CN105655551B - A kind of quick method for preparing and separating inorganic nanoparticles - Google Patents

A kind of quick method for preparing and separating inorganic nanoparticles Download PDF

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CN105655551B
CN105655551B CN201610001440.8A CN201610001440A CN105655551B CN 105655551 B CN105655551 B CN 105655551B CN 201610001440 A CN201610001440 A CN 201610001440A CN 105655551 B CN105655551 B CN 105655551B
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nano particle
water
suspension
inorganic nanoparticles
aqueous solution
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CN105655551A (en
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朱正曦
刘宁宁
薛怀国
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Yangzhou University
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Yangzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
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Abstract

A kind of quick method for preparing and separating inorganic nanoparticles, belong to the preparing technical field of inorganic nanoparticles.By the aqueous solution of at least two water-soluble inorganic salts and pH response polyelectrolyte class surfactants in blender airtight cavity; it is blended through online reactive turbulent flow; generate nano particle suspension; adjust the pH value of nano particle suspension; nano particle is assembled mutually and settled; it is separated from water by filtering with reaching, then it is scrubbed, dry, obtain the powder of inorganic nanoparticles.Present invention preparation is quick, power consumption is low, equipment is simple, easily operated.The nanoparticle size of preparation is small, is nanoscale.This method is simple, efficient, can avoid particle Ostwald ripening and particle diameter increase caused by long disengaging time.

Description

A kind of quick method for preparing and separating inorganic nanoparticles
Technical field
The invention belongs to the preparing technical field of inorganic nanoparticles.
Background technology
Lead sulfate is a kind of important chemical products as inorganic matter, energy-storage battery, Chinese white, quick drying paint and The fields such as printing have a wide range of applications.Although the quality of lead-acid accumulator is with energy density per unit volume less than cadmium nickel, metal hydride Nickel, lithium ion and polymer lithium-ion battery, but lead-acid accumulator still occupies storage by its excellent cost performance The energy Battery Market share of more than half.And it is of a relatively high because of the stability, reliability and security of lead-acid battery, it is applicable Environment is more extensive, so to being still most important energy-storage battery at present.Lead sulfate exists as the active material of lead-acid battery electrode Consumed during charging, formed during electric discharge, be the key chemical part of lead-acid battery.At the same time, nano material has big Specific surface area.After active electrode material nanosizing, per surface area current density reduces, therefore polarizes and reduce so that electric capacity Amount increase so that the stored energy capacitance of battery is improved, while the service life of battery is extended.Therefore, electrode activity material The particle diameter of material has on battery performance and significantly influenceed.Conventional lead-sulphate preparation technology long flow path, high energy consumption, is also easy to produce leaded Steam and dust, the health of operating personnel can be not only endangered, and environment can be caused seriously to pollute.
The content of the invention
The present invention seeks to propose it is a kind of simple, quick, efficiently, prepare and separate to energy-saving and environmental protection inorganic nanoparticles Method.
The technical scheme is that：The aqueous solution of at least two water-soluble inorganic salts and pH response surfactants is same When high speed injecting mixer airtight cavity in, be blended by online reactive turbulent flow, the slightly water-soluble of generation reacted between inorganic salts Inorganic matter instantaneous separate out in water forms nano particle, and pH response SURFACTANT ADSORPTIONs are received in nano grain surface with limiting Rice grain further growth, the suspension containing nano particle flow out from mixer outlet；Adjust the suspension of nano particle PH value, the pH responses surfactant of nano grain surface is changed into hydrophobicity from hydrophily, nano particle assemble mutually and Sedimentation, is filtered to reach the separation and concentration of nano particle；It is scrubbed again, dry, obtain the powder of inorganic nanoparticles.
The present invention first by least two water-soluble inorganic salting liquids in the airtight cavity of blender online reactive turbulent flow Blending generation difficultly water soluble salts, the salt of generation is because solubility is low and instantaneously separate out in water, from mixing in the form of suspension Device outlet outflow.Turbulent flow blending in cavity result in high-energy-density dissipation, the salt of precipitation is formed nano particle；Separately Outside, pH response surfactants are added with an at least solution in described two water-soluble inorganic salting liquids.On the one hand, The surfactant can be adsorbed in nano grain surface in nano particle forming process to limit further increasing for particle.Separately On the one hand, can mutually be changed between water-soluble and water is insoluble by adjusting the pH value surfactant.Therefore, by adjusting The pH value of the nano particle suspension arrived, it is possible to achieve the rapid aggregation of nano particle and sedimentation, then filtered, washing, drying, Obtain the dusty material of nano particle.PH is adjusted back, the nano particle can be dispersed in water again.
There is low energy to input, be quick, be efficient by the present invention, clean non-dusting feature.In addition, the conventional nano particle that compares Centrifugal separation method, have method equipment simple, efficiently, it is often more important that to be substantially shorter disengaging time, avoid nanometer The grain length time is in aqueous systems because Ostwald ripening causes the increase of particle size.
The mixing chamber is closed housing, and single entry injection rate is in 0.1 more than m/s, to ensure online reaction Property turbulent flow Blending Processes have the dissipation of high reynolds number and high-energy-density.
For the ease of two kinds of solution while injecting mixer cavity, and the nano particle suspension of generation is discharged immediately, Blender of the present invention is provided with least two fluid-infusing ports and a flow export.
In order to ensure that in cavity precipitation reaction can occur for two kinds of salt and separate out, two kinds of water-soluble inorganic salts of the present invention A kind of salt of solution is at least one of the lead of nitric acid or hydrochloric acid, calcium, barium, silver, zinc salt；Another salt be sulfuric acid, carbonic acid or At least one of sodium, potassium, ammonium, hydrogen sodium, hydrogen potassium or hydrogen ammonium salt of halogen.
The aqueous solution of pH responses polyelectrolyte class surfactant of the present invention, such as chitosan aqueous solution.Certain Under the conditions of pH, the polymer belt electric charge is water soluble surfactant active, can be adsorbed in nano grain surface, while provide particle Between steric hindrance and electrical charge rejection, played in particle precipitation process limitation particle size growth ensure that particle is in nanoscale, The time stability of nanoparticle size is provided after preparation.By adjusting the pH of nano particle suspension, adsorb in particle surface The electric charge of polymer be neutralized and be changed into from water solubility water-insoluble, nano grain surface is changed into hydrophobicity, between particle from And mutually agglomerate size increase, the sedimentation of particle and with water stratification accelerate.Meanwhile because particle size increase is advantageous to suspension Effectively filtering.
PH responses polyelectrolyte class surfactant of the present invention is chitosan.In pH<5 be positively charged, can To adsorb in particle surface, there is provided steric hindrance and Coulomb repulsion between particle, to improve the dispersiveness of particle.In pH>5, particle table The chitosan electric charge in face, which is neutralized, is changed into hydrophobicity, and particle also transitions into hydrophobicity, each other rapid reunion Accelerated subsidence.Cause This, the pH value of injecting mixer airtight cavity chitosan aqueous solution of the present invention is less than 5；Adjust the pH of the suspension of nano particle Value is more than 5.
Figure of description
Fig. 1 is preparation and the separation schematic diagram of inorganic nanoparticles.
The grain size distribution of lead sulfate nanometer suspension when Fig. 2 is 10 minutes after being prepared by embodiment one（DLS）.
Fig. 3 is the ESEM shape appearance figure of the lead sulfate powder prepared by embodiment one.
Fig. 4 is the grain size distribution for the lead sulfate nanometer suspension that the chitosan prepared by embodiment two is protected（DLS）.
Fig. 5 is the ESEM shape appearance figure for the lead sulfate powder that the chitosan prepared by embodiment two is protected.
Fig. 6 is that the lead sulfate nano particle that the chitosan prepared by embodiment two is protected adjusts back pH<Disperse again again after 5 The grain size distribution of suspension in water（DLS）.
Fig. 7 is that the lead sulfate nano particle suspension that the chitosan prepared by embodiment two is protected adjusts back pH<Weighed again after 5 The scanning electron microscope (SEM) photograph being newly dispersed in water.
Fig. 8 is the grain size distribution for the lead sulfate nanometer suspension that the chitosan prepared by embodiment three is protected（DLS）.
Fig. 9 is the CaCO prepared by example IV3The scanning electron microscope (SEM) photograph of nano particle.
Figure 10 is the Zn (OH) prepared by embodiment five2The scanning electron microscope (SEM) photograph of nano particle.
Figure 11 is the scanning electron microscope (SEM) photograph of the AgCl nano particles prepared by embodiment six.
Figure 12 is the BaSO prepared by embodiment seven4The scanning electron microscope (SEM) photograph of nano particle.
Embodiment
Non- open closed mixer is used in following examples, mixing chamber contains at least two fluid-infusing ports and one Flow export.
Embodiment one：
Sodium sulphate and plumbi nitras are weighed, is dissolved in the aqueous sodium sulfate for being made that concentration is 0.5 mol/L in deionized water respectively Liquid and the plumbi nitras aqueous solution that concentration is 0.05 mol/L.
Above-mentioned two solution of 10mL is taken, while blender is entered with identical speed injection, injects time-consuming about 10 s altogether.Two fluids Abundant turbulent closure scheme and reaction are carried out in blender cavity, the lead sulfate suspension of preparation flows out from mixer outlet, with appearance Device is collected.
The lead sulfate suspension of collection by centrifuging, washing, dry after lead sulfate powder of nanometric particles.Obtained nanometer Particle powder can not in water again mechanical dispersion into nano particle.With dynamic light scattering (DLS) and ESEM (SEM) to sulphur Lead plumbate powder of nanometric particles is characterized, as a result as shown in Figures 2 and 3.
PH response surfactant chitosans are not added in this embodiment, are opposed with the addition chitosan with embodiment two Than.Embodiment one shows that the average diameter of particles for being not added with chitosan acquisition is larger, and separates needs and take centrifugation.
Embodiment two：
Take a certain amount of plumbi nitras and chitosan soluble in water respectively, with hydrochloric acid conditioning solution pH<5, wherein plumbi nitras is molten Liquid concentration is 0.1 mol/L, and chitosan is 0.45 mg/mL；Another configuration aqueous sodium persulfate solution 0.5 mol/L.
Above-mentioned two solution of 10mL is taken, while blender is entered with identical speed injection, injects time-consuming about 10 s altogether.Two fluids Abundant turbulent closure scheme and reaction are carried out in blender cavity, the lead sulfate suspension of preparation flows out from mixer outlet, with appearance Device is collected.Its particle size and distribution are measured with dynamic light scattering method（Fig. 4）, regulation rise suspension pH>5, sulphur Lead plumbate nanoparticle precipitate separates out, to the precipitation lead sulfate powder of nanometric particles that is filtered, washed, be dried to obtain, and with sweeping Retouch Electronic Speculum and carry out morphology characterization（Fig. 5）.
The 0.01 g powder of nanometric particles weighed is dissolved in 10 mL water and adjusts pH<5, it is fast by the min of mechanical agitation 3 Speed is dispersed in water.The measure of dynamic light scattering is carried out to obtained suspension（Fig. 6）, and carry out morphology characterization with ESEM （Fig. 7）.
Embodiment three：
Take a certain amount of plumbi nitras and chitosan soluble in water respectively, with hydrochloric acid conditioning solution pH<5, wherein plumbi nitras Solution concentration is 0.01 mol/L, and chitosan is 0.45 mg/mL；Another configuration concentration is 0.1mol/L aqueous sodium persulfate solutions.
Above-mentioned two solution of 10mL is taken, while blender is entered with identical speed injection, injects time-consuming about 10 s altogether.Two fluids Abundant turbulent closure scheme and reaction are carried out in blender cavity, the lead sulfate suspension of preparation flows out from mixer outlet, with appearance Device is collected.Its particle size and distribution are measured with dynamic light scattering method, as a result as shown in Figure 8.
This embodiment reduces the concentration of two kinds of inorganic salts to be compared with example two, the nano particle of acquisition is as a result shown Average-size increased.
Example IV-six：
The aqueous solution of two kinds of inorganic salts and chitosan is respectively configured, solution concentration is shown in Table 1.
The particle diameter for the different inorganic salts nano particles that table 1. is prepared by example IV-six：
Above-mentioned two solution of 10 mL is taken, while blender is entered with identical speed injection, injects time-consuming about 10 s altogether.Two plumes Body carries out abundant turbulent closure scheme and reaction in blender cavity, and the suspension of preparation flows out from mixer outlet, received with container Collect suspension.Drying nano particle is separated, diameter characterization is carried out to powder of nanometric particles with ESEM, the results are shown in Table 1 and Fig. 9 Shown in Figure 12.

Claims (6)

  1. A kind of 1. quick method for preparing and separating inorganic nanoparticles, by least two water-soluble inorganic salts and pH response tables In injecting mixer airtight cavity, it is molten to generate shipwreck simultaneously by online reactive turbulent flow blending reaction for the aqueous solution of face activating agent Property inorganic matter, slightly water-soluble inorganic matter instantaneous separate out in water form nano particle, and pH responses SURFACTANT ADSORPTION is being received Rice grain surface forms the suspension containing nano particle and flowed out from blender flow export；Adjust the pH of the suspension of nano particle Value, makes the pH responses surfactant of nano grain surface be changed into hydrophobicity from hydrophily, nano particle is assembled mutually and sunk Drop, is filtered to reach the separation and concentration of nano particle；It is scrubbed again, dry, obtain the powder of inorganic nanoparticles.
  2. 2. method according to claim 1, it is characterised in that：During the online reactive turbulent flow blending, blender closed chamber The single entry injection rate of body is 0.1 more than m/s.
  3. 3. method according to claim 1, it is characterised in that：The blender is provided with least two fluid-infusing ports and one Flow export.
  4. 4. method according to claim 1, it is characterised in that：A kind of salt of described two water-soluble inorganic salting liquids is nitric acid Or at least one of the lead of hydrochloric acid, calcium, barium, silver, zinc salt；Another salt is sodium, potassium, ammonium, hydrogen sodium, the hydrogen potassium of sulfuric acid or carbonic acid Or at least one of hydrogen ammonium salt.
  5. 5. method according to claim 1, it is characterised in that：The aqueous solution of the pH responses surfactant is chitosan The aqueous solution.
  6. 6. method according to claim 5, it is characterised in that：The pH of injecting mixer airtight cavity chitosan aqueous solution Value is less than 5；The pH values for adjusting the suspension of nano particle are more than 5, and chitosan is changed into hydrophobicity from hydrophily.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1373083A (en) * 2001-03-07 2002-10-09 鞍山钢铁学院 Process for preparing size-controllable nano-powder
CN102698647A (en) * 2012-05-17 2012-10-03 武汉大学 PH sensitive-type gemini surface active agents and synthesis method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1373083A (en) * 2001-03-07 2002-10-09 鞍山钢铁学院 Process for preparing size-controllable nano-powder
CN102698647A (en) * 2012-05-17 2012-10-03 武汉大学 PH sensitive-type gemini surface active agents and synthesis method thereof

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