CN117735509A - Manganese iron hydrogen phosphate material and preparation method thereof - Google Patents
Manganese iron hydrogen phosphate material and preparation method thereof Download PDFInfo
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- CN117735509A CN117735509A CN202311765083.9A CN202311765083A CN117735509A CN 117735509 A CN117735509 A CN 117735509A CN 202311765083 A CN202311765083 A CN 202311765083A CN 117735509 A CN117735509 A CN 117735509A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- BLBDSGGFSRKCKK-UHFFFAOYSA-J [Fe+2].P(=O)(O)([O-])[O-].[Mn+2].P(=O)(O)([O-])[O-] Chemical compound [Fe+2].P(=O)(O)([O-])[O-].[Mn+2].P(=O)(O)([O-])[O-] BLBDSGGFSRKCKK-UHFFFAOYSA-J 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 21
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 19
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 19
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 19
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 19
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 19
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 19
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000011268 mixed slurry Substances 0.000 claims abstract description 15
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 14
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 14
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 14
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 235000012501 ammonium carbonate Nutrition 0.000 description 8
- 238000001354 calcination Methods 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AOBAVABSFWTQIX-UHFFFAOYSA-L hydrogen phosphate;iron(2+) Chemical compound [Fe+2].OP([O-])([O-])=O AOBAVABSFWTQIX-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention discloses a manganese iron hydrogen phosphate material and a preparation method thereof, relates to the technical field of chemical synthesis of battery materials, and aims to solve the problem that the existing LFMP precursor manganese iron hydrogen phosphate synthesis method is not beneficial to large-scale production; adding manganese sulfate and soluble carbonate into a reaction kettle, fully precipitating, filtering, washing and drying to obtain manganese carbonate; roasting manganese carbonate in a muffle furnace at a high temperature to obtain manganese sesquioxide; adding manganese sesquioxide and simple substance iron into a mixer according to the required proportion of manganese iron, fully mixing to obtain premix, adding water into the premix, and fully grinding the premix by a ball mill to obtain mixed slurry; drying the mixed slurry by using drying equipment to obtain mixed powder; adding the mixed powder into a phosphoric acid aqueous solution with a certain concentration, stirring for reaction, washing and drying to obtain ferric manganese hydrogen phosphate; the invention has simple process, low manufacturing cost, environment-friendly preparation process and mild process conditions, and is beneficial to large-scale production and application.
Description
Technical Field
The invention relates to the technical field of chemical synthesis of battery materials, in particular to a manganese iron hydrogen phosphate material and a preparation method thereof.
Background
Lithium iron phosphate (LFP) can be used as a positive electrode material of a lithium ion battery, and has been widely applied to industrialization due to the advantages of environmental friendliness, low cost, good electrochemical and thermal stability and the like. However, LFP has the drawbacks of low operating voltage (3.4V), insufficient rate performance, low conductivity, etc., and cannot meet the current market demand for high energy density batteries, and there is an urgent need to find an alternative material with high energy density and good safety performance. The lithium iron manganese phosphate (LFMP) is a material doped with manganese in the lithium iron phosphate, the energy density of the lithium iron manganese phosphate is improved by 10-20% compared with the lithium iron phosphate under the same specific capacity, the low-temperature performance is better, and the working voltage can reach 4.1V. In addition, compared with a ternary material, the LFMP has higher safety, thermal stability, low price and long service life, and is expected to become a new generation of high-energy-density power battery anode material.
Precursors such as ferromanganese phosphate and ferric manganese hydrogen phosphate are also receiving increasing attention due to the great potential for LFMP. However, there is still a lack of a mature LFMP precursor and a reliable synthesis route, and in the literature currently disclosed, most of researchers synthesize ferromanganese phosphate by coprecipitation, hydrothermal method, spray drying method, high temperature solid phase method, and the like. However, most of the methods have the defects of serious pollution of waste water or byproducts, high cost, complex process and the like, and are not beneficial to large-scale production. In addition, the precursor synthesized by the method is difficult to realize uniform mixing of manganese and iron in an atomic layer, which can cause the influence on the charging constant voltage section and the rate discharge performance of the LFMP prepared later.
Disclosure of Invention
The invention aims to provide a manganese iron hydrogen phosphate material and a preparation method thereof, which are used for solving the problem that the existing LFMP precursor manganese iron hydrogen phosphate synthesis method is not beneficial to large-scale production.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a ferromanganese hydrogen phosphate material comprises the following steps:
step S1: adding manganese sulfate and soluble carbonate into a reaction kettle, fully precipitating, filtering, washing and drying to obtain manganese carbonate;
step S2: roasting manganese carbonate in a muffle furnace at a high temperature to obtain manganese sesquioxide;
step S3: adding manganese sesquioxide and simple substance iron into a mixer according to the required proportion of manganese iron, fully mixing to obtain premix, adding water into the premix, and fully grinding the premix by a ball mill to obtain mixed slurry;
step S4: drying the mixed slurry by using drying equipment to obtain mixed powder;
step S5: and (3) putting the mixed powder into a phosphoric acid aqueous solution with a certain concentration, stirring for reaction, and washing and drying to obtain the ferric manganese hydrogen phosphate.
Preferably, in the step S1, the soluble carbonate is (NH 4 ) 2 CO 3 、NH 4 HCO 3 、Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 At least one of them.
Preferably, in the step S1, the ratio of the amounts of carbonate ions in the soluble carbonate to the amount of manganese ions in the manganese sulfate is (2 to 1): 1.
preferably, in the step S1, the pH of the system in the precipitation reaction is controlled to be 4 to 8.
Preferably, in the step S2, the roasting temperature of the manganese carbonate is 400-600 ℃ and the roasting time is 5-8 hours.
Preferably, in the step S3, the ball milling time of the premix is 3 to 8 hours, and the particle size D50 of the milled mixed slurry is 0.5 to 2 μm.
Preferably, in the step S4, the drying apparatus uses at least one of flash drying, spray drying, vacuum drying, and adsorption drying.
Preferably, in the step S5, the mass concentration of the phosphoric acid aqueous solution is 10 to 50%, and the molar ratio of manganese atoms, iron atoms and phosphorus atoms in the manganese trioxide, elemental iron and phosphoric acid aqueous solution is (0.8 to 0.4): (0.2-0.6): 1.
preferably, in the step S5, the temperature of the stirring reaction is 30-80 ℃, the stirring speed is 400-800 r/min, and the reaction time is 15-25 hours.
The invention provides another technical scheme that: the chemical formula of the ferric manganese hydrogen phosphate material prepared by the preparation method is Fe x Mn (1-x) HPO 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.6.
Compared with the prior art, the invention has the beneficial effects that:
1. the manganese iron hydrogen phosphate material and the preparation method thereof have simple process, low manufacturing cost, easy application to large-scale production, no unnecessary atoms in the final manganese sesquioxide, elemental iron and phosphoric acid aqueous solution, pure reaction and no new impurity.
2. According to the manganese iron hydrogen phosphate material and the preparation method thereof, manganese iron in the prepared product is uniformly mixed, the proportion of manganese iron is flexibly adjustable through control in the preparation process, and the manganese iron hydrogen phosphate material can be directly used for producing the lithium manganese iron phosphate anode material with higher specific capacity and good cycle performance.
3. The preparation process of the ferromanganese hydrogen phosphate material is environment-friendly, a large amount of wastewater, byproducts or pollutants are not generated, and the preparation process condition is mild, so that the mass production is facilitated.
Drawings
Fig. 1 is an SEM image of iron manganese hydrogen phosphate prepared in example 1 of the present invention.
Detailed Description
A preparation method of a ferromanganese hydrogen phosphate material comprises the following steps:
step S1: adding manganese sulfate and soluble carbonate into a reaction kettle, wherein the soluble carbonate can be (NH) 4 ) 2 CO 3 、NH 4 HCO 3 、Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 In a preferred embodiment, at least one of the components is carbonic acidThe ratio of the amounts of the substances of the root ion and the manganese ion is (2-1): 1, a step of; fully precipitating after the addition is finished for reference, and controlling the pH value of a system in the precipitation reaction to be 4-8; filtering, washing and drying the precipitate after the precipitation is sufficient to obtain manganese carbonate;
step S2: roasting manganese carbonate in a muffle furnace at a high temperature to obtain manganese sesquioxide, wherein the roasting temperature of the manganese carbonate is preferably 400-600 ℃, and the roasting time can be 5-8 hours;
step S3: adding manganese sesquioxide and simple substance iron into a mixer according to the required proportion of manganese iron, fully mixing to obtain premix, adding water into the premix, fully grinding the premix by using a ball mill to obtain mixed slurry, wherein the ball milling time can be 3-8 hours for reference, and the particle size D50 of the ground mixed slurry is preferably controlled to be 0.5-2 mu m;
step S4: the mixed slurry is dried by a drying device to obtain mixed powder, wherein the drying device can be flash evaporation drying, spray drying, vacuum drying, adsorption drying or a plurality of combinations;
step S5: the mixed powder is put into phosphoric acid aqueous solution with a certain concentration (for example, the mass concentration can be 10-50%) for stirring reaction, and the mole ratio of manganese atoms, iron atoms and phosphorus atoms in the reaction system can be further controlled to be (0.8-0.4): (0.2-0.6): 1, furthermore, the stirring reaction may take the following parameters as preferred embodiments: the temperature of the stirring reaction is 30-80 ℃, the stirring speed is 400-800 r/min, and the reaction time is 15-25 hours; washing and drying to obtain ferric manganese hydrogen phosphate with a chemical formula of Fe x Mn (1-x) HPO 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.6.
Example 1:
a ferromanganese hydrogen phosphate material, wherein the molar ratio of ferromanganese elements is 3:2, the preparation method comprises the following steps:
(1) Preparing 1000mL of manganese sulfate solution with the concentration of 1mol/L and 1000mL of ammonium carbonate solution with the concentration of 2mol/L, adding 200mL of bottom water into a reaction kettle in advance, slowly adding the manganese sulfate and the ammonium carbonate solution into the reaction kettle at the speed of 10mL/min, stirring at room temperature for reaction for 2 hours, wherein the pH value of a reaction system is 6, and filtering, washing and drying slurry to obtain manganese carbonate;
(2) Transferring the manganese carbonate powder into a muffle furnace, and calcining at 500 ℃ for 6 hours to obtain the manganese sesquioxide.
(3) Weighing 0.4 mole of iron powder (Fe content is more than 99.5%), 0.3 mole of manganese sesquioxide, premixing in a mixer for 1 hour, adding water, placing in a ball mill for ball milling, measuring the particle size D50 of the mixed slurry to be 2 mu m after 3 hours, stopping ball milling, and vacuum drying to obtain mixed powder.
(4) And (3) adding the mixed powder into a phosphoric acid aqueous solution (the mass concentration is 30%) containing 1 mole of phosphoric acid, stirring and reacting, setting the rotating speed to 600r/min, keeping the temperature at 80 ℃ for reacting for 20 hours, separating mother liquor after the reaction is finished, washing and drying to obtain the ferric manganese hydrogen phosphate material.
The SEM image of the iron hydrogen phosphate prepared in example 1 is shown in fig. 1, and it can be seen from the image that the iron hydrogen phosphate material prepared by the method is uniformly dispersed and has regular morphology, and most of particles have a particle size of about 100 μm.
Example 2:
a ferromanganese hydrogen phosphate material, wherein the molar ratio of ferromanganese elements is 1:1, the preparation method comprises the following steps:
(1) Preparing 1000mL of manganese sulfate solution with the concentration of 1mol/L and 1000mL of ammonium carbonate solution with the concentration of 1.5mol/L, adding 200mL of bottom water into a reaction kettle in advance, slowly adding the manganese sulfate and the ammonium carbonate solution into the reaction kettle at the speed of 10mL/min, stirring at room temperature for reaction for 2 hours, wherein the pH value of a reaction system is 5, and filtering, washing and drying slurry to obtain manganese carbonate;
(2) Transferring the manganese carbonate powder into a muffle furnace, and calcining at 500 ℃ for 6 hours to obtain the manganese sesquioxide.
(3) Weighing 1 mole of iron powder (Fe content is more than 99.5%), 0.5 mole of manganese sesquioxide, premixing in a mixer for 1 hour, adding water, placing in a ball mill for ball milling, measuring the particle size D50 of the mixed slurry to be 1 mu m after 5 hours, stopping ball milling, and vacuum drying to obtain mixed powder;
(4) And (3) adding the mixed powder into a phosphoric acid aqueous solution (the mass concentration is 30%) containing 2 moles of phosphoric acid, stirring and reacting, setting the rotating speed to 600r/min, keeping the temperature at 80 ℃ for reacting for 20 hours, and separating, washing and drying mother liquor after the reaction is finished to obtain the ferric manganese hydrogen phosphate material.
Example 3:
a ferromanganese hydrogen phosphate material, wherein the molar ratio of ferromanganese elements is 2:3, the preparation method comprises the following steps:
(1) Preparing 1000mL of manganese sulfate solution with the concentration of 1mol/L and 1000mL of ammonium carbonate solution with the concentration of 1.5mol/L, adding 200mL of bottom water into a reaction kettle in advance, slowly adding the manganese sulfate and the ammonium carbonate solution into the reaction kettle at the speed of 10mL/min, stirring at room temperature for reaction for 2 hours, wherein the pH value of a reaction system is 7, and filtering, washing and drying slurry to obtain manganese carbonate;
(2) Transferring the manganese carbonate powder into a muffle furnace, and calcining at 600 ℃ for 4 hours to obtain manganese sesquioxide;
(3) Weighing 0.6 mole of iron powder (Fe content is more than 99.5%), 0.2 mole of manganese sesquioxide, premixing in a mixer for 1 hour, adding water, placing in a ball mill for ball milling, measuring the particle size D50 of the mixed slurry to be 0.5 mu m after 8 hours, stopping ball milling, and vacuum drying to obtain mixed powder;
(4) And (3) adding the mixed powder into a phosphoric acid aqueous solution (the mass concentration is 10%) containing 1 mole of phosphoric acid, stirring and reacting, setting the rotating speed to 600r/min, keeping the temperature at 80 ℃ for reacting for 20 hours, separating mother liquor after the reaction is finished, washing and drying to obtain the ferric manganese hydrogen phosphate material.
Example 4:
a ferromanganese hydrogen phosphate material, wherein the molar ratio of ferromanganese elements is 4:1, the preparation method comprises the following steps:
(1) Preparing 1000mL of manganese sulfate solution with the concentration of 1mol/L and 1000mL of ammonium carbonate solution with the concentration of 1.5mol/L, adding 200mL of bottom water into a reaction kettle in advance, slowly adding the manganese sulfate and the ammonium carbonate solution into the reaction kettle at the speed of 10mL/min, stirring at room temperature for reaction for 2 hours, wherein the pH value of a reaction system is 6.5, and filtering, washing and drying slurry to obtain manganese carbonate;
(2) Transferring the manganese carbonate powder into a muffle furnace, and calcining at 500 ℃ for 6 hours to obtain manganese sesquioxide;
(3) Weighing 0.2 mole of iron powder (Fe content is more than 99.5%), 0.4 mole of manganese sesquioxide, premixing in a mixer for 1 hour, adding water, placing in a ball mill for ball milling, measuring the particle size D50 of the mixed slurry to be 0.5 mu m after 8 hours, stopping ball milling, and vacuum drying to obtain mixed powder;
(4) And (3) adding the mixed powder into a phosphoric acid aqueous solution (the mass concentration is 10%) containing 1 mole of phosphoric acid, stirring and reacting, setting the rotating speed to 500r/min, keeping the temperature at 80 ℃ for 25 hours, separating mother liquor after the reaction is finished, washing and drying to obtain the ferric manganese hydrogen phosphate material.
The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be covered by the present invention. Therefore, the protection scope of the present invention should be defined by the claims.
The present invention is not described in detail in the present application, and is well known to those skilled in the art.
Claims (10)
1. The preparation method of the ferromanganese hydrogen phosphate material is characterized by comprising the following steps of:
step S1: adding manganese sulfate and soluble carbonate into a reaction kettle, fully precipitating, filtering, washing and drying to obtain manganese carbonate;
step S2: roasting manganese carbonate in a muffle furnace at a high temperature to obtain manganese sesquioxide;
step S3: adding manganese sesquioxide and simple substance iron into a mixer according to the required proportion of manganese iron, fully mixing to obtain premix, adding water into the premix, and fully grinding the premix by a ball mill to obtain mixed slurry;
step S4: drying the mixed slurry by using drying equipment to obtain mixed powder;
step S5: and (3) putting the mixed powder into a phosphoric acid aqueous solution with a certain concentration, stirring for reaction, and washing and drying to obtain the ferric manganese hydrogen phosphate.
2. A according to claim 1The preparation method of the ferric manganese hydrogen phosphate material is characterized by comprising the following steps of: in the step S1, the soluble carbonate is (NH) 4 ) 2 CO 3 、NH 4 HCO 3 、Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 At least one of them.
3. The method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S1, the ratio of the amounts of carbonate ions in the soluble carbonate to the amount of manganese ions in the manganese sulfate is (2 to 1): 1.
4. the method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S1, the pH of the system in the precipitation reaction is controlled to be 4-8.
5. The method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S2, the roasting temperature of the manganese carbonate is 400-600 ℃, and the roasting time is 5-8 hours.
6. The method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S3, the ball milling time of the premix is 3-8 hours, and the particle size D50 of the ground mixed slurry is 0.5-2 mu m.
7. The method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S4, the drying device adopts at least one of flash drying, spray drying, vacuum drying and adsorption drying.
8. The method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S5, the mass concentration of the phosphoric acid aqueous solution is 10-50%, and the mole ratio of manganese atoms, iron atoms and phosphorus atoms in the manganese trioxide, the elemental iron and the phosphoric acid aqueous solution is (0.8-0.4): (0.2-0.6): 1.
9. the method for preparing the ferric manganese hydrogen phosphate material according to claim 1, wherein the method comprises the following steps: in the step S5, the temperature of the stirring reaction is 30-80 ℃, the stirring speed is 400-800 r/min, and the reaction time is 15-25 hours.
10. A ferromanganese hydrogen phosphate material prepared by the preparation method according to any one of claims 1 to 9, characterized in that: the chemical formula of the ferric manganese hydrogen phosphate material is Fe x Mn (1-x) HPO 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.6.
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