CN115893354A - Preparation method and application of phosphate anode material precursor - Google Patents
Preparation method and application of phosphate anode material precursor Download PDFInfo
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Abstract
The invention provides a preparation method and application of a phosphate anode material precursor, and belongs to the technical field of lithium ion battery anode materials. According to the method, the manganese phosphate aggregate can be generated by reacting the trimanganese tetroxide with the phosphoric acid under the condition of heating at normal pressure, the operation of the whole reaction process is simple and environment-friendly, the use of an organic solvent and an oxidant is avoided, the excessive phosphoric acid can be reused, almost no wastewater or waste salt is generated, and the method is very suitable for industrial popularization and application. The prepared manganese phosphate precursor is mixed with ferric phosphate and lithium carbonate or is independently mixed with lithium carbonate, ground and sintered to prepare the excellent lithium manganese phosphate or excellent lithium manganese phosphate positive electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method and application of a phosphate anode material precursor.
Background
Manganese phosphate is an important chemical raw material and is widely applied to the fields of catalysts, lubricants, pigments, adsorbents and the like. With the recent rise of positive electrode materials of lithium batteries, manganese phosphate is more and more receiving attention as a raw material of lithium manganese phosphate and lithium manganese iron phosphate which are positive electrode materials of phosphates.
At present, many research methods for preparing manganese phosphate exist, but the industrial production is difficult all the time, and the main reason is that Mn 3+ Easily disproportionate in water solution to generate Mn 2+ And MnO 2 It is not easy to prepare pure-phase manganese phosphate MnPO 4 ·H 2 And O. It is therefore common to prepare Mn using nitrates in ethanol or aqueous solution 2+ Oxidation to Mn 3+ Or with phosphoric acid or a phosphate to form manganese phosphate.
Such as Liu et al (Solid states ionics 254 (2014) 72-77) using a 50% manganese nitrate to 70% phosphoric acid solution in a volume ratio of 1:7 at room temperature for 12 hours to obtain manganese phosphate monohydrate. For another example, chinese patent CN105244497A provides a method for preparing a manganese iron phosphate intermediate by using manganese nitrate, ferric nitrate, other doped metal salts (optionally added), and phosphoric acid as main raw materials, and performing condensation, reflux and heating in an ethanol-water mixed system, wherein the method is easy to control, has a lower reaction temperature, and is simple in process, and the inventors found that, in the course of research, when the volume ratio of water to ethanol is greater than 1. By adjusting the proportion of water to ethanol, fe with high yield up to 99%, accurate Fe/Mn ratio and high reaction activity can be prepared x Mn (1-x-y) M y PO 4 ·zH 2 And (4) an O intermediate.
However, the use of nitrate and ethanol in the above method not only increases the production cost, but also increases the environmental protection cost (generation of waste liquid and waste gas), which is not favorable for mass production.
In order to develop a more environment-friendly and simple-to-operate preparation method of manganese phosphate, chinese patent CN112142028B is correspondingly improved on the basis of patent CN102849715A, the use of sulfuric acid and oxalic acid is directly abandoned, and KMnO is directly used 4 And 85% H 3 PO 4 Preparing the manganese phosphate at high temperature and high pressure. But due to KMnO 4 Belongs to chemical products which are easy to produce poison and explosion, is not beneficial to industrial purchase, and simultaneously limits the industrial large-scale production of the chemical products under high temperature and high pressure.
Therefore, it is required to develop a preparation method of the manganese phosphate precursor, which is simple to operate, is beneficial to environmental protection and is suitable for large-scale production.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a novel preparation method of a manganese phosphate precursor. According to the method, the manganous-manganic oxide and the phosphoric acid react under the normal-pressure heating condition to generate the aggregated manganese phosphate, the whole reaction process is simple to operate and environment-friendly, the use of an organic solvent and an oxidant is avoided, the excessive phosphoric acid can be reused, wastewater and waste salt are hardly generated, and the method is very suitable for industrial popularization and application. And the prepared manganese phosphate precursor is mixed with ferric phosphate and lithium carbonate or is independently mixed with lithium carbonate, ground and sintered to prepare the excellent lithium manganese phosphate or excellent lithium manganese phosphate positive electrode material.
The general reaction equation in the whole manganese phosphate preparation process is as follows:
Mn 3 O 4 +nH 3 PO 4 →MnPO 4 ·H 2 O↓+(n-1)H 3 PO 4 +H 2 o (n is more than or equal to 2 at normal temperature and normal pressure)
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
in one aspect, the application provides a preparation method of a manganese phosphate precursor, which comprises the following steps:
(1) Adding manganous-manganic oxide powder into a dilute phosphoric acid solution at a certain temperature;
(2) After the manganous manganic oxide powder is added, raising the reaction temperature to a certain temperature, and reacting at the temperature;
(3) After the reaction is finished, filtering and washing a reaction product to obtain a manganese phosphate precursor filter cake, and drying the manganese phosphate precursor filter cake in a blast drying oven at 100 ℃ for 12 hours to finally obtain a dark green manganese phosphate monohydrate precursor;
(4) And placing the dried manganese phosphate precursor in a muffle furnace at a certain temperature for high-temperature dehydration to finally obtain the dehydrated manganese phosphate precursor.
Further, the certain temperature in the step (1) is 40-60 ℃; the concentration of the dilute phosphoric acid is 20-40%;
preferably, the certain temperature in the step (1) is 50-60 ℃, and the concentration of the dilute phosphoric acid is 30-35%;
further, the molar weight ratio of the phosphoric acid to the manganese source in the manganous-manganic oxide in the step (1) is 2-3.
Further, the certain temperature in the step (2) is 85-100 ℃, and the reaction time is 4-8 hours.
Preferably, the certain temperature in the step (2) is 90-100 ℃, and the reaction time is 4-6 hours.
Furthermore, the excess phosphoric acid mother liquor after filtration in the step (3) can be reused and recycled.
Further, the high temperature in the step (4) is 400-600 ℃, and the dehydration time is 3-6 hours.
Preferably, the high temperature in the step (4) is 500-550 ℃, and the dehydration time is 3-4 hours.
In another aspect, the present application provides a manganese phosphate precursor prepared by the above method.
On the other hand, the application also provides the application of the manganese phosphate precursor prepared by the method in the preparation of the lithium manganese phosphate/carbon composite material.
The preparation method of the lithium ferric manganese phosphate/carbon composite material comprises the following steps:
s1, taking a lithium source, anhydrous iron phosphate, a dehydrated manganese phosphate precursor, a carbon source and an additive, grinding, mixing and drying in a liquid phase system to obtain a lithium manganese phosphate/carbon composite material precursor;
and S2, sintering the obtained lithium manganese iron phosphate/carbon composite material precursor in an inert gas protection atmosphere to finally obtain the lithium manganese iron phosphate/carbon composite material.
Further, the lithium source in the step S1 is any one or more of lithium carbonate, lithium hydroxide and lithium acetate;
preferably, the lithium source in step S1 is lithium carbonate;
in the step S1, the carbon source is any one or more of glucose, rock candy, cane sugar, fructose, polyethylene glycol, cyclodextrin, starch and cellulose;
preferably, the carbon source in step S1 is any one or more of glucose, polyethylene glycol, cyclodextrin and starch;
the additive in the step S1 is any one or more of titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium oxide, magnesium hydroxide, magnesium nitrate, zirconium dioxide, zirconium hydroxide, niobium pentoxide, nickel acetate, nickel nitrate and nickel hydroxide, and the dosage of the additive is 0-0.5% of the mass of the final lithium manganese iron phosphate;
preferably, the additive mentioned in the step S1 is any one or more of titanium dioxide, magnesium oxide, magnesium hydroxide, zirconium dioxide, nickel acetate and nickel hydroxide, and the amount of the additive is 0-0.5% of the final lithium manganese iron phosphate.
The liquid phase system medium in the step S1 is any one of water, methanol or ethanol;
preferably, the liquid phase system medium in the step S1 is water or ethanol.
Further, the Fe/P molar ratio of the anhydrous molten iron phosphate described in the above step S1
=0.97-0.98; the molar ratio of manganese phosphate to iron phosphate and manganese, iron and manganese phosphate metal is more than or equal to 0.5 and less than or equal to nMn/nFe + nMn and less than or equal to 1; and the mass of the lithium source is fed according to the mol ratio Li/P = 1.0-1.05.
Further, the grinding in step S1 is coarse grinding with a basket grinder for 30-60 min, with the grinding particle size being controlled at D 50 =1-2um; and then, finely grinding by using a fine sand grinder, wherein the finely grinding time is 60-120min, and the granularity of the finely ground slurry is controlled to be 200-400nm.
Further, the drying manner in the step S1 is static drying or spray drying.
Further, the sintering temperature in the step S1 is 650-750 ℃, and the sintering time is 7-10 hours.
The inert gas in the step S2 is any one or more of argon, helium, nitrogen and carbon dioxide.
And (3) carrying out graded crushing treatment on the sintered lithium iron phosphate/carbon composite material in the step (S2) to obtain the lithium manganese iron phosphate/carbon composite material with the carbon content of 1.5-2.5wt%.
Compared with the prior art, the invention has the technical advantages that:
(1) The invention aims to provide a preparation method of a manganese phosphate precursor, which is simple in process and environment-friendly. The method can generate the aggregate manganese phosphate by reacting the trimanganese tetroxide with the phosphoric acid under the condition of normal pressure heating, the operation of the whole reaction process is simple and environment-friendly, the use of organic solvents and oxidants is avoided, the excessive phosphoric acid can be reused, almost no waste water and waste salt are generated, and the method is very suitable for industrial popularization and application.
(2) The invention also provides a preparation method of the lithium iron manganese phosphate; the excellent lithium manganese phosphate or the excellent lithium manganese phosphate positive electrode material can be prepared by mixing, grinding and sintering the self-made manganese phosphate precursor with ferric phosphate and lithium carbonate or independently mixing, grinding and sintering the self-made manganese phosphate precursor with the lithium iron phosphate and the lithium carbonate.
Drawings
FIG. 1: SEM photograph 2 ten thousand times of manganese phosphate monohydrate prepared in example 1;
FIG. 2 is a schematic diagram: SEM photograph at 5 ten thousand times of manganese phosphate monohydrate prepared in example 1;
FIG. 3: XRD pattern of manganese phosphate monohydrate prepared in example 1.
Detailed Description
The present invention will be described below with reference to specific examples to make the technical aspects of the present invention easier to understand and grasp, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available; and different sources have no significant influence on the product performance.
Example 1
(1) Preparing a manganese phosphate precursor:
76.27g of trimanganese tetroxide (99 wt%) was slowly added into a 2L Erlenmeyer flask containing 817g of 30% hot diluted phosphoric acid solution (solution temperature 60 degrees) with stirring, after the addition of trimanganese tetroxide was completed, a temperature rising mode was started, when the reaction temperature reached 90 degrees, the reaction time was counted, and the reaction was thermostatically carried out at the temperature for 6 hours. After the reaction is finished, filtering and washing the product (the excessive phosphoric acid mother liquor can be recycled), and drying the obtained manganese phosphate precursor filter cake in a 100-DEG C air-blast drying oven for 12 hours to finally obtain 110g of dark green manganese phosphate precursor.
The manganese phosphate specific surface was analyzed to be 18.19m 2 In terms of/g, the Mn content was 32.27%, and the P content was 18.56%. Observing the obtained manganese phosphate precursor by a scanning electron microscope, wherein the result is shown in figure 1; and simultaneously, carrying out XRD characterization on the obtained manganese phosphate precursor, and carrying out phase analysis, wherein the characterization result is shown in figure 2.
As can be seen from FIG. 1, the prepared manganese phosphate precursor is an aggregate composed of primary non-uniform particles, and the primary particles are different in size, and the particle size is between 30 and 150 nm. As can be seen from FIG. 2, the XRD pattern of the prepared manganese phosphate precursor can well conform to MnPO 4 ·H 2 A standard map of O (PDF card number 44-0071), which indicates that the prepared manganese phosphate precursor is manganese phosphate monohydrate.
(2) Preparing a lithium ferric manganese phosphate/carbon composite material:
placing 100g of manganese phosphate monohydrate in a muffle furnace at 500 ℃ for heating and dehydrating for 4 hours to obtainA dehydrated manganese phosphate precursor; feeding according to the raw material molar ratio Li/P = 1.03; the dehydrated manganese phosphate precursor, 59.76g of anhydrous iron phosphate (Fe/P = 0.975), 39.42g of lithium carbonate (99.5 wt%), 12.64g of glucose, 6.2g of polyethylene glycol 20000, 0.4g of nickel hydroxide, and 0.35g of magnesium hydroxide were added to a 2L measuring cup containing 800mL of water, the cup was ground in a basket grinder at a rotation speed of 2000r/min for 30 minutes, the slurry was introduced into a sand mill for grinding after the grinding was completed, and the slurry was spray-dried after the slurry particle size reached 300 nm. After the spray drying is finished, the dried and crushed material is placed in a tubular furnace under the nitrogen atmosphere for sintering, the sintering temperature is 675 ℃, and the constant temperature is kept for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.4 Mn 0.6 PO 4 a/C composite material.
To prepare LiFe 0.4 Mn 0.6 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, electrode plates are manufactured according to the mass ratio of 90. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 152.9mAh/g, and the initial reversible capacity of charging and discharging at 1C is 145.8mAh/g.
Example 2
(1) Preparing a manganese phosphate precursor:
76.27g of manganous manganic oxide (99 wt%) was slowly added into a 2L Erlenmeyer flask containing 784g of 30% hot dilute phosphoric acid solution (solution temperature 60 degrees) under stirring, after the completion of the manganous manganic oxide addition, a temperature raising mode was started, when the reaction temperature reached 95 degrees, the reaction time was counted, and the reaction was thermostatically carried out at this temperature for 4 hours. After the reaction is finished, filtering and washing the product (the excessive phosphoric acid mother liquor can be recycled), drying the obtained manganese phosphate precursor filter cake in a blast drying oven at 100 ℃ for 12 hours to finally obtain 120g of dark green manganese phosphate precursor, and analyzing that the specific surface of the manganese phosphate is 16.20m 2 (ii)/g, wherein the Mn content is 32.48%, and the P content is 18.47%;
(2) Preparing a lithium ferric manganese phosphate/carbon composite material:
heating 117g of manganese phosphate monohydrate in a muffle furnace at 500 ℃ for dehydration for 4 hours to obtain a dehydrated manganese phosphate precursor; the raw materials are fed according to the molar ratio Li/P =1.04, the dehydrated manganese phosphate precursor, 44.88g of anhydrous iron phosphate (Fe/P = 0.975), 39.65g of lithium carbonate (99.5 wt%), 10.2g of cyclodextrin, 6.2g of polyethylene glycol 20000, 0.45g of titanium dioxide and 0.3g of magnesium oxide are added into a 2L measuring cup containing 800mL of anhydrous ethanol, the cup is placed into a basket mill to be ground for 30 minutes at the rotating speed of 2000r/min, the slurry is led into a sand mill to be ground after the grinding is finished, and the slurry is subjected to spray drying after the particle size of the slurry reaches 300 nm. After the spray drying is finished, the dried and crushed material is placed in a tubular furnace under the nitrogen atmosphere for sintering, the sintering temperature is 675 ℃, and the constant temperature is kept for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.8 percent 0.3 Mn 0.7 PO 4 a/C composite material.
To prepare LiFe 0.3 Mn 0.7 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, electrode plates are manufactured according to the mass ratio of 90. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 151.5mAh/g, and the initial reversible capacity of charging and discharging at 1C is 143.8mAh/g.
Example 3
(1) Preparing a manganese phosphate precursor:
76.27g of manganous manganic oxide (99 wt%) was slowly added into a 2L Erlenmeyer flask containing 700g of 35% hot dilute phosphoric acid solution (solution temperature is 50 degrees) under stirring, after the manganous manganic oxide addition was completed, a temperature raising mode was started, when the reaction temperature reached 100 degrees, the reaction time was counted, and the reaction was thermostatically carried out at this temperature for 4 hours. After the reaction is finished, filtering and washing the product (the excessive phosphoric acid mother liquor can be recycled), and drying the obtained manganese phosphate precursor filter cake in a blast drying oven at 100 ℃ for 12 hours, wherein the maximum time is115g of greenish black manganese phosphate precursor is finally obtained, and the manganese phosphate specific surface is 12.12m by analysis 2 (ii)/g, wherein the Mn content is 32.15%, and the P content is 18.66%;
(2) Preparing a lithium ferric manganese phosphate/carbon composite material:
placing 84g of manganese phosphate monohydrate in a muffle furnace at 550 ℃ for heating and dehydrating for 3 hours to obtain a dehydrated manganese phosphate precursor; the raw materials are fed according to the molar ratio Li/P =1.04, the dehydrated manganese phosphate precursor, 74.5g of anhydrous iron phosphate (Fe/P = 0.970), 39.45g of lithium carbonate (99.5 wt%), 11.2g of starch, 3.2g of polyethylene glycol 20000, 0.45g of zirconium dioxide and 0.3g of titanium dioxide are added into a 2L measuring cup containing 800mL of anhydrous ethanol, the cup is placed into a basket mill to be ground for 30 minutes at the rotating speed of 2000r/min, the slurry is led into a sand mill to be ground after the grinding is finished, and the slurry is subjected to spray drying after the particle size of the slurry reaches 300 nm. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.6 percent 0.5 Mn 0.5 PO 4 a/C composite material.
To prepare LiFe 0.3 Mn 0.7 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, electrode plates are manufactured according to the mass ratio of 90. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 153.5mAh/g, and the initial reversible capacity of charging and discharging at 1C is 146.9mAh/g.
Example 4
(1) Preparing a manganese phosphate precursor:
76.27g of trimanganese tetroxide (99 wt%) was slowly added into a 2L Erlenmeyer flask containing 644g of 35% hot dilute phosphoric acid solution (solution temperature 50 ℃ C.) with stirring, after the completion of the trimanganese tetroxide addition, a temperature-raising mode was started, when the reaction temperature reached 100 ℃ C., the reaction time was counted, and the isothermal reaction was performed at this temperature for 6 hours. Knot to be reactedAnd after the reaction, filtering and washing the product (the excessive phosphoric acid mother liquor can be recycled), drying the obtained manganese phosphate precursor filter cake in a 100-DEG air drying oven for 12 hours to finally obtain 120g of dark green manganese phosphate precursor, and analyzing that the manganese phosphate specific surface is 10.12m 2 (ii)/g, wherein the Mn content is 32.18%, and the P content is 18.79%;
(2) Preparing a lithium ferric manganese phosphate/carbon composite material:
heating 117g of manganese phosphate monohydrate in a muffle furnace at 500 ℃ for dehydration for 4 hours to obtain a dehydrated manganese phosphate precursor; charging according to the raw material molar ratio Li/P =1.04, adding 28.07g of lithium carbonate (99.5 wt%), 12.1g of cyclodextrin, 4.2g of polyethylene glycol 20000, 0.35g of nickel acetate and 0.2g of magnesium oxide into a 2L measuring cup containing 800mL of absolute ethyl alcohol, placing the measuring cup into a basket mill, milling for 30 minutes at the rotating speed of 2000r/min, introducing the slurry into a sand mill for milling after the milling is finished, and performing spray drying on the slurry after the slurry granularity reaches 250 nm. After the spray drying is finished, the dried and crushed material is placed in a tubular furnace under the nitrogen atmosphere for sintering, the sintering temperature is 675 ℃, and the constant temperature is kept for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiMnPO with the carbon content of 2.0 percent 4 a/C composite material.
To prepared LiMnPO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, electrode plates are manufactured according to the mass ratio of 90. Under the conditions of 2-4.5V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 152.5mAh/g, and the initial reversible capacity of charging and discharging at 1C is 144.8mAh/g.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. A preparation method of a manganese phosphate precursor is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding manganous-manganic oxide powder into a dilute phosphoric acid solution at a certain temperature;
(2) After the manganous-manganic oxide powder is added, raising the reaction temperature to a certain temperature, and reacting at the temperature;
(3) After the reaction is finished, filtering and washing a reaction product to obtain a manganese phosphate precursor filter cake, and drying the manganese phosphate precursor filter cake in an air drying oven at the temperature of 100 ℃ for 12 hours to finally obtain a dark green manganese phosphate monohydrate precursor;
(4) And placing the dried manganese phosphate precursor in a muffle furnace at a certain temperature for high-temperature dehydration to finally obtain the dehydrated manganese phosphate precursor.
2. The method of claim 1, wherein: the certain temperature in the step (1) is 40-60 ℃; the concentration of the dilute phosphoric acid is 20-40%; the molar weight ratio of the phosphoric acid to the manganese source in the mangano-manganic oxide is 2-3:1.
3. the production method according to claim 1, characterized in that: the certain temperature in the step (2) is 85-100 ℃, and the reaction time is 4-8 hours; the high temperature in the step (4) is 400-600 ℃, and the dehydration time is 3-6 hours.
4. A manganese phosphate precursor prepared by the preparation method of any one of claims 1 to 3 and application of the prepared manganese phosphate precursor in preparing lithium manganese iron phosphate/carbon composite materials.
5. Use according to claim 4, characterized in that: the preparation method of the lithium ferric manganese phosphate/carbon composite material comprises the following steps:
s1, taking a lithium source, anhydrous iron phosphate, a dehydrated manganese phosphate precursor, a carbon source and an additive, grinding, mixing and drying in a liquid phase system to obtain a lithium manganese phosphate/carbon composite material precursor;
and S2, sintering the obtained lithium manganese iron phosphate/carbon composite material precursor in an inert gas protection atmosphere to finally obtain the lithium manganese iron phosphate/carbon composite material.
6. Use according to claim 5, characterized in that: the lithium source in the step S1 is any one or more of lithium carbonate, lithium hydroxide and lithium acetate; the carbon source is any one or more of glucose, rock candy, sucrose, fructose, polyethylene glycol, cyclodextrin, starch and cellulose.
7. Use according to claim 5, characterized in that: the additive in the step S1 is any one or more of titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium oxide, magnesium hydroxide, magnesium nitrate, zirconium dioxide, zirconium hydroxide, niobium pentoxide, nickel acetate, nickel nitrate and nickel hydroxide, and the dosage of the additive is 0-0.5% of the mass of the final lithium manganese iron phosphate.
8. Use according to claim 5, characterized in that: the liquid phase system medium in the step S1 is any one of water, methanol or ethanol;
the Fe/P molar ratio of ferric phosphate in the anhydrous ferric phosphate is =0.97-0.98; the molar ratio of manganese phosphate to iron phosphate and manganese iron manganese phosphate metal is more than or equal to 0.5 and less than or equal to nMn/nFe + nMn and less than or equal to 1, and the mass of the lithium source is fed according to the molar ratio Li/P = 1.0-1.05;
the grinding process comprises the steps of firstly carrying out coarse grinding by using a basket grinder, wherein the grinding time is 30-60 min, and the grinding granularity is controlled to be D 50 =1-2um; and then, finely grinding by using a fine sand grinder, wherein the finely grinding time is 60-120min, and the granularity of the finely ground slurry is controlled to be 200-400nm.
9. Use according to claim 5, characterized in that: the drying mode in the step S1 is static drying or spray drying; the sintering temperature is 650-750 ℃, and the sintering time is 7-10 hours; the inert gas is any one or more of argon, helium, nitrogen and carbon dioxide.
10. Use according to claim 5, characterized in that: and (3) carrying out graded crushing treatment on the sintered lithium iron phosphate/carbon composite material in the step (S2) to obtain the lithium manganese iron phosphate/carbon composite material with the carbon content of 1.5-2.5wt%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413943A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
| WO2014134969A1 (en) * | 2013-03-04 | 2014-09-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous manganese lithium phosphate-carbon composite material, preparation method and application thereof |
| US20160118658A1 (en) * | 2014-10-27 | 2016-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Particle, electrode, power storage device, electronic device, and method for manufacturing electrode |
| CN114583155A (en) * | 2022-03-11 | 2022-06-03 | 上海鑫忆丹新材料有限公司 | Preparation method of lithium ferric manganese phosphate material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014134969A1 (en) * | 2013-03-04 | 2014-09-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous manganese lithium phosphate-carbon composite material, preparation method and application thereof |
| CN103413943A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
| US20160118658A1 (en) * | 2014-10-27 | 2016-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Particle, electrode, power storage device, electronic device, and method for manufacturing electrode |
| CN114583155A (en) * | 2022-03-11 | 2022-06-03 | 上海鑫忆丹新材料有限公司 | Preparation method of lithium ferric manganese phosphate material |
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Inventor after: Huang Changjing Inventor after: Gao Wei Inventor before: Huang Changjing Inventor before: Gao Wei Inventor before: Zhou Dan |