CN102030352A - Method for preparing nano material - Google Patents

Method for preparing nano material Download PDF

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CN102030352A
CN102030352A CN 201010517639 CN201010517639A CN102030352A CN 102030352 A CN102030352 A CN 102030352A CN 201010517639 CN201010517639 CN 201010517639 CN 201010517639 A CN201010517639 A CN 201010517639A CN 102030352 A CN102030352 A CN 102030352A
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nano
preparing
precursor
liquid
metal
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CN102030352B (en
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周继承
肖伶俐
谢放华
孟翔
曾敏
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Xiangtan University
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Xiangtan University
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Abstract

The invention relates to a method for preparing a nano material, which comprises the step of: preparing a nano material precursor and a nano material. The method for preparing the nano material precursor comprises the step of: placing reacting raw materials in a supergravity filed reactor for gas-liquid reaction or liquid-liquid reaction to obtain the nano material precursor. The method for preparing the nano material comprises the step of heating and roasting the nano material precursor with a microwave field to ensure that the nano material precursor generates decomposition or recrystallization to obtain the nano material. The method for preparing the nano material precursor also comprises the step of: in a process of accelerating and enhancing the mass transfer with the supergravity filed, enabling a metal salt water solution in the reactor to be uniformly mixed with a liquid precipitator or gas precipitator in a molecule size manner for chemical reaction to obtain the nano material precursor of carbonate materials or nano oxyhydrate materials or hydrous oxide materials of the metal, wherein the prepared nano material is used as a nano metal oxide. The method has the advantages of scientific and reasonable structure, high quality of products, energy saving, no secondary pollution and the like.

Description

A kind of method for preparing nano material
Technical field
The present invention relates to a kind of method for preparing nano material.
Background technology
Research to nano material is field, a forward position in the current scientific research, also is the focus of the many scientific worker's researchs in the whole world.The magical part of nano material and also do not caused people's extensive concern especially for aspect that people knew; To research and present especially focus and the difficult point of application that nano material is prepared, also be the emphasis of develop high-tech.
Through constantly research and exploration, worked out some at present and prepared the method for nano material.These methods comprise: physical vaporous deposition (physical vapor deposition), chemical Vapor deposition process (chemical vapor deposition), the chemical reaction precipitator method (reactive precipitation), sol-gel method (sol-gel), microemulsion method (microemulsion), sonochemistry processing (sonochemical processing), overcritical chemical process (supercritical chemical processing) etc.Also favourablely synthesize some nano material with hydrothermal method.Wherein, the chemical reaction precipitator method are easy to process, and cost is low, but mass production, thereby be hopeful to be used for suitability for industrialized production most.But because the traditional chemical reaction precipitation course of processing is usually carried out in stirred pot or filler tower reactor, therefore be difficult to control quality product, there are very big difference in the distribution and the crystalline phase of the product particle diameter of different processing batch.
With the method for preparing Alpha-alumina is example: solid phase method is with after aluminium or the aluminium salt grinding calcining generation solid state reaction, directly obtain nano aluminium oxide, but the Granularity Distribution inequality that makes reunion takes place easily reunites; Liquid phase method is the most frequently used method of present nano materials, yet this method is introduced impurity easily, makes product purity not high; The product reunion that obtains by vapor phase process is few, good dispersity, and the little and narrowly distributing of particle diameter, but productive rate is low, and powder is easily collecting not, the cost costliness.Aluminum oxide is easy to take place particle agglomeration in the crystal conversion process, so be difficult to obtain the nano level product; In addition, because aluminum oxide crystalline phase purity is not high, assorted peak is many, be sintered into finished product α-Al by different precursors 2O 3Temperature range fluctuation usually between 1000 to 1500 ℃.Therefore, common production method of alumina is difficult to make the degree of crystallinity high product.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of efficient, method that fine prepares nano material is provided.
Purpose of the present invention is achieved by following technical proposals: comprise preparation nano material precursor and nano material; The described method for preparing the nano material precursor is reaction raw materials to be placed carry out in the super gravity field reactor obtaining the nano material precursor behind gas-liquid reaction or the liquid-liquid reactions; The described method for preparing nano material is with microwave field the nano material precursor to be carried out heating and calcining, makes the nano material precursor take place to obtain nano material behind decomposition or the commentaries on classics crystalline substance.
The described method for preparing the nano material precursor comprises, quicken and the reinforcing mass transfer process with super gravity field, make aqueous metal salt in the reactor and liquid precipitation agent or gas precipitation agent reach mixing of molecular scale, carry out chemical reaction, obtain the carbonate material of this metal or the nano material precursor of nanometer oxyhydroxide class material or hydrous oxide class material, its nano material for preparing is the oxide compound of nano level this metal.
The carbonate material of described metal is nano level zinc subcarbonate, manganous carbonate, magnesiumcarbonate etc.; Described nanometer oxyhydroxide class material is nano level zinc hydroxide, magnesium hydroxide or aluminium hydroxide etc.; Described hydrous oxide class material is nano level monohydrate alumina or hibbsite; The oxide compound of described metal is zinc oxide, Manganse Dioxide, trimanganese tetroxide, aluminum oxide, magnesium oxide.
The described method for preparing the nano material precursor comprises, the aqueous solution of at least a metal-salt or liquid mixture and liquid precipitation agent or gas precipitation agent coprecipitation reaction in the super gravity field reactor, generate the composite salt precursor of corresponding metal, its nano material for preparing is the composite salt of nano level metal.
The composite salt of described metal is BaTiO 3, SrTiO 3, BaSrTiO 3, ZrBa (Sr) TiO 3, nano-grade lithium iron phosphate, nanometer lithium manganese phosphate etc.
The described method for preparing the nano material precursor comprises, in super gravity field, make mixing solutions and liquid precipitation agent or gas precipitation agent coprecipitation reaction in reactor of yttrium salt and aluminium salt, generate nanometer LED fluorescent material YAG:Ce precursor, its nano material for preparing is nano level LED fluorescent material YAG:Ce.
Described liquid precipitation agent is the aqueous solution of ammoniacal liquor, aqueous solution of urea, ammonium bicarbonate aqueous solution, sodium hydroxide or potassium hydroxide; Described gas precipitation agent is a carbonic acid gas.
Centrifugal acceleration in the described super gravity field is 180-10000m/s 2, microwave frequency is 500-2450MHz in the described microwave field, the incinerating temperature is a 500-1600 degree Celsius, calcination time 10-240 minute.
Centrifugal acceleration in the described super gravity field is 5000-10000m/s 2, microwave frequency is 1800-2200MHz in the described microwave field, calcining temperature is a 700-1500 degree Celsius, calcination time 60-120 minute.
The average particulate diameter of described nano material is the 10-60 nanometer.
Compared with prior art, method of the present invention has scientific and reasonable, quality product height, save energy, advantages such as non-secondary pollution.
Description of drawings
Fig. 1 is the TEM figure of the pseudo-boehmite of embodiment 1.1 preparations.
Fig. 2 is the nanometer α-Al of comparative example 1 preparation 2O 3XRD figure.
Fig. 3 is the nanometer α-Al of embodiment 1.6 preparations 2O 3XRD figure.
Fig. 4 is the nanometer α-Al of embodiment 1.6 preparations 2O 3Crystal lines figure.
Fig. 5 is the nanometer α-Al of embodiment 1.6 preparations 2O 3TEM figure.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Method of the present invention comprises preparation nano material precursor and nano material; The described method for preparing the nano material precursor is reaction raw materials to be placed carry out in the super gravity field reactor obtaining the nano material precursor behind gas-liquid reaction or the liquid-liquid reactions; The described method for preparing nano material is with microwave field the nano material precursor to be carried out heating and calcining, makes the nano material precursor take place to obtain nano material behind decomposition or the commentaries on classics crystalline substance.
The described method for preparing the nano material precursor comprises, quicken and the reinforcing mass transfer process with super gravity field, make aqueous metal salt in the reactor and liquid precipitation agent or gas precipitation agent reach mixing of molecular scale, carry out chemical reaction, obtain the carbonate material of this metal or the nano material precursor of nanometer oxyhydroxide class material or hydrous oxide class material, its nano material for preparing is the oxide compound of nano level this metal.
According to well known to a person skilled in the art technology and method, to the mixing solutions of the carbonate material that generates described metal or nanometer oxyhydroxide class material or hydrous oxide class material carry out ageing, filtration, aging, separate and dry, dried solids is exactly the nano material precursor.
The carbonate material of described metal is nano level zinc subcarbonate, manganous carbonate, magnesiumcarbonate etc.; Described nanometer oxyhydroxide class material is nano level zinc hydroxide, magnesium hydroxide or aluminium hydroxide etc.; Described hydrous oxide class material is nano level monohydrate alumina or hibbsite; The oxide compound of described metal is zinc oxide, Manganse Dioxide, trimanganese tetroxide, aluminum oxide, magnesium oxide.
The described method for preparing the nano material precursor comprises, the aqueous solution of at least a metal-salt or liquid mixture and liquid precipitation agent or gas precipitation agent coprecipitation reaction in the super gravity field reactor, generate the composite salt precursor of corresponding metal, its nano material for preparing is the composite salt of nano level metal.
The composite salt of described metal is BaTiO 3, SrTiO 3, BaSrTiO 3, ZrBa (Sr) TiO 3, nano-grade lithium iron phosphate, nanometer lithium manganese phosphate etc.
The described method for preparing the nano material precursor comprises, in super gravity field, make mixing solutions and liquid precipitation agent or gas precipitation agent coprecipitation reaction in reactor of yttrium salt and aluminium salt, generate nanometer LED fluorescent material YAG:Ce precursor, its nano material for preparing is nano level LED fluorescent material YAG:Ce.
Described liquid precipitation agent is the aqueous solution of ammoniacal liquor, aqueous solution of urea, ammonium bicarbonate aqueous solution, sodium hydroxide or potassium hydroxide; Described gas precipitation agent is a carbonic acid gas.
Centrifugal acceleration in the described super gravity field is 180-10000m/s 2, microwave frequency is 500-2450MHz in the described microwave field, the incinerating temperature is a 500-1600 degree Celsius, calcination time 10-240 minute.
Centrifugal acceleration in the described super gravity field is 5000-10000m/s 2, microwave frequency is 1800-2200MHz in the described microwave field, calcining temperature is a 700-1500 degree Celsius, calcination time 60-120 minute.
The average particulate diameter of described nano material is the 10-60 nanometer.
Embodiment:
It will be understood by those skilled in the art that following examples should not be considered as limitation of the present invention.
In following embodiment, the rotating bed with helix channel supergravity reactor of developing with University Of Xiangtan provides described super gravity field, and rotating speed generally is controlled to be 600-3000rpm, and the centrifugal acceleration in the super gravity field is controlled to be 180-10000m/s 2The microwave Muffle furnace of producing with U.S. CE M company provides described microwave field, and microwave frequency range can be adjusted in 500-2450MHz, preferably adjusts in 1800-2200MHz.
Embodiment 1: the preparation of nano-alpha aluminium oxide
In super gravity field, prepare the nano pseudo boehmite precursor earlier: make sodium aluminate solution and carbon dioxide contact reacts in hypergravity obtain pseudo-boehmite suspension, after carrying out ageing, filtration, burin-in process successively, isolating solid product, drying, obtain solid nano level pseudo-boehmite precursor.Specifically, the vapour-liquid ratio of the sodium metaaluminate aqueous solution and carbon dioxide is at 1-10: 1, be preferably 1-5: 1; The carbon dioxide that feeds has consumed sodium hydroxide excessive in the solution, and destroys the equilibrium system in the sodium aluminate solution, generates pseudo-boehmite precipitation (AlOOHnH 2O).Therefore, the temperature of reacting is 0-35 ℃, and rotating speed is controlled to be 1000rpm, and the centrifugal acceleration in the super gravity field is 180-10000m/s 2, be preferably 1000-6000g/m 2Preferred sodium metaaluminate concentration is lower than 1.0mol/L, more preferably 0.1-0.5mol/L.The poly(oxyethylene glycol) 400 organic polymer surface dispersant that preferably in carbonation reaction, adds weight percentage 1-2%.
Concrete operations: sodium aluminate solution and carbon dioxide carry out contact reacts in the reactor of super gravity field, write down temperature of reaction and pH value in the reactor at regular intervals, after the pH value stops ventilation near 10.5 the time, makes feed liquid recirculation for some time, unload feed liquid.After leaving standstill 1-3h at room temperature, filter, for several times with the deionized water wash filter cake; Add appropriate amount of deionized water then and carry out the hydrothermal aging processing in filter cake, aging temperature is controlled at 60-100 ℃, keeps digestion time 0.5-3h; Afterwards slurries are filtered, use rare NH 4NO 3Solution washing filter cake, the small amount of N a ion that contains in the flush away filter cake as far as possible.Add an amount of pure organic solvent and carry out pure burin-in process in the gained filter cake, 60-100 ℃ of control aging temperature keeps digestion time 0.1-1h, afterwards slurries filtered pure carrying out washing treatment.The filter cake of dry gained promptly obtains the nano pseudo boehmite precursor, and drying temperature is 90-110 ℃, time of drying 0.5-3h.
High-temperature calcination decomposition commentaries on classics crystalline substance prepares nanometer α-Al in microwave field 2O 3: the nano level pseudo-boehmite precursor that will make as stated above heats in microwave field and carries out high-temperature calcination, decomposes and changes the brilliant nanometer α-Al of one-tenth 2O 3Specifically, this method comprises a certain amount of above-mentioned nano pseudo boehmite precursor is placed corundum crucible, put into for frequency be 500-2450MHz, be preferably in the microwave field of 1800-2200MHz and carry out heating and calcining, the mode of heating comprises temperature programming or directly is rapidly heated, carrying out the incinerating temperature is 900-1200 ℃, is preferably 1100-1500 ℃, and calcination time is 1/6-4h.
Nanometer α-Al that the method according to this invention is prepared 2O 3The particle average particulate diameter is 10-20nm, and particle diameter distribution is narrow, and degree of crystallinity height and lines are clear, complete in crystal formation.
Embodiment 1.1
The concentration of getting certain mass is the sodium aluminate solution of 0.15-0.30mol/L, and by the poly(oxyethylene glycol) 400 organic polymer surface dispersant of its mass ratio adding 1-2%, the mixed solution behind the uniform mixing is standby.CO 2Gas is standby.Start helical channel type rotation field hypergravity bed and drive the reactor rotation, controlling its rotating speed is 1000-1200rpm, and mixed solution is joined by the valve that can regulate flow in the reactor of rotation, and regulating control mixed solution flow is 400L/h, after treating stability of flow, open CO 2It is 1.5: 1 that air valve, adjustments of gas flow make the gas-liquid throughput ratio, makes CO 2Also enter in the reactor of rotation, and with reactor in existing sodium aluminate solution carry out carburizing reagent, control reaction temperature is below 35 ℃, measure pH value of solution in the reaction process, close all valves when reaching near 10.5, helical channel type rotation field hypergravity bed reduces rotating speed and worked 10-20 minute again.
Take out feed liquid, at room temperature leave standstill 2h, filter and for several times with deionized water wash; Filter cake adds appropriate amount of deionized water and carries out hydrothermal aging and handle in filter cake, and it is 90 ℃ that aging temperature is set, digestion time 1h, and suction filtration with rare ammonium nitrate solution washing several, is removed the sodium ion in the filter cake as far as possible once more; Filter cake is added an amount of organic alcohol place 90 ℃ of water-bath 0.5h, filter and for several times with washing with alcohol.The gained filter cake is dry 2h in 90 ℃ of loft drier, promptly obtains nano pseudo boehmite.
From the product XRD figure shown in the accompanying drawing 1 as can be seen, the precursor nano pseudo boehmite that makes is fibrous, average particulate diameter at 5-10nm, be about 100nm.
Embodiment 1.2
Prepare pseudo-boehmite according to the method identical with embodiment 1.1, different is: the concentration of sodium aluminate solution is 0.3-0.5mol/L.Experiment shows: increased concentration of reactants, will prolong the time of carburizing reagent, when concentration was higher than 0.5mol/L, the phenomenon of the solution accumulation of salt in the surface soil appearred in carbonization process, was unfavorable for that carburizing reagent prepares nano pseudo boehmite.
Embodiment 1.3
Prepare pseudo-boehmite according to the method identical with embodiment 1.1, different is: the rotor speed of helical channel type rotation field hypergravity bed is respectively 600-900rpm and 1200-1600rpm.Experiment shows: the change of rotating speed is little to the speed influence of carburizing reagent, but rotating speed is big more, and microcosmic mixes even more, and the quality of nano pseudo boehmite is good more.
Embodiment 1.4
Prepare pseudo-boehmite according to the method identical with embodiment 1.1, different is: make vapour-liquid ratio be controlled to be 1.0: 1 and 2.0: 1.Experiment shows: vapour-liquid ratio is crossed when hanging down, and carbon divides reaction process to prolong, and it is not obvious to detect the pseudo-boehmite characteristic peak through XRD; When vapour-liquid ratio was too high, carbon divided in the process crystal nucleation phase and crystal growth phase boundary not obvious, made long big and inhomogeneous of crystal, and agglomeration easily takes place.
Embodiment 1.5
Take by weighing a certain amount of nano pseudo boehmite and place corundum crucible, put into microwave Muffle furnace, use the mode of being rapidly heated to be heated to 1200 ℃ and keep 2h by embodiment 1.1 preparation.The performance of product has tangible α-Al by the XRD detected result as can be known 2O 3Characteristic peak, particle diameter distribution is little, and assorted peak is little.
Comparative example 1
Take by weighing a certain amount of nano pseudo boehmite by embodiment 1.1 preparations and place corundum crucible, put into common retort furnace and calcine, it is 1200 ℃ that temperature is set, and calcination time is 2h.From product XRD figure shown in Figure 2 as can be seen, α-Al that this method makes 2O 3Degree of crystallinity is not high, and assorted peak is a lot, and by the SEM detected result as can be known, the product agglomeration is serious.
Embodiment 1.6
Prepare nanometer α-Al according to embodiment 1.5 identical methods 2O 3, different is: adopt temperature programming to heat, according to the TG-DTA detected result of pseudo-boehmite microwave procedure being heated up is provided with.From product XRD figure shown in Figure 3, can calculate the crystal grain diameter at 10-20nm according to the Scherrer formula; Can find that from Fig. 4 and TEM figure shown in Figure 5 the product particle diameter Distribution is narrow, the crystallization lines is clear, complete in crystal formation.
In sum, nanometer α-Al of preparing of the method according to this invention 2O 3The average particulate diameter of particle is about 10-20nm, and particle diameter distribution is narrow, and degree of crystallinity height and lines are clear, complete in crystal formation.
This method has following beneficial effect:
I), this method can adopt industrial production intermediate product NaAlO 2Solution and CO 2Gas is as raw material, and the nano pseudo boehmite precursor for preparing in super gravity field is fibrous, and average particulate diameter is 5-10nm, be about 100nm; Super gravity field can be provided by helical channel type rotation hypergravity bed RBHC, has solved the rotating packed bed RPB that adopts in the traditional method thus and has been easy to blocking problem, for a brand-brand-new way has been opened up in the production of nano-functional material;
Ii), can wait form and the granular size of controlling the pseudo-boehmite precursor that makes by reaction conditions, terminal point pH, weathering process condition, the drying conditions that is adjusted in the hypergravity;
Iii), nanometer α-Al of preparing of this method 2O 3Average particulate diameter be about 10-20nm, particle diameter distribution is narrow, degree of crystallinity height and lines are clear, complete in crystal formation has overcome the nanometer α-Al that makes with conventional art 2O 3The particle diameter distribution inequality, crystalline phase is impure, the not high shortcoming of degree of crystallinity.
Embodiment 2: the preparation of nano zine oxide
Zinc salt solution is joined in the reactor of helical channel type rotation hypergravity bed, the adjusting rotating speed is 600-3000rpm, the ON cycle pump, the flow of control zinc salt solution is 100-600L/h, behind stability of flow, feed the liquid precipitation agent, make it in rotating bed with helix channel, carry out liquid-liquid reactions.Unload feed liquid after reacting completely, filter, subsequent disposal operations such as drying promptly obtain nano-calcium carbonate zinc precipitation presoma.Described zinc salt is zinc nitrate, zinc sulfate or zinc chloride, and the liquid precipitation agent is ammoniacal liquor or ammonium bicarbonate aqueous solution.
Nano-calcium carbonate zinc precipitation presoma is decomposed in high-temperature calcination in microwave field: the nanometer grade zinc carbonate precipitation presoma that will make as stated above heats in microwave field and carries out high-temperature calcination, resolves into nano zine oxide.Specifically, this method comprises that a certain amount of above-mentioned nano-calcium carbonate zinc is precipitated presoma places corundum crucible, put into to microwave Muffle furnace and carry out heating and calcining, the mode of heating comprises temperature programming or directly is rapidly heated, carrying out the incinerating temperature is 500-800 ℃, be preferably 500-700 ℃, calcination time is 1/6-4h.
Embodiment 3: the preparation of nano manganic manganous oxide, nano-manganese dioxide
Manganese salt solution is joined in the reactor of helical channel type rotation hypergravity bed, the adjusting rotating speed is 600-3000rpm, Qidong recycle pump, the flow of control manganese salt solution is 100-600L/h, behind stability of flow, feed the liquid precipitation agent, make it in rotating bed with helix channel, carry out liquid-liquid reactions.Unload feed liquid after reacting completely, filter, pure carrying out washing treatment.The filter cake of gained is carried out drying treatment, and drying temperature is 90-110 ℃, and time of drying, 0.5-3h promptly obtained nano-calcium carbonate manganese precipitation presoma.Described manganese salt is manganous nitrate, manganous sulfate or Manganous chloride tetrahydrate, and the liquid precipitation agent is ammoniacal liquor or ammonium bicarbonate aqueous solution.
Nano-calcium carbonate manganese precipitation presoma is decomposed in high-temperature calcination in microwave field: the nano level carbonic acid manganese precipitation presoma that will make as stated above heats in microwave field and carries out high-temperature calcination, resolves into nano manganese oxide.Specifically, this method comprises that a certain amount of above-mentioned nano-calcium carbonate manganese is precipitated presoma places corundum crucible, put into to microwave Muffle furnace and carry out heating and calcining, the mode of heating comprises temperature programming or directly is rapidly heated, carrying out the incinerating temperature is 500-800 ℃, be preferably 500-700 ℃, calcination time is 1/6-4h.
Embodiment 4: the preparation of nano barium phthalate
Preparation is earlier reacted with barium titanium mixed solution: take by weighing a certain amount of TiCl 4In ice-water bath, be hydrolyzed and obtain TiOCl 2The aqueous solution, concentration is controlled at 1-2mol/L.In n (Ba): n (Ti) mol ratio is that 1.02: 1 ratio takes by weighing BaCl22H2O, behind a certain amount of dissolved in distilled water, with TiOCl 2Aqueous solution obtains barium titanium mixed solution.
Join in the reactor of helical channel type rotation hypergravity bed to the barium titanium mixed solution that makes,, mix the back solution is heated to wherein adding certain amount of surfactant.Be heated to (being preferably 35-70 ℃) after the certain temperature, start helical channel type rotation hypergravity bed, the adjusting rotating speed is 600-3000rpm (being preferably rotating speed is 600-2000rpm), start recycle pump, the flow of control barium titanium mixed solution is 100-600L/h, behind stability of flow, adds the NaOH aqueous solution, make it carry out liquid-liquid reactions in rotating bed with helix channel, liquid-liquor ratio is 1-5: 1.Reaction 1-2h generates BaTiO 3Post precipitation unloads feed liquid, filters, and washing obtains nanometer BaTiO to there not being chlorion 60 ℃ of following dryings 3Presoma is 20-60nm by XRD figure count particles diameter.
Take by weighing a certain amount of above-mentioned nanometer BaTiO 3Presoma places corundum crucible, puts into microwave Muffle furnace and carries out high-temperature calcination commentaries on classics crystalline substance, and heating mode is temperature programming or directly is rapidly heated that calcining temperature is 950-1200 ℃, calcination time 1/6-4h.The reaction finish after by nanometer BaTiO 3Presoma changes the brilliant cubic phase nano BaTiO of one-tenth 3Material, particle diameter are at 20-60nm.
Thus, thereby the method according to this invention can be simply rotating speed by operating device be that the field acceleration of may command super gravity field is prepared the particle diameter of nanometer presoma, and can control finished product cubic phase nano BaTiO easily by the particle diameter of controlling the nanometer presoma 3The particle diameter of material.
Embodiment 5: the preparation of nano-grade lithium iron phosphate
Adopt coprecipitation method in the reactor of helical channel type rotation hypergravity bed, to carry out liquid-liquid reactions and prepare the nano-grade lithium iron phosphate precursor.Fe in molar ratio 2+: Li +: PO 4 3-: OH -=1: 1.05: 1: 2 relation is added drop-wise to FeSO lentamente with LiOH solution and ammoniacal liquor 4And H 3PO 4Mixing solutions in, stir, the pH value with ammoniacal liquor control reaction is 8 to 10 simultaneously.After reaction is finished, precipitation is washed and suction filtration, place 60 ℃ of dry 6h of vacuum drying oven.Obtain the nano-grade lithium iron phosphate precursor.
At N 2Under the gas shield, in microwave Muffle furnace above-mentioned nano-grade lithium iron phosphate precursor is calcined the commentaries on classics crystalline substance, calcining temperature is 650-800 ℃, and calcination time is 1.5-2h, obtains the nanometer iron lithium phosphate of olivine structural.
The temperature that method of the present invention prepares iron lithium phosphate is low, and batch mixing is even, makes product all be better than existing method at aspects such as composition, structure, size-grade distribution; Method of the present invention can be prepared the nanometer iron lithium phosphate of epigranular, high-purity, good dispersity, narrow diameter distribution, charge-discharge performance excellence.
Embodiment 6: the preparation of nanometer YAG:Ce fluorescent material
The mixing solutions of preparation yttrium aluminium salt: the mol ratio according to aluminium and yttrium is 5: 3, takes by weighing nine water aluminum nitrate 18.75g, and six water Yttrium trinitrate 11.49g add water to 1000ml and mix (total cation concentration should between 0.01 to 0.05), adding Ce (NO 3) 3, what add 20g in mixing solutions adds PEG (400).
According to the mol ratio of bicarbonate of ammonia and ammoniacal liquor 1: 2, take by weighing bicarbonate of ammonia 15.14g, ammoniacal liquor 10g adds deionized water and is mixed with mixed precipitant to 200ml.
Carry out liquid-liquid reactions then in the reactor of helical channel type rotation hypergravity bed: at room temperature add the mixing solutions of the above-mentioned yttrium aluminium salt of 10L, the mode that adopts the forward dropping is to wherein adding above-mentioned mixed precipitant.Every 2min surveys a pH value, reaches about 7.0 until the pH value, stops to drip precipitation agent.After stopping to drip, continue reaction 1h.Wore out 12 hours at 60 ℃ of following constant temperature then.Be placed in the air dry oven through suction filtration, washing, freeze-day with constant temperature 12h obtains the nanometer YAG:Ce fluorescent material precursor of white powder under 60 ℃ of conditions.
Two corundum crucibles that above-mentioned nanometer YAG:Ce fluorescent material precursor and gac are housed are respectively put into the microwave high-temperature stove, calcine 2h down at 1000 ℃ or 1100 ℃ and be prepared into LED fluorescent material nanometer YAG:Ce powder.
This method is in super gravity field, with Y (NO 3) 3, Ce (NO 3) 3And Al (NO 3) 3For preparation of raw material becomes solution and NH 4HCO 3Solution prepares presoma by the liquid phase reaction precipitator method, the presoma for preparing is carried out the LED fluorescent material that high-temperature roasting both can have been prepared efficient nano under the microwave field again, i.e. the YAG:Ce powder.
Method of the present invention provides combines the method for carrying out mass transfer reaction and carrying out pyroprocessing in overweight in microwave field and can prepare epigranular, high-purity, ultra-fine spherical, good dispersity, particle diameter distribution is narrow, luminescent properties is excellent good fluorescent material.

Claims (10)

1. a method for preparing nano material comprises preparation nano material precursor and nano material; It is characterized in that the described method for preparing the nano material precursor is reaction raw materials to be placed carry out in the super gravity field reactor obtaining the nano material precursor behind gas-liquid reaction or the liquid-liquid reactions; The described method for preparing nano material is with microwave field the nano material precursor to be carried out heating and calcining, makes the nano material precursor take place to obtain nano material behind decomposition or the commentaries on classics crystalline substance.
2. the method for preparing nano material according to claim 1, it is characterized in that, the described method for preparing the nano material precursor comprises, quicken and the reinforcing mass transfer process with super gravity field, make aqueous metal salt in the reactor and liquid precipitation agent or gas precipitation agent reach mixing of molecular scale, carry out chemical reaction, obtain the carbonate material of this metal or the nano material precursor of nanometer oxyhydroxide class material or hydrous oxide class material, its nano material for preparing is the oxide compound of nano level this metal.
3. the method for preparing nano material according to claim 2 is characterized in that, the carbonate material of described metal is nano level zinc subcarbonate, manganous carbonate, magnesiumcarbonate etc.; Described nanometer oxyhydroxide class material is nano level zinc hydroxide, magnesium hydroxide or aluminium hydroxide etc.; Described hydrous oxide class material is nano level monohydrate alumina or hibbsite; The oxide compound of described metal is zinc oxide, Manganse Dioxide, trimanganese tetroxide, aluminum oxide, magnesium oxide.
4. the method for preparing nano material according to claim 1, it is characterized in that, the described method for preparing the nano material precursor comprises, the aqueous solution of at least a metal-salt or liquid mixture and liquid precipitation agent or gas precipitation agent coprecipitation reaction in the super gravity field reactor, generate the composite salt precursor of corresponding metal, its nano material for preparing is the composite salt of nano level metal.
5. the method for preparing nano material according to claim 4 is characterized in that, the composite salt of described metal is BaTiO 3, SrTiO 3, BaSrTiO 3, ZrBa (Sr) TiO 3, nano-grade lithium iron phosphate, nanometer lithium manganese phosphate etc.
6. the method for preparing nano material according to claim 1, it is characterized in that, the described method for preparing the nano material precursor comprises, in super gravity field, make mixing solutions and liquid precipitation agent or gas precipitation agent coprecipitation reaction in reactor of yttrium salt and aluminium salt, generate nanometer LED fluorescent material YAG:Ce precursor, its nano material for preparing is nano level LED fluorescent material YAG:Ce.
7. according to the described method for preparing nano material of any claim among the claim 2-6, it is characterized in that described liquid precipitation agent is the aqueous solution of ammoniacal liquor, aqueous solution of urea, ammonium bicarbonate aqueous solution, sodium hydroxide or potassium hydroxide; Described gas precipitation agent is a carbonic acid gas.
8. according to any described method for preparing nano material among the claim 1-6, it is characterized in that the centrifugal acceleration in the described super gravity field is 180-10000m/s 2, microwave frequency is 500-2450MHz in the described microwave field, the incinerating temperature is a 500-1600 degree Celsius, calcination time 10-240 minute.
9. according to any described method for preparing nano material among the claim 1-6, it is characterized in that the centrifugal acceleration in the described super gravity field is 5000-10000m/s 2, microwave frequency is 1800-2200MHz in the described microwave field, calcining temperature is a 700-1500 degree Celsius, calcination time 60-120 minute.
10. according to any described method for preparing nano material among the claim 1-6, it is characterized in that the average particulate diameter of described nano material is the 10-60 nanometer.
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