CN107697899B - Preparation method of battery-grade iron manganese phosphate, lithium iron manganese phosphate, battery positive electrode material and secondary battery - Google Patents
Preparation method of battery-grade iron manganese phosphate, lithium iron manganese phosphate, battery positive electrode material and secondary battery Download PDFInfo
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Abstract
The invention discloses a preparation method of battery-grade iron manganese phosphate, lithium iron manganese phosphate, a battery anode material and a secondary battery, and particularly discloses a method for preparing battery-grade iron manganese phosphate by oxidation-precipitation reaction under a single aqueous solution system, which comprises the following steps: dissolving a mixed salt of a divalent manganese salt and a divalent iron salt in water, adding a prepared pH regulator into a reaction kettle while stirring through a peristaltic pump, adjusting the pH value of a reaction system to 7.5-12.0, and continuing stirring after the reaction is finished; adding an oxidant into the reaction kettle, and continuing stirring after finishing the reaction; after the temperature in the reaction kettle reaches 60-165 ℃, adding a soluble phosphorus source solution by using a peristaltic pump, reacting for 2-8 hours, naturally cooling the iron-manganese phosphate slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final product MnxFe1‑xPO4·yH2And O, the method has no pollution, simple process and high yield, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery anode materials, and particularly relates to a method for preparing battery-grade ferric manganese phosphate by oxidation-precipitation reaction in a single aqueous solution system.
Background
The iron-manganese phosphate lithium battery material has the same specific capacity (the theoretical capacity is 170mAh/g) as the lithium iron phosphate, but has a higher voltage platform (4.1V), and can be applied to LiFePO4The energy density is improved by about 20 percent on the basis of the total energy density. Based on the above-mentioned two advantages, the utility model,lithium manganese iron phosphate battery materials have received extensive attention and research. The method has the advantages that the molar ratio of Mn to Fe is reasonably adjusted, and the preparation of the high-activity iron-manganese phosphate precursor is the key point for preparing the high-energy-density and high-conductivity lithium manganese iron phosphate battery material.
Many reports on the preparation methods of the iron phosphate manganese lithium battery material and the precursor thereof are found at present. The current methods for preparing lithium manganese iron phosphate mainly comprise a high-temperature solid phase method, a sol-gel method and a coprecipitation method. Wherein, the high-temperature solid phase method is widely used and is also suitable for industrial production. However, the solid-phase reaction is difficult to control the nucleation rate and the ion diffusion rate of the product phase, so that the synthesized lithium manganese iron phosphate product has poor consistency, uneven particle morphology and wider particle size distribution, and the whole high-temperature solid-phase reaction process can produce more waste gas pollution, mainly NH3、CO2And the like. In order to solve the above disadvantages, the preparation of iron manganese phosphate precursor by coprecipitation method is the focus of research. For example, Chinese patent publication No. CN104518217A discloses a method for preparing battery-grade manganese iron phosphate, which comprises placing an iron source, a manganese source and a phosphorus source in a reaction kettle by a hydrothermal oxidation-coprecipitation method, adding a surfactant and nitric acid, and respectively oxidizing Mn with the added nitric acid at 100-250 deg.C2+And Fe2+Is Mn3+And Fe3+Then with PO4 3-Combined to prepare Mn with crystal waterxFe1-xPO4·yH2And O. Although the method prepares the iron-manganese phosphate mixed with manganese in atomic level, the added nitric acid oxidizes Mn at 100-250 DEG C2+And Fe2+In the process, a large amount of nitrogen oxide waste gas is released, the environment is seriously polluted, and the reaction temperature is also higher. Chinese patent publication No. CN105449207A discloses a preparation method of manganese iron phosphate and a product thereof, wherein an iron source, a manganese source and a phosphorus source are placed in a reaction kettle, an oxidant and a dispersant are added, the reaction is carried out for 2-24 hours at 50-150 ℃, and Mn is prepared by washing, filtering and dryingxFe1- xPO4·yH2And O. However, there are also pollutants which release nitrogen oxides by adding nitric acid or sodium nitrate as an oxidizing agentAnd a dispersant absolute ethyl alcohol is also needed to be added in the dyeing and synthesizing process. Chinese patent publication No. CN105244497A discloses a preparation method of a manganese iron phosphate intermediate and a lithium manganese iron phosphate/carbon composite material, wherein the manganese iron phosphate intermediate is prepared by using manganese nitrate, ferric nitrate and phosphoric acid as main raw materials and performing condensation reflux heating under an ethanol-water mixed system, and the lithium manganese iron phosphate/carbon composite material with excellent performance is prepared by using a lithium source, a carbon source and the manganese iron phosphate intermediate and adopting a one-step mixing and sintering process. In order to prevent the oxidation of metal salt, inert gas is introduced into a reaction kettle for protection before feeding, and meanwhile, the reaction system is an ethanol-water mixed system, and the molar ratio n of phosphoric acid to doped metal M saltPhosphoric acid/n(Mn+Fe+M)2-4, volume ratio V of ethanol to phosphoric acidEthanol/VPhosphoric acidThe method has the problems of excessive use amounts of ethanol and phosphoric acid, high raw material cost and the like, and is complex in process and not suitable for industrial production because condensation reflux heating is required to reduce the loss of the solvent.
Disclosure of Invention
The invention aims to solve the problems and provide a preparation method of battery grade manganese iron phosphate, which has no pollution, simple process and high yield and is suitable for industrial production. The method has the advantages that the oxidation-precipitation reaction is carried out in a single aqueous solution system, the reaction can be completed after 2-8 hours at the temperature of 60-165 ℃, no waste gas is released in the oxidation process, the method is environment-friendly, the product yield is high, the manganese and iron yield is over 99.5%, the iron and manganese phosphate product has high purity and low impurity content, Na is less than or equal to 100ppm, S is less than or equal to 100ppm, and the iron and manganese phosphate products with different Mn/Fe molar ratios can be prepared according to market demands.
The chemical formula of the iron phosphate manganese is MnxFe1-xPO4·yH2O, x is more than or equal to 0.5 and less than or equal to 0.8, and y is 0 or 1. The valence of manganese and iron is positive trivalent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention discloses a method for preparing iron manganese phosphate by adopting an oxidation-precipitation process under a single aqueous solution system, which comprises the following steps:
1) adding a mixed salt of a divalent manganese salt and a divalent ferric salt into a reaction kettle, adding water, stirring at room temperature to completely dissolve the mixed salt, and preparing aqueous solutions of the divalent manganese salt and the divalent ferric salt with the concentrations of 0.2-4 mol/L respectively, preferably 0.2-2 mol/L;
2) adding the prepared pH regulator into the reaction kettle through a peristaltic pump while stirring, adjusting the pH value of the reaction system to 7.5-12.0, and continuing stirring for 10-20 minutes after the reaction is finished;
3) adding an oxidant into the reaction kettle at a feeding speed of 30-100 r/min through a peristaltic pump, and continuously stirring for 20-60 minutes after finishing the adding;
4) after the temperature in the reaction kettle reaches 60-165 ℃, adding a soluble phosphorus source solution by using a peristaltic pump, reacting for 2-8 hours, naturally cooling the iron-manganese phosphate slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final product MnxFe1- xPO4·yH2O。
More specifically, the divalent manganese salt is one or more of manganous sulfate, manganous nitrate, manganous chloride and manganous acetate;
the ferrous salt is one or more of ferrous sulfate, ferrous nitrate and ferrous chloride;
the pH regulator is one or more of sodium hydroxide, ammonia water, sodium acetate and ammonium acetate;
the oxidant is one or more of sodium peroxide, hydrogen peroxide and ozone, wherein the molar ratio of the oxidant to manganese to iron is 1-4, and the preferred ratio is 1-2;
the phosphorus source is one or more of phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and ammonium phosphate, and the molar ratio of the phosphorus source to manganese to iron is 1.1-2, preferably 1.1-1.6;
by adjusting the feeding molar ratio of Mn/Fe to 1-4 of manganese salt and ferric salt, the iron manganese phosphate Mn with different Mn/Fe molar ratios can be obtainedxFe1-xPO4·yH2O, x is more than or equal to 0.5 and less than or equal to 0.8, and y is 0 or 1.
The method for preparing the iron-manganese phosphate by adopting the oxidation-precipitation process under the single aqueous solution system can also comprise the following steps:
1) adding a divalent manganese salt into a reaction kettle, adding water, stirring at room temperature to completely dissolve the divalent manganese salt, and preparing an aqueous solution of the divalent manganese salt with the concentration of 0.2-4 mol/L, preferably 0.2-2 mol/L;
2) adding the prepared pH regulator into the reaction kettle through a peristaltic pump while stirring, adjusting the pH value of the reaction system to 7.5-12.0, and continuing stirring for 10-20 minutes after the reaction is finished;
3) adding an oxidant into the reaction kettle at a feeding speed of 30-100 r/min through a peristaltic pump, and continuously stirring for 20-60 minutes after finishing the adding;
4) adding the prepared ferric iron salt solution into the reaction kettle through a peristaltic pump, and continuing stirring for 30 minutes after the reaction is finished; the concentration of the ferric salt solution is 0.2-4 mol/L, preferably 0.2-2 mol/L;
5) after the temperature in the reaction kettle reaches 60-165 ℃, adding a certain amount of soluble phosphorus source solution by using a peristaltic pump, reacting for 2-8 hours, naturally cooling the iron-manganese phosphate slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final product MnxFe1-xPO4·yH2O。
More specifically, the divalent manganese salt is one or more of manganous sulfate, manganous nitrate, manganous chloride and manganous acetate;
the pH regulator is one or more of sodium hydroxide, ammonia water, sodium acetate and ammonium acetate;
the oxidant is one or more of sodium peroxide, hydrogen peroxide and ozone, wherein the molar ratio of the oxidant to manganese to iron is 1-4, and the preferred ratio is 1-2;
the ferric iron salt is one or more of ferric sulfate, ferric nitrate and ferric chloride;
the phosphorus source is one or more of phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and ammonium phosphate, and the molar ratio of the phosphorus source to manganese to iron is 1.1-2, preferably 1.1-1.6;
by adjusting manganese saltThe feeding molar ratio of the iron salt to the iron salt is Mn/Fe ═ 1-4, and iron manganese phosphate Mn with different Mn/Fe molar ratios can be obtainedxFe1-xPO4·yH2O, x is more than or equal to 0.5 and less than or equal to 0.8, and y is 0 or 1.
Furthermore, the invention also relates to a manganese iron phosphate product prepared by any one of the methods.
Furthermore, the invention also relates to lithium ferric manganese phosphate which is synthesized by the ferric manganese phosphate prepared by any one of the methods and a lithium compound. The lithium compound may be any lithium salt capable of synthesizing lithium ferric manganese phosphate with ferric manganese phosphate, and preferably is one or more of lithium carbonate, lithium hydroxide and lithium acetate.
The present invention also relates to a battery positive electrode material mainly composed of lithium manganese iron phosphate synthesized by the above method, which is used as a positive electrode material for a secondary battery in which charge and discharge are repeated by a battery electrode reaction.
Furthermore, the invention also relates to a secondary battery which is made of the battery anode material.
Compared with the existing preparation method of the iron phosphate and the manganese phosphate, the preparation method of the invention has the following characteristics:
1) the method solves the problems that nitric acid or nitrate is used as an oxidant in oxidation of bivalent manganese salt and bivalent iron salt in the process of synthesizing iron manganese phosphate by oxidation-coprecipitation, nitrogen oxide waste gas is released, and the environment is polluted;
2) the method comprises the steps of preparing iron and manganese phosphate by an oxidation-precipitation method, wherein the oxidation process is carried out in an alkaline environment, namely, the pH value of a system is adjusted to 7.5-12.0 by a pH regulator, then an oxidant is added to oxidize a divalent manganese salt and a divalent iron salt into a trivalent manganese salt and a trivalent iron salt, and the oxidation process is carried out in an extremely acidic system by other oxidation-precipitation methods;
3) the method of the invention replaces an organic solvent-water system with a single aqueous solution system, and the organic solvent-water system needs to add a large amount of organic solvent in the synthesis process, and a heating mode of condensation reflux and the like is also needed in order to reduce the loss of the solvent, so the method of the invention simplifies the process flow and is more suitable for industrial production;
4) according to different market demands, the raw material addition proportion of manganese salt and ferric salt is adjusted, the feeding molar ratio is Mn/Fe (1-4), and iron manganese phosphate (Mn) with different Mn/Fe molar ratios can be obtainedxFe1-xPO4·yH2O) product, x is more than or equal to 0.5 and less than or equal to 0.8, and y is 0 or 1;
5) the manganese and iron precipitation rate of the method reaches more than 99.5 percent, the iron and manganese phosphate product has high purity, the main impurity content S is less than 200ppm, and the Na content is less than 100 ppm.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weighing 75.00g of manganous sulfate monohydrate (0.4437mol) and 30.84g of ferrous sulfate heptahydrate (0.1109mol), dissolving the manganous sulfate monohydrate (0.4437mol) and the ferrous sulfate heptahydrate (0.1109mol) in 200mL of water, adding 100mL of 10mol/L sodium hydroxide solution (1.0000mol) through a peristaltic pump while stirring, adjusting the pH value of the system to 8.51, continuing to stir for 15 minutes after the addition is finished, then adding 60mL of 30% hydrogen peroxide (0.5876mol) through the peristaltic pump at a feeding speed of 50r/min while stirring, continuing to stir for 30 minutes after an oxidation reaction is finished, then heating a reaction kettle to 85 ℃, then adding 45mL of 85% phosphoric acid (0.6557mol) through stirring, reacting for 5 hours, naturally cooling a slurry to room temperature after the reaction is finished, and obtaining a final iron manganese phosphate (with a crystal water) product with a chemical formula of Mn0.8Fe0.2PO4·H2O。
Example 2
Weighing 75.00g of manganous sulfate monohydrate (0.4437mol) and 52.87g of ferrous sulfate heptahydrate (0.1902mol), dissolving the manganous sulfate monohydrate and the ferrous sulfate heptahydrate in 300mL of water, adding 115mL of 10mol/L sodium hydroxide solution (1.1500mol) through a peristaltic pump while stirring, adjusting the pH value of the system to 8.98, continuing stirring for 15 minutes after the addition is finished, and then adding 68mL of 30 mass percent sodium sulfate through the peristaltic pump at a feeding speed of 80r/min while stirringHydrogen oxide (0.6660mol), continuously stirring for 30 minutes after the oxidation reaction is finished, then heating the reaction kettle to 85 ℃, then adding 51mL phosphoric acid (0.7431mol) with the mass concentration of 85%, reacting for 6 hours, naturally cooling the slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain the final iron manganese phosphate (with a crystal water) product, wherein the chemical formula is Mn0.7Fe0.3PO4·H2O。
Example 3
Weighing 75.00g of manganous sulfate monohydrate (0.4437mol) and 82.24g of ferrous sulfate heptahydrate (0.2958mol), dissolving the manganous sulfate monohydrate (0.4437mol) and the ferrous sulfate heptahydrate (0.2958mol) in 400mL of water, adding 135mL of 10mol/L sodium hydroxide solution (1.3500mol) through a peristaltic pump while stirring, adjusting the pH value of the system to 8.64, continuing to stir for 15 minutes after the addition is finished, then adding 80mL of hydrogen peroxide (0.7835mol) with the mass concentration of 30% through the peristaltic pump while stirring at the feeding speed of 30r/min, continuing to stir for 30 minutes after the oxidation reaction is finished, then heating the reaction kettle to 85 ℃, then adding 60mL of phosphoric acid (0.8743mol) with the mass concentration of 85%, reacting for 5.5 hours, naturally cooling the slurry to room temperature after the reaction is finished, and obtaining a final ferric manganese phosphate (with a crystal water) product with the chemical formula of Mn through water washing, filtering and drying0.6Fe0.4PO4·H2O。
Example 4
Weighing 100mL of 47.62% manganous nitrate solution (0.3984mol) and 27.68g of iron sulfate heptahydrate (0.0996mol) to dissolve in 200mL of water, adding 115mL of 10mol/L sodium hydroxide solution (1.1500mol) through a peristaltic pump while stirring, adjusting the pH value of the system to 11.53, continuing to stir for 10 minutes after the addition is finished, then adding 60mL of 30% hydrogen peroxide (0.5876mol) through the peristaltic pump at a feeding speed of 100r/min while stirring, continuing to stir for 45 minutes after the oxidation reaction is finished, then heating the reaction kettle to 90 ℃, then adding 55mL of 85% phosphoric acid (0.8014mol) to react for 6 hours, naturally cooling the slurry to room temperature after the reaction is finished, washing with water, filtering and drying to obtain a final iron manganese phosphate (with a crystal water) product, wherein the chemical formula is Mn0.8Fe0.2PO4·H2O。
Example 5
Weighing 100mL of manganous nitrate solution (0.3984mol) with the concentration of 47.62%, adding 100 water, uniformly mixing, adding 100mL of sodium hydroxide solution (1.0000mol) with the concentration of 10mol/L through a peristaltic pump while stirring, adjusting the pH value of the system to 11.08, continuously stirring for 10 minutes after the addition is finished, then adding 60mL of hydrogen peroxide (0.5876mol) with the mass concentration of 30% through the peristaltic pump while stirring at the feeding speed of 50r/min, continuously stirring for 60 minutes after the oxidation reaction is finished, then adding 50mL of ferric nitrate nonahydrate solution (0.0996mol) with the concentration of 1.99mol/L into the system, uniformly mixing and stirring for 30 minutes, then heating the reaction kettle to 115 ℃, then adding 45mL of phosphoric acid (0.6557mol) with the mass concentration of 85%, reacting for 6 hours, naturally cooling the slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain the final ferric manganese phosphate (with a crystal water) product, the chemical formula is Mn0.8Fe0.2PO4·H2O。
Example 6
Weighing 100mL of 47.62% manganous nitrate solution (0.3984mol), adding 100 water, uniformly mixing, adding 80mL of 25% ammonia water (1.035mol) by mass concentration through a peristaltic pump while stirring, adjusting the pH value of the system to 8.12, continuously stirring for 10 minutes after the addition is finished, then adding 65mL of 30% hydrogen peroxide (0.5876mol) by mass concentration through the peristaltic pump while stirring at a feeding speed of 80r/min, continuously stirring for 40 minutes after the oxidation reaction is finished, then adding 50mL of 1.99mol/L ferric nitrate nonahydrate solution (0.0996mol) into the system, uniformly mixing and stirring for 30 minutes, then heating a reaction kettle to 165 ℃, then adding 45mL of 85% phosphoric acid (0.6557mol) by mass concentration, reacting for 6 hours, naturally cooling the slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final ferric manganese phosphate (with one crystal water) product, the chemical formula is Mn0.8Fe0.2PO4·H2O。
Example 7
75.00g of manganous sulfate monohydrate (0.4437mol) and 123.37g of ferrous sulfate heptahydrate (0.4437mol) are weighed and dissolved in 500mAdding 115mL of 25% ammonia water (1.4882mol) into L water by a peristaltic pump while stirring, adjusting the pH value of the system to 7.52, continuing to stir for 10 minutes after the addition is finished, then adding 95mL of 30% hydrogen peroxide (0.9304mol) at a feeding speed of 50r/min by the peristaltic pump while stirring, continuing to stir for 30 minutes after the oxidation reaction is finished, then heating the reaction kettle to 85 ℃, then adding 75mL of 85% phosphoric acid (1.0929mol), reacting for 8 hours, naturally cooling the slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain the final iron manganese phosphate (with a crystal water) product, wherein the chemical formula of the product is Mn0.5Fe0.5PO4·H2O。
Example 8
Weighing 100mL of 47.62% manganous nitrate solution (0.3984mol), adding 100 water, uniformly mixing, adding 80mL of 25% ammonia water (1.035mol) by mass concentration through a peristaltic pump while stirring, adjusting the pH value of the system to 8.12, continuously stirring for 10 minutes after the addition is finished, then adding 65mL of 30% hydrogen peroxide (0.5876mol) by mass concentration through the peristaltic pump while stirring at a feeding speed of 80r/min, continuously stirring for 40 minutes after the oxidation reaction is finished, then adding 50mL of 1.99mol/L ferric nitrate nonahydrate solution (0.0996mol) into the system, uniformly mixing and stirring for 30 minutes, then heating a reaction kettle to 165 ℃, then adding 45mL of 85% phosphoric acid (0.6557mol) by mass concentration, reacting for 6 hours, naturally cooling the slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final ferric manganese phosphate (with one crystal water) product, the chemical formula is Mn0.8Fe0.2PO4·H2And O. Pre-roasting 100g of prepared iron-manganese phosphate product in air at 550 ℃ for 3 hours, and naturally cooling to room temperature for later use. The preparation method comprises the steps of weighing raw materials according to the mol ratio Li/(Mn + Fe) ═ 1.10, sequentially adding lithium carbonate, pre-roasted ferric manganese phosphate and 9.38g of starch into a sand mill containing 1600mL of ethanol, grinding for 4 hours, taking out slurry after the particle size of the materials is 200-300 nm, drying and crushing. Under the protection of nitrogen, placing the crushed material in a tube furnace to be sintered for 8 hours, wherein the sintering temperature is 680 ℃, and waiting for the tube furnace to naturally cool downTaking out the material after the temperature is high to obtain lithium manganese iron phosphate product Li1.1Mn0.8Fe0.2PO4。
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications and additions may be made thereto by those skilled in the art without departing from the spirit of the invention or exceeding the scope defined by the claims.
Claims (9)
1. The preparation method of the iron-manganese phosphate is characterized by comprising the following steps:
1) adding a mixed salt of a divalent manganese salt and a divalent ferric salt into a reaction kettle, adding water, stirring at room temperature to completely dissolve the mixed salt, and preparing aqueous solutions of the divalent manganese salt and the divalent ferric salt with the concentrations of 0.2-4 mol/L respectively;
2) adding the prepared pH regulator into the reaction kettle through a peristaltic pump while stirring, adjusting the pH value of the reaction system to 7.5-12.0, and continuing stirring for 10-20 minutes after the reaction is finished;
3) adding an oxidant into the reaction kettle at a feeding speed of 30-100 r/min through a peristaltic pump, and continuously stirring for 20-60 minutes after finishing the adding; the oxidant is one or more of sodium peroxide, hydrogen peroxide and ozone;
4) after the temperature in the reaction kettle reaches 60-165 ℃, adding a soluble phosphorus source solution by using a peristaltic pump, reacting for 2-8 hours, naturally cooling the iron-manganese phosphate slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final product MnxFe1-xPO4·yH2O。
2. The method of claim 1, wherein:
1) the manganous salt is one or more of manganous sulfate, manganous nitrate, manganous chloride and manganous acetate;
2) the ferrous salt is one or more of ferrous sulfate, ferrous nitrate and ferrous chloride;
3) the pH regulator is one or more of sodium hydroxide, ammonia water, sodium acetate and ammonium acetate;
4) the molar ratio of the oxidant to manganese and iron, namely oxidant/(Mn + Fe) is 1-4;
5) the phosphorus source is one or more of phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and ammonium phosphate, and the molar ratio of the phosphorus source to manganese to iron is 1.1-2/(Mn + Fe);
6) by adjusting the feeding molar ratio of Mn/Fe to 1-4 of manganese salt and ferric salt, the iron manganese phosphate Mn with different Mn/Fe molar ratios can be obtainedxFe1-xPO4·yH2O, x is more than or equal to 0.5 and less than or equal to 0.8, and y is 0 or 1.
3. The method of claim 1, wherein:
1) adding a divalent manganese salt into a reaction kettle, adding water, stirring at room temperature to completely dissolve the divalent manganese salt, and preparing an aqueous solution of the divalent manganese salt with the concentration of 0.2-4 mol/L;
2) adding the prepared pH regulator into the reaction kettle through a peristaltic pump while stirring, adjusting the pH value of the reaction system to 7.5-12.0, and continuing stirring for 10-20 minutes after the reaction is finished;
3) adding an oxidant into the reaction kettle at a feeding speed of 30-100 r/min through a peristaltic pump, and continuously stirring for 20-60 minutes after finishing the adding; the oxidant is one or more of sodium peroxide, hydrogen peroxide and ozone;
4) adding the prepared ferric iron salt solution into the reaction kettle through a peristaltic pump, and continuing stirring for 30 minutes after the reaction is finished; the concentration of the ferric salt solution is 0.2-4 mol/L;
5) after the temperature in the reaction kettle reaches 60-165 ℃, adding a certain amount of soluble phosphorus source solution by using a peristaltic pump, reacting for 2-8 hours, naturally cooling the iron-manganese phosphate slurry to room temperature after the reaction is finished, washing, filtering and drying to obtain a final product MnxFe1-xPO4·yH2O。
4. The method of claim 3, wherein:
1) the manganous salt is one or more of manganous sulfate, manganous nitrate, manganous chloride and manganous acetate;
2) the pH regulator is one or more of sodium hydroxide, ammonia water, sodium acetate and ammonium acetate;
3) the molar ratio of the oxidant to manganese to iron is 1-4/(Mn + Fe);
4) the ferric iron salt is one or more of ferric sulfate, ferric nitrate and ferric chloride;
5) the phosphorus source is one or more of phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and ammonium phosphate, and the molar ratio of the phosphorus source to manganese to iron is 1.1-2/(Mn + Fe);
6) by adjusting the feeding molar ratio of Mn/Fe to 1-4 of manganese salt and ferric salt, the iron manganese phosphate Mn with different Mn/Fe molar ratios can be obtainedxFe1-xPO4·yH2O, x is more than or equal to 0.5 and less than or equal to 0.8, and y is 0 or 1.
5. A ferro-manganese phosphate product produced according to the process of any one of claims 1 to 4.
6. A lithium manganese iron phosphate synthesized from the lithium compound and the manganese iron phosphate produced by the method according to any one of claims 1 to 4.
7. The lithium manganese iron phosphate according to claim 6, wherein said lithium compound is one or more of lithium carbonate, lithium hydroxide, and lithium acetate.
8. A positive electrode material for a secondary battery in which charge and discharge are repeated by a battery electrode reaction, comprising the lithium manganese iron phosphate according to claim 6 as a main component.
9. A secondary battery produced from the positive electrode material for a battery according to claim 8.
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| CN113659133A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Preparation method of high-compaction lithium ferric manganese phosphate cathode material |
| CN114057177B (en) * | 2021-11-23 | 2023-05-23 | 湖北融通高科先进材料集团股份有限公司 | Ferrous manganese phosphate and preparation method and application thereof |
| CN114497519B (en) * | 2022-01-28 | 2024-01-30 | 中南大学 | Preparation method for synthesizing lithium iron manganese phosphate anode material by wet method lithium intercalation |
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| CN114940485B (en) * | 2022-07-25 | 2022-10-28 | 蜂巢能源科技股份有限公司 | Lithium manganese iron phosphate precursor and preparation method and application thereof |
| CN115321507B (en) * | 2022-08-25 | 2023-07-07 | 广东邦普循环科技有限公司 | Method for preparing ferric manganese phosphate by coprecipitation and application thereof |
| GB2627026A (en) * | 2022-08-25 | 2024-08-14 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing ferromanganese phosphate by coprecipitation and use thereof |
| CN115849324A (en) * | 2022-11-23 | 2023-03-28 | 中国科学院深圳先进技术研究院 | Lithium iron manganese phosphate precursor and preparation method and application thereof |
| CN116216682A (en) * | 2023-02-23 | 2023-06-06 | 广东邦普循环科技有限公司 | Preparation method and application of ferric manganese phosphate precursor |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605722A (en) * | 2006-12-22 | 2009-12-16 | 尤米科尔公司 | Crystalline nanometer LiFeMPO 4Synthetic |
| CN104518217A (en) * | 2015-01-20 | 2015-04-15 | 杨志宽 | Battery grade iron and manganese phosphate and preparation method thereof |
| CN104681795A (en) * | 2015-01-29 | 2015-06-03 | 北大先行科技产业有限公司 | Preparation method for lithium ferric manganese phosphate/carbon composite material |
| CN105226273A (en) * | 2014-05-30 | 2016-01-06 | 比亚迪股份有限公司 | A kind of iron manganese phosphate for lithium and preparation method thereof and application |
| CN105655584A (en) * | 2016-03-07 | 2016-06-08 | 昆明理工大学 | Preparation method of ferromanganese ammonium phosphate for preparing lithium-ion battery anode material |
| CN106340620A (en) * | 2016-08-31 | 2017-01-18 | 深圳市沃特玛电池有限公司 | Preparation method of lithium manganese ferric phosphate/carbon composite positive electrode material for lithium battery |
| CN106486668A (en) * | 2016-10-14 | 2017-03-08 | 山东省科学院能源研究所 | A kind of phosphoric acid ferrimanganic vanadium presoma, phosphoric acid ferrimanganic vanadium lithium/carbon positive electrode and preparation method |
-
2017
- 2017-10-31 CN CN201711039832.4A patent/CN107697899B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605722A (en) * | 2006-12-22 | 2009-12-16 | 尤米科尔公司 | Crystalline nanometer LiFeMPO 4Synthetic |
| CN105226273A (en) * | 2014-05-30 | 2016-01-06 | 比亚迪股份有限公司 | A kind of iron manganese phosphate for lithium and preparation method thereof and application |
| CN104518217A (en) * | 2015-01-20 | 2015-04-15 | 杨志宽 | Battery grade iron and manganese phosphate and preparation method thereof |
| CN104681795A (en) * | 2015-01-29 | 2015-06-03 | 北大先行科技产业有限公司 | Preparation method for lithium ferric manganese phosphate/carbon composite material |
| CN105655584A (en) * | 2016-03-07 | 2016-06-08 | 昆明理工大学 | Preparation method of ferromanganese ammonium phosphate for preparing lithium-ion battery anode material |
| CN106340620A (en) * | 2016-08-31 | 2017-01-18 | 深圳市沃特玛电池有限公司 | Preparation method of lithium manganese ferric phosphate/carbon composite positive electrode material for lithium battery |
| CN106486668A (en) * | 2016-10-14 | 2017-03-08 | 山东省科学院能源研究所 | A kind of phosphoric acid ferrimanganic vanadium presoma, phosphoric acid ferrimanganic vanadium lithium/carbon positive electrode and preparation method |
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