CN111017899A - Iron phosphate with nano-microporous structure and preparation method thereof - Google Patents
Iron phosphate with nano-microporous structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses iron phosphate with a nano-microporous structure, wherein nano-microporous channels are distributed on the outer surface and inside of the iron phosphate, the nano-microporous channels extend inside and outside the iron phosphate, and the pore diameter of the nano-microporous channels is less than 50 nm. The invention also discloses a preparation method of the iron phosphate with the nano-microporous structure, which comprises the following steps: carrying out molecular polymerization treatment on an iron source, converting the iron source from a monomolecular state into a high-molecular polymerization state, mixing and stirring the iron source and a phosphoric acid solution under the condition of controlling the temperature, and replacing phosphate radicals with acid radicals of the iron source under the condition of not damaging the polymerization state of the iron source to form an iron phosphate solution with a polymerization structure; adding a diluted alkaline solution into the iron phosphate solution under the condition of controlling the temperature to adjust the pH value for reaction to form a mixed suspension of iron phosphate and soluble salts; ball milling or sanding is carried out on mixed suspension containing the ferric phosphate and soluble salts, the soluble salts in the mixed suspension are washed by water and then dried, and the ferric phosphate is obtainedHas a specific surface area of up to 90m2More than g.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to iron phosphate with a nano microporous structure and a preparation method thereof.
Background
Ferric phosphate, also known as ferric phosphate, ferric orthophosphate, of the molecular formula FePO4It is white and off-white monoclinic crystal powder. The high-purity ferric phosphate dihydrate is nearly white or light (pale) yellowish white powder, the color gradually turns yellow along with the loss of crystal water, and pure anhydrous ferric phosphate is yellowish white powder, is mainly used for manufacturing lithium iron phosphate battery materials, can also be used as a catalyst and for manufacturing lithium iron phosphate batteriesCeramics, and the like.
Ferric phosphate is one of the most approved molluscicides used in organic agriculture, and unlike metaldehyde which has been used previously, it is not toxic to pets and wildlife. The use of this material in steel and metal manufacturing processes to bond iron phosphate to the metal surface prevents further oxidation of the metal, the presence of which may explain in part the corrosion resistance of the drite column. Iron phosphate coatings are also used primarily as base coatings to increase adhesion to iron or steel surfaces and are commonly used for rust prevention treatments. It can also be used to bond facings, wood, or other materials to the surface of such materials, with ferric phosphate being applied as part of the painting or dusting process. Although iron phosphate has low conductivity, it can also be used as an embedded electrode of a lithium ion battery, however, as the conductivity problem is overcome by material engineers, it is more and more common to be used as an electrode material in recent years, because of FePO4Is stable to heat, is generally easy to recycle, and is an ideal electrode material for batteries of electric vehicles.
The iron phosphate has rich chemical structure, so that the iron phosphate has important application in the fields of catalysis, lithium battery electrode materials and the like. In addition, the ferric phosphate also has a rich framework structure, and can be used for synthesizing a microporous ferric phosphate material with a hollow framework structure.
At present, the installed scale of a global electrochemical energy storage project reaches 697.1MW, wherein the installed scale of a Chinese electrochemical energy storage project reaches 100.4MW, and in the technical distribution of electrochemical energy storage, a lithium ion battery reaches 99% of market share and is far higher than a lead-acid battery and a flow battery, wherein the lithium iron phosphate battery occupies most shares, and the demand of the lithium iron phosphate battery is also increased rapidly along with the main raw material of the lithium iron phosphate positive electrode material.
At present, the preparation process of the iron phosphate is various, and the prepared iron phosphate has mixed components and various structures. The lithium iron phosphate prepared by using the iron phosphate as a matrix material seriously affects various performances of the lithium iron phosphate material and indirectly affects various performances of the lithium iron phosphate battery.
Chinese patent 110104624A discloses a preparation method of porous iron phosphate, which physically expands in iron phosphate to generate a pore diameter channel by using a mode that a foaming microsphere expands in the heating process; chinese patent 110182779a discloses a "method for preparing porous material of iron phosphate", wherein during the preparation process, when the intermediate product is sintered in air, acetylene black is oxidized and volatilized, so that the iron phosphate covering the surface of the acetylene black forms sphere-like particles with open pores ", and the pore diameter channel is physically expanded in the iron phosphate, when the intermediate product is sintered in nitrogen, the acetylene black can be well dispersed in the iron phosphate, …" can deduce that only the acetylene black on the surface of the iron phosphate contacting with air volatilizes to form a pore diameter, and the acetylene black inside the iron phosphate or not enough contacting with air does not volatilize, so that the pore diameter is not formed, and the acetylene black still remains in the iron phosphate in the form of the acetylene black.
The pore-forming methods disclosed in the two patents are both physical molding, in which a substance capable of being oxidized and volatilized at high temperature is added into iron phosphate, and a pore-diameter channel is physically expanded in the iron phosphate in a manner of oxidizing and volatilizing the substance at high temperature. The holes are formed physically, the holes cannot be communicated with each other, although a certain specific surface area can be increased, the holes cannot be communicated with each other, the lithium ion channels in the crystals are not effectively communicated, and due to the fact that the pore diameters are in micron-sized, the overlarge pore diameters occupy the volume of the excessive iron phosphate, so that effective ingredients are greatly reduced, the number of the pore channels is reduced, and the energy density of finished products is influenced.
The impurities in the Chinese patent 110104624A are two types, namely soluble salts generated by synthesizing iron phosphate; one type is "expanded microspheres". The method for removing soluble salt impurities is washing, the method for removing the 'foaming microspheres' is sintering, the 'foaming microspheres' coated by the ferric phosphate cannot be confirmed to be completely volatilized in actual production, and residues of the 'foaming microspheres' coated by the ferric phosphate cannot be completely removed; in addition, the reducing gas generated when the 'foaming microspheres' expand and volatilize can reduce part of the iron phosphate into ferrous phosphate.
The impurities in the Chinese patent 110182779A are two types, namely soluble salts generated by synthesizing iron phosphate; one is "acetylene black". The method for removing soluble salt impurities is washing, the method for removing acetylene black is sintering, the volatile part in the actual preparation process is the part of the acetylene black which can be contacted with air, the part of the acetylene black coated by the ferric phosphate cannot be contacted with air and oxidized to be volatile, and the residue cannot be completely removed after being coated by the ferric phosphate; in addition, the reducing gas generated when the acetylene black is volatilized can reduce part of the ferric phosphate into ferrous phosphate.
That is, the pore-forming methods disclosed in the above two patents have a high impurity content in the final product.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the iron phosphate material with the nanometer microporous structure and the preparation method, wherein the iron phosphate material has more pore passages, high purity and good stability, and can be used for preparing a high-performance lithium iron phosphate anode.
The technical scheme adopted by the invention for solving the technical problems is as follows: the iron phosphate with the nano-microporous structure is characterized in that nano-scale microporous channels are distributed on the outer surface and inside of the iron phosphate, the nano-scale microporous channels extend inside and outside the iron phosphate, and the pore diameter of the nano-scale microporous channels is smaller than 50 nm.
Preferably, the nano-microporous channel is communicated with the inside of the iron phosphate.
Preferably, the specific surface area of the iron phosphate is greater than or equal to 90m 2/g.
The invention also discloses a preparation method of the iron phosphate with the nano-microporous structure, which comprises the following steps:
1) dissolving an iron source in deionized water, performing molecular polymerization treatment, and converting the iron source from a monomolecular state to a macromolecular polymerization state at the temperature of 40-120 ℃ under the pressure of 0.3-0.7Mpa to obtain an iron source polymer;
2) stirring and mixing the iron source polymer and 30-65% phosphoric acid solution at 10-40 ℃ according to the speed of 10-60r/min, and replacing phosphate radicals and acid radicals of the iron source under the condition of not destroying the polymerization state of the iron source to form iron phosphate solution with a polymerization state structure, wherein the mixing ratio is 1: 0.9-1.15;
3) adding alkali liquor diluted to 1.5-6% into the iron phosphate solution at the temperature of 20-35 ℃, and adjusting the pH value to 2.5-7.0 to obtain mixed suspension containing iron phosphate and soluble salts;
4) and 3) performing ball milling or sanding on the suspension obtained in the step 3), washing to remove soluble salts in the suspension, and drying at 80-160 ℃ to obtain the iron phosphate with the nano microporous structure.
Further, the temperature of the polymerization treatment in the step 1) is 40-80 ℃.
Further, the pressure of the polymerization treatment in the step 1) is 0.4-0.6 MPa.
Further, in the step 1), the iron source is one or a combination of two or more of ferric sulfate, ferric hydroxide, ferric chloride and polymeric ferric sulfate.
Further, the mixing temperature of the iron source polymer and the phosphoric acid solution in the step 2) is 15-30 ℃; the mixing ratio of the iron source polymer to the phosphoric acid solution is 1: 0.95-1.1.
Further, the concentration of the alkali liquor in the step 3) is 2-4.5%; the pH value is 3.0-6.0; the alkali solution is one or two or more of sodium hydroxide, potassium hydroxide, ammonia water and lithium hydroxide.
Further, the drying temperature in the step 4) is 90-140 ℃; the ball milling treatment adopts 0.5-5cm zirconium balls, and the sanding treatment adopts 0.1-1.2mm zirconium balls.
The invention carries out molecular polymerization treatment on an iron source, converts the iron source from a single molecule into a multi-molecular polymer structure by a chemical mode, and reacts with phosphoric acid on the basis of the structure, namely, under the condition of not destroying the polymerization state of the iron source, acid radicals of the iron source are replaced by phosphate radicals, and the formed iron phosphate has the structural characteristics of the multi-molecular polymer and belongs to the configuration of a nano microporous structure. The chemical polymerization is used for forming pores, and the pores uniformly distributed inside and outside the crystal are communicated with each other, so that the problem of ion channels inside the crystal is effectively solved.
In this application patent, through the polymerization technology to iron source and synthesis process handle, make its ferric phosphate have nanometer micropore, need not add pore-forming material, impurity only soluble salt does not have the second class, also can not have follow-up influence to the ferric phosphate, and the mode of getting rid of does: the active ingredients are either re-reacted to form by ball milling or sanding, washing with water, or dissolved in water and separated upon filtration. The impurity content in the processed ferric phosphate is less than or equal to 0.5 percent.
The invention has the beneficial effects that: 1) the pore canal with the nanometer-level pore diameter is produced, so that the effective components of the material can not be reduced while the specific surface area is increased; 2) the pore canal penetrates through the interior of the iron phosphate to form an effective internal ion channel; 3) the specific surface area of the iron phosphate is far larger than that of the iron phosphate prepared by the prior art; 4) high purity and less impurities.
Drawings
Fig. 1 is a SEM image of a structure of iron phosphate prepared by the prior art.
Fig. 2 is a SEM image of the iron phosphate structure prepared by the prior art.
Fig. 3 is an SEM image of the external porous structure of iron phosphate according to the present invention.
Fig. 4 is an SEM image of the internal cross-sectional porous structure of the iron phosphate according to the present invention.
Fig. 5 is a schematic view showing the pore diameter of the pore canal in the internal cross section of the iron phosphate according to the present invention.
Fig. 6 is a schematic diagram of the pore diameter of the pore canal in the internal cross section of the iron phosphate according to the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 200g of 35% ferric sulfate, adding 200mL of deionized water to prepare a ferric sulfate solution, placing the ferric sulfate solution into a reaction kettle, and stirring for 2 hours at 85 ℃ and 0.3Mpa to perform molecular polymerization treatment to obtain a polymeric ferric sulfate solution;
2) weighing 43g of 82.4% phosphoric acid at a constant temperature of 25 ℃, adding 50ml of deionized water, stirring, mixing and stirring with a polymerized ferric sulfate solution for 1h at a speed of 30r/min, and replacing phosphate radicals with acid radicals of an iron source under the condition of not damaging the polymerization state of the iron source to form a ferric phosphate solution with a polymerization structure;
3) adding a potassium hydroxide solution with the concentration of 4% into an iron phosphate solution at the constant temperature of 25 ℃ at the speed of 20ml/min, adjusting the pH value to 5.0, and stirring for reaction for 1h to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 150ml of deionized water, ball-milling for 1h in a ball mill with a 5mm zirconium ball, adding 800ml of deionized water, washing and stirring for 0.5h, filtering, adding 350ml of deionized water into the filtered iron phosphate, sanding for 1h in a sand mill with a 0.6mm zirconium ball, adding 800ml of deionized water, washing and stirring for 0.5h, filtering, and drying the filtered iron phosphate in an oven at 160 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 1 was measured to be 104.2m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
Example 2
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 140g of 30% ferric hydroxide, adding 150mL of deionized water to prepare a ferric sulfate solution, placing the ferric sulfate solution into a reaction kettle, and stirring for 4 hours at 65 ℃ and 0.4Mpa to perform molecular polymerization treatment to obtain a polymerized ferric hydroxide solution;
2) weighing 44g of 82.4% phosphoric acid at a constant temperature of 30 ℃, adding 60ml of deionized water, stirring, mixing and stirring with a polymerized ferric sulfate solution for 2 hours at a speed of 20r/min, and replacing phosphate radicals with acid radicals of an iron source under the condition of not damaging the polymerization state of the iron source to form a ferric phosphate solution with a polymerization structure;
3) adding a 5% sodium hydroxide solution into an iron phosphate solution at a constant temperature of 25 ℃ at a rate of 20ml/min, adjusting the pH value to 4.5, and stirring for reaction for 3 hours to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 200ml of deionized water, ball-milling for 2h in a ball mill with a zirconium ball of 8mm, adding 1000ml of deionized water, washing and stirring for 1h, filtering, adding 450ml of deionized water into the filtered iron phosphate, sanding for 2h in a sand mill with a zirconium ball of 0.4mm, adding 1000ml of deionized water, washing and stirring for 1h, filtering, and drying the filtered iron phosphate in an oven at 140 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 2 was measured to be 96.3m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
Example 3
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 220g of 20% ferric chloride, adding into 200mL of deionized water to prepare a ferric sulfate solution, putting into a reaction kettle, and stirring for 4 hours at 80 ℃ and 0.6Mpa to perform molecular polymerization treatment to obtain a polymerized ferric chloride solution;
2) weighing 35g of 82.4% phosphoric acid at a constant temperature of 30 ℃, adding 30ml of deionized water, stirring, mixing and stirring with a polymeric ferric sulfate solution at a speed of 45r/min for 3h, and replacing phosphate radicals with acid radicals of an iron source under the condition of not damaging the polymeric state of the iron source to form a ferric phosphate solution with a polymeric structure;
3) adding a 3% potassium hydroxide solution into an iron phosphate solution at a constant temperature of 30 ℃ at a rate of 20ml/min, adjusting the pH value to 3.5, and stirring for reacting for 6 hours to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 150ml of deionized water, ball-milling for 6h in a ball mill with a zirconium ball of 8mm, adding 800ml of deionized water, washing and stirring for 3h, filtering, adding 400ml of deionized water into the filtered iron phosphate, sand-milling for 6h in a sand mill with a zirconium ball of 0.6mm, adding 800ml of deionized water, washing and stirring for 4h, filtering, and drying the filtered iron phosphate in an oven at 80 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 3 was measured to be 92.3m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
Example 4
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 300g of polymeric ferric sulfate with the concentration of 11%, adding 300mL of deionized water to prepare a ferric sulfate solution, putting the ferric sulfate solution into a reaction kettle, and stirring for 3 hours at 50 ℃ and 0.5Mpa to perform molecular polymerization treatment to obtain a polymeric ferric sulfate solution;
2) at a constant temperature of 25 ℃, 5.3g of phosphoric acid with the concentration of 82.4 percent is weighed, 5ml of deionized water is added, the mixture and the polymeric ferric sulfate solution are stirred, mixed and stirred for 3 hours at a speed of 50r/min, and under the condition that the polymeric state of the iron source is not damaged, phosphate radicals and acid radicals of the iron source are replaced to form the ferric phosphate solution with the polymeric structure;
3) adding an ammonia water solution with the concentration of 2% into an iron phosphate solution at the constant temperature of 25 ℃ at the speed of 20ml/min, adjusting the pH value to 3.0, and stirring for reacting for 4 hours to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 150ml of deionized water, ball-milling for 6h in a ball mill with 2cm of zirconium balls, adding 600ml of deionized water, washing and stirring for 2h, filtering, adding 400ml of deionized water into the filtered iron phosphate, sanding for 6h in a sand mill with 0.6mm of zirconium balls, adding 600ml of deionized water, washing and stirring for 2h, filtering, and drying the filtered iron phosphate in an oven at 120 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 4 was measured to be 93.7m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
Example 5
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 200g of 30% ferric sulfate, adding 200mL of deionized water to prepare a ferric sulfate solution, placing the ferric sulfate solution into a reaction kettle, and stirring for 4 hours at 120 ℃ and 0.4Mpa to perform molecular polymerization treatment to obtain a polymeric ferric sulfate solution;
2) at a constant temperature of 25 ℃, 36g of phosphoric acid with the concentration of 82.4 percent is weighed, added into 20ml of deionized water, stirred, mixed and stirred with a polymeric ferric sulfate solution for 3 hours at a speed of 60r/min, and under the condition of not damaging the polymeric state of an iron source, phosphate radicals and acid radicals of the iron source are replaced to form a ferric phosphate solution with a polymeric structure;
3) adding a lithium hydroxide solution with the concentration of 5.5% into an iron phosphate solution at the constant temperature of 25 ℃ at the speed of 20ml/min, adjusting the pH value to 3.5, and stirring for reaction for 3 hours to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 150ml of deionized water, ball-milling for 8h in a ball mill with a zirconium ball of 8mm, adding 800ml of deionized water, washing and stirring for 2h, filtering, adding 500ml of deionized water into the filtered iron phosphate, sand-milling for 8h in a sand mill with a zirconium ball of 0.6mm, adding 800ml of deionized water, washing and stirring for 2h, filtering, and drying the filtered iron phosphate in an oven at 140 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 5 was found to be 91.4m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
Example 6
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 205g of 20% ferric chloride, adding the ferric chloride into 200mL of deionized water to prepare a ferric sulfate solution, putting the ferric sulfate solution into a reaction kettle, and stirring the mixture for 6 hours at 135 ℃ and 0.6Mpa to perform molecular polymerization treatment to obtain a polymeric ferric sulfate solution;
2) weighing 31.6g of phosphoric acid with the concentration of 82.4 percent at the constant temperature of 35 ℃, adding 15ml of deionized water, stirring, mixing and stirring with the polymerized ferric sulfate solution for 3 hours at a speed of 40r/min, and replacing phosphate radicals with acid radicals of an iron source under the condition of not damaging the polymerization state of the iron source to form the ferric phosphate solution with a polymerization structure;
3) adding a 5% sodium hydroxide solution into an iron phosphate solution at a constant temperature of 35 ℃ at a rate of 20ml/min, adjusting the pH value to 4.0, and stirring for reaction for 3 hours to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 150ml of deionized water, ball-milling for 6h in a ball mill with a 6mm zirconium ball, adding 600ml of deionized water, washing and stirring for 2h, filtering, adding 500ml of deionized water into the filtered iron phosphate, sanding for 6h in a sand mill with a 0.6mm zirconium ball, adding 600ml of deionized water, washing and stirring for 2h, filtering, and drying the filtered iron phosphate in an oven at 160 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 6 was measured to be 99.8m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
Example 7
The preparation method of the iron phosphate with the nano-microporous structure comprises the following steps:
1) weighing 450g of 10% polymeric ferric sulfate, adding the polymeric ferric sulfate into 50mL of deionized water to prepare a ferric sulfate solution, putting the ferric sulfate solution into a reaction kettle, and stirring for 6 hours at 120 ℃ and 0.7Mpa to perform molecular polymerization treatment to obtain a polymeric ferric sulfate solution;
2) weighing 7.2g of phosphoric acid with the concentration of 82.4 percent at the constant temperature of 20 ℃, adding 10ml of deionized water, stirring, mixing and stirring with the polymerized ferric sulfate solution for 2 hours at the speed of 10r/min, and replacing phosphate radicals with acid radicals of an iron source under the condition of not damaging the polymerization state of the iron source to form the ferric phosphate solution with a polymerization structure;
3) adding a 5% sodium hydroxide solution into an iron phosphate solution at a constant temperature of 20 ℃ at a rate of 20ml/min, adjusting the pH value to 7.0, and stirring for reacting for 4 hours to obtain a mixed suspension containing iron phosphate and soluble salts;
4) filtering mixed suspension containing iron phosphate and soluble salts, adding 150ml of deionized water, ball-milling for 6h in a ball mill with a 6mm zirconium ball, adding 600ml of deionized water, washing and stirring for 2h, filtering, adding 500ml of deionized water into the filtered iron phosphate, sanding for 6h in a sand mill with a 0.6mm zirconium ball, adding 600ml of deionized water, washing and stirring for 2h, filtering, and drying the filtered iron phosphate in an oven at 100 ℃ for 12h to obtain the iron phosphate with the nano-microporous structure.
The specific surface area of the iron phosphate prepared in example 7 was measured to be 92.2m2And the outer surface and the interior of the iron phosphate are distributed with nano-scale microporous channels which are communicated with each other in the iron phosphate.
The specific surface area of the iron phosphate obtained by the invention reaches 90m2(ii) at least 2 times the surface area of the iron phosphate obtained in CN 110104624.
Paragraph [0019] of the specification of Chinese patent 110104624 states that "the foamed microsphere is a core-shell structure microsphere with very uniform particle size before foaming, the outer shell is a thermoplastic acrylic resin polymer, the inner shell is an alkane gas, and the diameter is generally between 0.1 and 45 μm. When the expanded microspheres are heated to between 50-300 ℃, the alkane gas expands, pushing the softened thermoplastic shell, causing the microsphere volume to expand several to tens of times rapidly. "the pore diameter formed by the method is more than or equal to 0.1 μm, but the pore diameters are all nano-scale in the invention, and under the condition of the same volume of the material, more nano-scale pore diameters, namely, higher specific surface area, can be kept in the material, and simultaneously, more effective material entities can be kept.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (10)
1. The iron phosphate with the nano microporous structure is characterized in that: nanometer microporous channels are distributed on the outer surface and the inner part of the iron phosphate, the nanometer microporous channels extend in the inner part and the outer surface of the iron phosphate, and the pore diameter of the nanometer microporous channels is less than 50 nm.
2. The nanoporous iron phosphate according to claim 1, wherein: the nanometer micropore channel is communicated with the inside of the iron phosphate.
3. The nanoporous iron phosphate according to claim 1, wherein: the specific surface area of the iron phosphate is more than or equal to 90m2/g。
4. A preparation method of iron phosphate with a nano-microporous structure is characterized by comprising the following steps:
1) dissolving an iron source in deionized water, performing molecular polymerization treatment, and converting the iron source from a monomolecular state to a macromolecular polymerization state at the temperature of 40-120 ℃ under the pressure of 0.3-0.7Mpa to obtain an iron source polymer;
2) stirring and mixing the iron source polymer and 30-65% phosphoric acid solution at 10-40 ℃ according to the speed of 10-60r/min, and replacing phosphate radicals and acid radicals of the iron source under the condition of not destroying the polymerization state of the iron source to form iron phosphate solution with a polymerization state structure, wherein the mixing ratio is 1: 0.9-1.15;
3) adding alkali liquor diluted to 1.5-6% into the iron phosphate solution at the temperature of 20-35 ℃, and adjusting the pH value to 2.5-7.0 to obtain mixed suspension containing iron phosphate and soluble salts;
4) and 3) performing ball milling or sanding on the suspension obtained in the step 3), washing to remove soluble salts in the suspension, and drying at 80-160 ℃ to obtain the iron phosphate with the nano microporous structure.
5. The iron phosphate with a nano-microporous structure and the preparation method thereof according to claim 4, wherein the iron phosphate with a nano-microporous structure is prepared by the following steps: the temperature of the polymerization treatment in the step 1) is 40-80 ℃.
6. The iron phosphate with a nano-microporous structure and the preparation method thereof according to claim 4, wherein the iron phosphate with a nano-microporous structure is prepared by the following steps: the pressure of the polymerization treatment in the step 1) is 0.4-0.6 Mpa.
7. The iron phosphate with nano-nano microporous structure and the preparation method thereof according to claim 4 are characterized in that: in the step 1), the iron source is one or a combination of two or more of ferric sulfate, ferric hydroxide, ferric chloride and polymeric ferric sulfate.
8. The iron phosphate with a nano-microporous structure and the preparation method thereof according to claim 4, wherein the iron phosphate with a nano-microporous structure is prepared by the following steps: the mixing temperature of the iron source polymer and the phosphoric acid solution in the step 2) is 15-30 ℃; the mixing ratio of the iron source polymer to the phosphoric acid solution is 1: 0.95-1.1.
9. The iron phosphate with a nano-microporous structure and the preparation method thereof according to claim 4, wherein the iron phosphate with a nano-microporous structure is prepared by the following steps: the concentration of the alkali liquor in the step 3) is 2-4.5%; the pH value is 3.0-6.0; the alkali solution is one or two or more of sodium hydroxide, potassium hydroxide, ammonia water and lithium hydroxide.
10. The iron phosphate with a nano-microporous structure and the preparation method thereof according to claim 4, wherein the iron phosphate with a nano-microporous structure is prepared by the following steps: the drying temperature in the step 4) is 90-140 ℃; the ball milling treatment adopts 0.5-5cm zirconium balls, and the sanding treatment adopts 0.1-1.2mm zirconium balls.
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