CN110002418B - Preparation method of manganese phosphate - Google Patents
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Abstract
The invention discloses a preparation method of manganese phosphate. Adding manganese salt into pure water, adding a complexing agent and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, and adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution; adding a base solution into the reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, starting stirring, enabling the stirring speed to be 200-year-round 300r/min, then adding the manganese solution, the precipitator solution and the phosphoric acid solution into the base solution in a parallel flow manner, and continuously overflowing and discharging; and aging the continuous overflow discharge in a transfer tank, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by adopting a cooling coil pipe, and then filtering, washing, drying, screening and removing iron to obtain the manganese phosphate. The method has the advantages of simple process and low cost, and the obtained manganese phosphate has uniform particle size distribution, good crystallinity, small primary particle size, compact growth and high tap density.
Description
Technical Field
The invention relates to a preparation method of manganese phosphate, belonging to the field of new energy materials of lithium batteries.
Background
Manganese phosphate is Mn3(PO4)2.3H2And O. The lithium manganese phosphate anode material is applied to the pharmaceutical industry and the glass and ceramic industry, along with the development of lithium battery materials, the lithium manganese phosphate anode material receives great attention, and the lithium manganese phosphate anode material has the chemical formula of LiMnPO4The material is a natural mineral or artificially synthesized ternary lithium battery electrode material. The material has an olivine-like crystal structure, resulting in physical and chemical stability as an electrode material. And the lithium manganese phosphate has the specific capacity of 171mAh/g and the discharge platform (vs Li/Li) of about 4.1V+) This also makes lithium manganese phosphate an ideal material for the new generation of lithium ion power cells.
The common laboratory preparation methods of lithium manganese phosphate mainly comprise a solid-phase method and a liquid-phase method. The solid phase method adopts solid lithium salt, manganese salt and phosphate to be ball-milled and mixed and burnt at high temperature in the atmosphere of protective gas. The liquid phase method is divided into a polyol method, a sol-gel method and a hydrothermal method, the shape and purity of the lithium manganese phosphate synthesized by the liquid phase method are easier to control, but the method also has the problem of incomplete crystallization and often needs further annealing and firing.
And the manganese phosphate is used as a precursor, so that the oxidation-reduction reaction in a sintering furnace can be avoided, and the crystal structure, the particle size distribution and the primary particle size of the manganese phosphate have important influence on the manganese lithium phosphate.
Disclosure of Invention
In view of the above, the invention provides a preparation method of manganese phosphate, which has the advantages of simple process, low cost, uniform particle size distribution of the obtained manganese phosphate, good crystallinity, small primary particle size, compact growth and high tap density.
The invention solves the technical problems by the following technical means:
a preparation method of manganese phosphate comprises the following steps:
(1) adding manganese salt into pure water, adding a complexing agent and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, and adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution;
(2) adding a base solution into a reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, the pH value of the mixed solution is 2.5-3, heating to 90-95 ℃, starting stirring to ensure that the stirring speed is 200 ion-doped 300r/min, then adding a manganese solution, a precipitator solution and a phosphoric acid solution into the base solution in a cocurrent manner, maintaining the pH value of the reaction process to be 2.5-3, the reaction temperature to be 90-95 ℃, the manganese ion content in a supernatant to be 100 ion-doped 300mg/L, the retention time to be 7-10h, and continuously overflowing and discharging;
(3) and aging the continuous overflow discharge in a transfer tank for 1-2h, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by adopting a cooling coil pipe, and then filtering, washing, drying, screening and removing iron to obtain the manganese phosphate.
The manganese salt is at least one of battery-grade manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, the complexing agent is DETA, the concentration of manganese ions in the obtained manganese solution is 1-1.5mol/L, the concentration of the complexing agent is 0.01-0.05mol/L, and the mass fraction of polyethylene glycol 4000 is 0.1-0.5%.
The concentration of urea in the precipitant solution is 2-3mol/L, and the concentration of MAP is 1-1.5 mol/L.
The concentration of the phosphoric acid solution is 1-2 mol/L.
The volume of the base solution added in the step (2) is 0.15-0.2 time of the volume of the reaction kettle.
And (3) in the aging process, the stirring speed is maintained at 150-200r/min, cold pure water is adopted in a cooling coil for cooling, and the manganese phosphate is washed by hot pure water after heat exchange.
The screening adopts a 150-plus-200-mesh ultrasonic vibration screen, and the iron removal adopts an electromagnetic iron remover.
Adding calcium oxide into the mother liquor obtained by filtering in the step (3), adjusting the pH value of the solution to 8-8.5, then filtering, concentrating and crystallizing the obtained filtrate to obtain a nitrogen fertilizer, adding sulfuric acid into the obtained precipitation slag, heating to 50-70 ℃, then filtering to obtain calcium sulfate slag and a phosphoric acid-containing solution, adding TBP into the phosphoric acid-containing solution for extraction, performing back extraction on pure water to obtain the phosphoric acid solution, and returning to the step (1) for use.
The invention adopts a controlled crystallization precipitation method to prepare manganese phosphate, complexation of EDTA and manganese is carried out, polyethylene glycol 4000 is added to play a role in complexation and dispersion, then a mixed solution of urea and MAP is prepared, urea has two roles, namely the complexation effect can be carried out, and at the same time, urea can be decomposed to obtain carbon dioxide and ammonia at high temperature, the ammonia is very easy to dissolve in water, and the carbon dioxide can escape from the solution, so that the urea has a controlled precipitant for controlling precipitation crystallization, and phosphoric acid is added to play a role in regulating and stabilizing the pH value of the solution.
The invention produces manganese phosphate by a continuous method, and can obtain products with uniform particle size distribution, good crystallinity, small primary particle size, compact growth and high tap density by controlling and maintaining the steady state of the process, the pH value of the process is 2.5-3, the reaction temperature is 90-95 ℃, the manganese ion content in the supernatant is 100-ion-containing water 300mg/L, and the retention time is 7-10 h.
The continuous method for producing the manganese phosphate has high production efficiency, can realize automatic feeding and has less labor.
And the invention can realize the recovery of phosphate radicals and ammonium radicals in the wastewater, the mother liquor obtained by filtering in step (3) is added with calcium oxide, the pH of the solution is adjusted to 8-8.5, then the filtration is carried out, the obtained filtrate is concentrated and crystallized to obtain nitrogen fertilizer, the obtained precipitation slag is added with sulfuric acid, the temperature is raised to 50-70 ℃, then the filtration is carried out to obtain calcium sulfate slag and phosphoric acid-containing solution, after the phosphoric acid-containing solution is added with TBP for extraction, pure water is back extracted to obtain phosphoric acid solution, the phosphoric acid solution is returned to step (1) for use, and the following reactions are carried out specifically:
2PO4 3-+3Ca2+----Ca3(PO4)2
Ca3(PO4)2+3H2SO4----3CaSO4↓+2H3PO4
the obtained phosphoric acid-containing solution contains impurities such as sulfuric acid and calcium ions in addition to phosphoric acid, and phosphoric acid with high purity is obtained through extraction separation and is returned for use.
The invention has the beneficial effects that: the method has the advantages of simple process and low cost, and the obtained manganese phosphate has uniform particle size distribution, good crystallinity, small primary particle size, dense growth and high tap density.
Detailed Description
The present invention will be described in detail with reference to the following specific examples, in which the preparation method of manganese phosphate of this example comprises the following steps:
(1) adding manganese salt into pure water, adding a complexing agent and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, and adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution;
(2) adding a base solution into a reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, the pH value of the mixed solution is 2.5-3, heating to 90-95 ℃, starting stirring to ensure that the stirring speed is 200 ion-doped 300r/min, then adding a manganese solution, a precipitator solution and a phosphoric acid solution into the base solution in a cocurrent manner, maintaining the pH value of the reaction process to be 2.5-3, the reaction temperature to be 90-95 ℃, the manganese ion content in a supernatant to be 100 ion-doped 300mg/L, the retention time to be 7-10h, and continuously overflowing and discharging;
(3) and aging the continuous overflow discharge in a transfer tank for 1-2h, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by adopting a cooling coil pipe, and then filtering, washing, drying, screening and removing iron to obtain the manganese phosphate.
The manganese salt is at least one of battery-grade manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, the complexing agent is DETA, the concentration of manganese ions in the obtained manganese solution is 1-1.5mol/L, the concentration of the complexing agent is 0.01-0.05mol/L, and the mass fraction of polyethylene glycol 4000 is 0.1-0.5%.
The concentration of urea in the precipitant solution is 2-3mol/L, and the concentration of MAP is 1-1.5 mol/L.
The concentration of the phosphoric acid solution is 1-2 mol/L.
The volume of the base solution added in the step (2) is 0.15-0.2 time of the volume of the reaction kettle.
And (3) in the aging process, the stirring speed is maintained at 150-200r/min, cold pure water is adopted in a cooling coil for cooling, and the manganese phosphate is washed by hot pure water after heat exchange.
The screening adopts a 150-plus-200-mesh ultrasonic vibration screen, and the iron removal adopts an electromagnetic iron remover.
Adding calcium oxide into the mother liquor obtained by filtering in the step (3), adjusting the pH value of the solution to 8-8.5, then filtering, concentrating and crystallizing the obtained filtrate to obtain a nitrogen fertilizer, adding sulfuric acid into the obtained precipitation slag, heating to 50-70 ℃, then filtering to obtain calcium sulfate slag and a phosphoric acid-containing solution, adding TBP into the phosphoric acid-containing solution for extraction, performing back extraction on pure water to obtain the phosphoric acid solution, and returning to the step (1) for use.
Example 1
A preparation method of manganese phosphate comprises the following steps:
(1) adding battery-grade manganese chloride into pure water, adding complexing agent DETA and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution, wherein the manganese ion concentration in the obtained manganese solution is 1.3mol/L, the complexing agent concentration is 0.04mol/L, and the mass fraction of polyethylene glycol 4000 is 0.3%.
The concentration of urea in the precipitant solution is 2.4mol/L, and the concentration of MAP is 1.3 mol/L.
The concentration of the phosphoric acid solution is 1.5 mol/L.
(2) Adding a base solution into a reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, the pH value of the mixed solution is 2.8, heating to 93 ℃, starting stirring, enabling the stirring speed to be 250r/min, then adding a manganese solution, a precipitator solution and a phosphoric acid solution into the base solution in a parallel flow manner, maintaining the pH value of the reaction process to be 2.8, the reaction temperature to be 93 ℃, the manganese ion content in a supernatant to be 180mg/L, the retention time to be 8h, and continuously overflowing and discharging; the volume of the base solution added in the step (2) is 0.18 time of the volume of the reaction kettle; after the base solution is prepared, sampling and detecting are carried out, and the results are as follows:
| item | pH/25℃ | NH4 + | PO4 3- | Ca | Na | Mg |
| Numerical value | 2.8 | 0.11mol/L | 0.04mol/L | 2.7ppm | 8.9ppm | 1.6ppm |
The overflow material, having a solids content of 12.5%, was sampled to determine the particle size, with the following results:
| laser particle size | Dmin | D10 | D50 | D90 | Dmax |
| Data of | 1.48μm | 3.19μm | 4.52μm | 5.91μm | 6.87μm |
And meanwhile, filtering, sampling and measuring supernatant, wherein the detection data are as follows:
| item | Mn | pH/25℃ | NH4 + | PO4 3- | Ca | Cl- |
| Numerical value | 180mg/L | 2.8 | 0.21mol/L | 0.02mol/L | 4.6ppm | 0.21mol/L |
| Mg | Na | Ni | Co | Cu | Zn | Cd |
| 2.1ppm | 9.2ppm | 2.8ppm | 1.9ppm | 0.3ppm | 5.9ppm | 6.1ppm |
| Al | Cr | Pb | Fe | Ti | Sulfate radical | |
| 0.9ppm | 1.3ppm | 1.2ppm | 6.1ppm | 1.6ppm | 39.9ppm |
(3) And aging the continuous overflow discharge in a transfer tank for 2h, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by using a cooling coil pipe, and then filtering, washing, drying, screening and removing iron to obtain the manganese phosphate. And (3) in the aging process, the stirring speed is kept at 180r/min, cold pure water is adopted for cooling in a cooling coil, and the manganese phosphate is washed by hot pure water after heat exchange. The screening adopts a 150-mesh ultrasonic vibration screen, and the iron removal adopts an electromagnetic iron remover. The data for manganese phosphate was obtained as follows:
adding calcium oxide into the mother liquor obtained by filtering in the step (3), adjusting the pH value of the solution to 8.4, then filtering, concentrating and crystallizing the obtained filtrate to obtain a nitrogen fertilizer, adding sulfuric acid into the obtained precipitation slag, heating to 65 ℃, then filtering to obtain calcium sulfate slag and a phosphoric acid-containing solution, adding TBP into the phosphoric acid-containing solution for extraction, performing back extraction by pure water to obtain the phosphoric acid solution, and returning to the step (1) for use.
Example 2
A preparation method of manganese phosphate comprises the following steps:
(1) adding manganese salt into pure water, adding a complexing agent and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, and adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution;
(2) adding a base solution into a reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, the pH value of the mixed solution is 2.7, heating to 90 ℃, starting stirring to enable the stirring speed to be 280r/min, then adding a manganese solution, a precipitator solution and a phosphoric acid solution into the base solution in a parallel flow manner, maintaining the pH value of the reaction process to be 2.7, the reaction temperature to be 90 ℃, the manganese ion content in a supernatant to be 250mg/L, the retention time to be 9h, and continuously overflowing and discharging;
(3) and aging the continuous overflow discharge in a transfer tank for 1.5h, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by using a cooling coil pipe, and then filtering, washing, drying, screening and removing iron to obtain the manganese phosphate.
The manganese salt is battery-grade manganese sulfate, the complexing agent is DETA, the concentration of manganese ions in the obtained manganese solution is 1.4mol/L, the concentration of the complexing agent is 0.035mol/L, and the mass fraction of polyethylene glycol 4000 is 0.4%.
The concentration of urea in the precipitant solution is 2.8mol/L, and the concentration of MAP is 1.45 mol/L.
The concentration of the phosphoric acid solution is 1.8 mol/L.
The volume of the base solution added in the step (2) is 0.16 time of the volume of the reaction kettle.
And (3) in the aging process of the step (3), the stirring speed is kept at 185r/min, cold pure water is adopted in a cooling coil for cooling, and the manganese phosphate is washed by hot pure water after heat exchange.
The screening adopts a 200-mesh ultrasonic vibration screen, and the iron removal adopts an electromagnetic iron remover.
Adding calcium oxide into the mother liquor obtained by filtering in the step (3), adjusting the pH value of the solution to 8.4, then filtering, concentrating and crystallizing the obtained filtrate to obtain a nitrogen fertilizer, adding sulfuric acid into the obtained precipitation slag, heating to 65 ℃, then filtering to obtain calcium sulfate slag and a phosphoric acid-containing solution, adding TBP into the phosphoric acid-containing solution for extraction, performing back extraction by pure water to obtain the phosphoric acid solution, and returning to the step (1) for use.
The data for manganese phosphate was obtained as follows:
| index (I) | Mn | Moisture content | D10 | D50 | D90 |
| Numerical value | 40.29％ | 0.43％ | 3.45μm | 4.59μm | 5.69μm |
| Fe | Cd | Co | Pb | Ca | Na |
| 4.6ppm | 1.4ppm | 7.9ppm | 1.9ppm | 18.5ppm | 8.8ppm |
| Ni | Mg | Zn | Cr | Al | Ti |
| 12.1ppm | 23.7ppm | 6.1ppm | 14.9ppm | 1.2ppm | 1.2ppm |
| Tap density | Sulfate radical | Chloride ion | BET | Magnetic foreign matter | Primary particle diameter |
| 1.89g/mL | 46.8ppm | 11.9ppm | 5.3m2/g | 0.39ppm | 42nm |
Example 3
A preparation method of manganese phosphate comprises the following steps:
(1) adding manganese salt into pure water, adding a complexing agent and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, and adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution;
(2) adding a base solution into a reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, the pH value of the mixed solution is 3, heating to 95 ℃, starting stirring to ensure that the stirring speed is 260r/min, then adding a manganese solution, a precipitator solution and a phosphoric acid solution into the base solution in a concurrent flow manner, maintaining the pH value of the reaction process to be 3, the reaction temperature to be 95 ℃, the manganese ion content in a supernatant to be 135mg/L, the retention time to be 9h, and continuously overflowing and discharging;
(3) and aging the continuous overflow discharge in a transfer tank for 1.8h, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by using a cooling coil pipe, and then filtering, washing, drying, screening and removing iron to obtain the manganese phosphate.
The manganese salt is battery-grade manganese acetate, the complexing agent is DETA, the concentration of manganese ions in the obtained manganese solution is 1.5mol/L, the concentration of the complexing agent is 0.05mol/L, and the mass fraction of polyethylene glycol 4000 is 0.25%.
The concentration of urea in the precipitant solution is 2.8mol/L, and the concentration of MAP is 1.2 mol/L.
The concentration of the phosphoric acid solution is 2 mol/L.
The volume of the base solution added in the step (2) is 0.16 time of the volume of the reaction kettle.
And (3) in the aging process of the step (3), the stirring speed is kept at 165r/min, cold pure water is adopted for cooling in a cooling coil, and the manganese phosphate is washed by hot pure water after heat exchange.
The screening adopts a 150-mesh ultrasonic vibration screen, and the iron removal adopts an electromagnetic iron remover.
Adding calcium oxide into the mother liquor obtained by filtering in the step (3), adjusting the pH value of the solution to 8.3, then filtering, concentrating and crystallizing the obtained filtrate to obtain a nitrogen fertilizer, adding sulfuric acid into the obtained precipitation slag, heating to 65 ℃, then filtering to obtain calcium sulfate slag and a phosphoric acid-containing solution, adding TBP into the phosphoric acid-containing solution for extraction, performing back extraction by pure water to obtain the phosphoric acid solution, and returning to the step (1) for use.
The data for manganese phosphate was obtained as follows:
| index (I) | Mn | Moisture content | D10 | D50 | D90 |
| Numerical value | 40.17％ | 0.38％ | 3.37μm | 4.45μm | 5.73μm |
| Fe | Cd | Co | Pb | Ca | Na |
| 4.3ppm | 1.3ppm | 8.5ppm | 3.3ppm | 19.9ppm | 8.1ppm |
| Ni | Mg | Zn | Cr | Al | Ti |
| 12.7ppm | 23.1ppm | 5.7ppm | 13.1ppm | 1.7ppm | 1.2ppm |
| Tap density | Sulfate radical | Chloride ion | BET | Magnetic foreign matter | Primary particle diameter |
| 1.78g/mL | 14.7ppm | 10.3ppm | 5.7m2/g | 0.32ppm | 45nm |
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (6)
1. The preparation method of manganese phosphate is characterized by comprising the following steps:
(1) adding manganese salt into pure water, adding a complexing agent and polyethylene glycol 4000, stirring and dissolving completely to obtain a manganese solution, adding urea and MAP into pure water, dissolving completely to obtain a precipitator solution, and adding phosphoric acid into pure water to dilute to obtain a phosphoric acid solution;
(2) adding a base solution into a reaction kettle, wherein the base solution is a mixed solution of ammonia water and phosphoric acid, the pH value of the mixed solution is 2.5-3, the volume of the added base solution is 0.15-0.2 times of the volume of the reaction kettle, then heating to 90-95 ℃, starting stirring, enabling the stirring speed to be 200-fold at 300r/min, then adding a manganese solution, a precipitator solution and a phosphoric acid solution into the base solution in a parallel flow manner, maintaining the pH value in the reaction process to be 2.5-3, the reaction temperature to be 90-95 ℃, keeping the manganese ion content in a supernatant to be 100-fold at 300mg/L, keeping the residence time to be 7-10h, and continuously overflowing and discharging;
(3) and (2) aging the continuous overflow discharge in a transfer tank for 1-2h, cooling the continuous overflow discharge to a temperature lower than 50 ℃ by using a cooling coil, filtering, washing, drying, screening and deironing to obtain manganese phosphate, adding calcium oxide into mother liquor obtained by filtering, adjusting the pH value of the solution to 8-8.5, filtering, concentrating and crystallizing the obtained filtrate to obtain a nitrogen fertilizer, adding sulfuric acid into the obtained precipitate, heating to a temperature of 50-70 ℃, filtering to obtain calcium sulfate slag and a phosphoric acid-containing solution, adding TBP into the phosphoric acid-containing solution for extraction, performing pure water back extraction to obtain the phosphoric acid solution, and returning to the step (1) for use.
2. The method for preparing manganese phosphate according to claim 1, characterized in that: the manganese salt is at least one of battery-grade manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, the complexing agent is DETA, the concentration of manganese ions in the obtained manganese solution is 1-1.5mol/L, the concentration of the complexing agent is 0.01-0.05mol/L, and the mass fraction of polyethylene glycol 4000 is 0.1-0.5%.
3. The method for preparing manganese phosphate according to claim 1, characterized in that: the concentration of urea in the precipitant solution is 2-3mol/L, and the concentration of MAP is 1-1.5 mol/L.
4. The method for preparing manganese phosphate according to claim 1, characterized in that: the concentration of the phosphoric acid solution is 1-2 mol/L.
5. The method for preparing manganese phosphate according to claim 1, characterized in that: and (3) in the aging process, the stirring speed is maintained at 150-200r/min, cold pure water is adopted in a cooling coil for cooling, and the manganese phosphate is washed by hot pure water after heat exchange.
6. The method for preparing manganese phosphate according to claim 1, characterized in that: the screening adopts a 150-plus-200-mesh ultrasonic vibration screen, and the iron removal adopts an electromagnetic iron remover.
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| WO2013093017A2 (en) * | 2011-12-21 | 2013-06-27 | Chemische Fabrik Budenheim Kg | Metal phosphates and process for the preparation thereof |
| CN103000898A (en) * | 2012-12-11 | 2013-03-27 | 中国电子科技集团公司第十八研究所 | Preparation method for carbon compounded lithium ferromanganese phosphate used for lithium ion battery |
| CN105645370A (en) * | 2016-01-06 | 2016-06-08 | 昆明理工大学 | Preparation method of flaky manganwentzelite |
| CN107394203A (en) * | 2017-07-13 | 2017-11-24 | 扬州大学 | A kind of preparation method of two-dimensional ultrathin sheet manganese phosphate |
| CN109119615A (en) * | 2018-08-28 | 2019-01-01 | 重庆大学 | A kind of lithium manganese phosphate composite positive pole and preparation method thereof that doped metallic elements are modified |
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