Fig. 9 gives the XRD datagrams of products therefrom, and it is layered rock salt structure that product is determined after being compared with standard database
LiNi0.65Co0.25Mn0.1O2±δ。
Embodiment 6
Prepare LiNi0.333Co0.333Mn0.333O2±δTernary lithium electricity nano-powder
1. the CoO powders that 0.0333 mole of grain size is about 2 microns are added in 100-150 milliliters according to stoichiometric ratio
In ionized water, it is sufficiently stirred.
2. add in 0.0333 mole of Ni (NO3)2, 0.1 mole of C2H3O2Li, 0.0333 mole of Mn (NO3)2It adds in
It is quick to stir in 100-150 ml deionized waters, and mixed with the NiO suspension in step 1, it stirs evenly, adds in a small amount of
Surfactant (P123, PVP, Triton-100, PEG400-2000 etc.), forms stable suspension.
3. the suspension in step 2 is transferred in spray dryer, inlet air flow temperature is set to 120-200 DEG C, air-flow
Measure 160-200L/min, residence time 1-4s.
4. the powder that step 3 is dried is put into baking oven, when 120 DEG C of dryings 4 are small, then it is sintered at 800-1000 DEG C
When 2-4 is small, ternary composite electrode material is obtained.Ingredient and structural analysis test report to resulting materials are shown in Figure 10.Test knot
Fruit shows that resulting materials ingredient is LiNi0.333Co0.333Mn0.333O2±δTypical crystal structure.
In above embodiment, although only using a kind of nano-metal-oxide of major metal component as nanometer mould
Plate however, in the present invention, can also use the nano-metal-oxide of the metal ingredient of two or more as nanometer mould
Plate.Other nano-metal-oxide templates can be the oxide of major metal component or non-principal metal ingredient
Oxide, that is to say, that the molar content of other nano-metal-oxide templates can be greater than, equal to or less than above-mentioned
A kind of molar content of the nano-metal-oxide template of major metal component.For example, including two or more major metals
During ingredient, a kind of major metal component can be used only as nano-form, two kinds of major metal component conducts can also be used
Nano-form can also use a kind of major metal component and one or more non-principal metal ingredients.It is aoxidized in other metals
When object template is less than a kind of molar content of the nano-metal-oxide template of above-mentioned major metal component, as aided nano
Template.In view of the dispersiveness of metal oxide template, the molar content of preferably other metal oxide templates accounts for all nanometers
The ratio of the molar content of template is less than 30%.
The preparation method of the nano composite metal oxide of the present invention has the following advantages：
1) compared to solid phase method, synthesis temperature is low, and grain size is small, and uniformity is good.
2) template grain size is highly uniform, is synthesized compared to conventional sol gel, at low cost, green syt.
3) organic precursor can not had to, exhaust is decomposed in high temperature from the operation of gel expansion process may be not present, need not added
Increasing amount complexing agent is even without complexing agent.Even if using complexing agent, the present invention can be used only a small amount of complexing agent, complexing agent with
The molar ratio of metal ion is less than 0.5：1.
4) process is simple, and solution usage is few, and quickly, production efficiency is high for dry water removal, can amplification it is fine.
5) (need to ensure during amplification each when refined conditions control requirement there is no the such temperature acidity complexing agent of collosol and gel
Condition has high uniformity in large scale reaction kettle),
6) outside removing template, as long as predecessor is solvable (requirement of this condition is insensitive to reaction kettle size), amplification life
There is no obstacles for production.
In conclusion using the method synthesis metal composite oxide nanoparticle in the present invention, not only operating process letter
It is single, and can be carried out in normal pressure and water phase, compared to existing liquid phase method, the method for the present invention requires not for preparation condition
Harshness can significantly reduce equipment cost and operation difficulty, it is often more important that inventive process avoids big weight organic compounds
It uses, so as to greatly reduce pollutant emission and the production cost in subsequent preparation process, belongs to green synthesis techniques；It compares
In solid phase method, the method for the present invention is accurately controlled by the homodisperse accurate control product component of molecular level by original template
Particle size and pattern, avoid that solid phase method batch mixing is uneven and ball milling impurity introduces and caused by the not pure and mild microstructure of ingredient it is difficult
The problem of to control.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can readily occur in change or replacement, should all contain
Lid is within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nano composite metal oxide, which is characterized in that including：
The nano-metal-oxide of one of major metal component using the metal composite oxide makes described as nano-form
Nano-form is dispersed in the aqueous solution of the water soluble salt of other metal ingredients in the metal composite oxide to obtain
To mixed dispersion liquid, the major metal component refers to that its molar content accounts for the ratio of the molar content of all metal ingredients and is more than
30% metal ingredient；
The mixed dispersion liquid is dried to obtain powder mixture by spray drying or vacuum freeze-drying method；
The powder mixture is heated so that the water soluble salt decomposes the oxide of generation and the nanogold
Belong to oxide and combine to form the nano composite metal oxide.
2. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The nano-form
Further include the nano-metal-oxide of other at least one metal ingredients.
3. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The nano-form
Form be the one or more in nano particle, nanotube, nanometer rods and nano-hollow ball.
4. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The water soluble salt
For the one or more in nitrate, acetate, carbonate, sulfate and oxalates.
5. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The composition metal
Oxide is fluorite structure, perovskite structure, spinel structure or layered rock salt structure.
6. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The composition metal
Oxide is SrxTi(1-y)ByO3±δ, wherein B is one or both of Nb, Ta, Co, Ni, Fe；X=0.9-1, y=0-0.9, δ
Represent the oxygen nonstoichiometry generated by doping.
7. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The composition metal
Oxide is AxCe(1-x)O2±δ, wherein A is one or both of for Gd, Sm, Pr, Nd, La, and 0<X≤0.6, δ represent to produce because of doping
Raw oxygen nonstoichiometry.
8. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The composition metal
Oxide is AxZr(1-x)O2±δ, wherein A is one or both of for Y, Sc, Ce, and 0<X≤0.4, δ represent the oxygen generated by doping
Non-stoichiometry value.
9. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The composition metal
Oxide is LiAO2±δ, wherein A is one or more of Ni, Mn, Co, Al, Ti, and δ is represented because the oxygen of doping generation is non-chemical
Variable.
10. the preparation method of nano composite metal oxide according to claim 1, it is characterised in that：The nanometer is answered
The grain size for closing metal oxide is 5-1000nm.
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| CN113072091A (en) * | 2021-03-25 | 2021-07-06 | 南昌航空大学 | Five-membered cerium neodymium yttrium based high-entropy rare earth oxide and preparation method thereof |
| CN113371756A (en) * | 2021-07-13 | 2021-09-10 | 河南工业大学 | La-Sc-ZrO2 nano-crystal material and preparation method thereof |
| CN114873656A (en) * | 2022-05-20 | 2022-08-09 | 浙江大学 | Preparation method of transition metal ion modified La-Sr-Co-X-O composite oxide with high-conductivity layered structure |
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