CN110002418A - A kind of preparation method of manganese phosphate - Google Patents
A kind of preparation method of manganese phosphate Download PDFInfo
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- CN110002418A CN110002418A CN201910313466.XA CN201910313466A CN110002418A CN 110002418 A CN110002418 A CN 110002418A CN 201910313466 A CN201910313466 A CN 201910313466A CN 110002418 A CN110002418 A CN 110002418A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/377—Phosphates of heavy metals of manganese
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Abstract
The present invention discloses a kind of preparation method of manganese phosphate.Pure water is added in manganese salt, adds complexing agent and Macrogol 4000, stirring and dissolving is complete, obtains manganese solution, and pure water is added in urea and MAP, and dissolution obtains precipitant solution completely, dilutes phosphoric acid addition pure water to obtain phosphoric acid solution；Bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, stirring opened, so that mixing speed is 200-300r/min, then manganese solution, precipitant solution and phosphoric acid solution cocurrent are added in the liquid of bottom, continuous overflow discharging；Continuous overflow discharging is aged in transfer tank, while continuous overflow discharging is cooled below 50 DEG C using cooling coil, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.Present invention process is simple, at low cost, obtained manganese phosphate even particle size distribution, better crystallinity degree, and primary particle size is small and growth is closely knit, and tap density is high.
Description
Technical field
The present invention relates to a kind of preparation methods of manganese phosphate, belong to lithium battery new energy materials field.
Background technique
Manganese phosphate is that a kind of molecular formula is Mn3(PO4)2.3H2O.It is applied to pharmaceuticals industry and glass, china and pottery industry, with
The development of lithium battery material, manganese-lithium phosphate anode material is by everybody attention, lithium manganese phosphate (lithium manganese
(II) phosphate), chemical formula: LiMnPO4, it is a kind of natural minerals or artificial synthesized ternary electrode material of lithium battery.
The substance has the crystal structure of olivine shape, and physicochemical properties are stablized when leading to it as electrode material.And lithium manganese phosphate
Discharge platform (the vs Li/Li of specific capacity and 4.1V or so with 171mAh/g+) this is but also lithium manganese phosphate becomes newly
The ideal material of generation lithium-ion-power cell.
The common preparation method in the laboratory of lithium manganese phosphate mainly has solid phase method and liquid phase method.Solid phase method uses solid lithium
Salt, manganese salt and phosphate ball milling mixing and the high temperature sintering under the atmosphere of protection gas.It is solidifying that liquid phase method is divided into polyol process, colloidal sol again
Glue method and hydro-thermal method, liquid phase method synthesis lithium manganese phosphate pattern and purity are easier to control, but there is also crystallization is incomplete
Problem, it is often necessary to calcination of further annealing.
And use manganese phosphate to be used as presoma, can to avoid in sintering furnace generation redox reaction, so that crystal structure,
So the crystal structure of manganese phosphate, size distribution, primary particle size size have vital influence to lithium manganese phosphate.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of manganese phosphate, simple process and low cost, obtained phosphoric acid
Manganese even particle size distribution, better crystallinity degree, primary particle size is small and growth is closely knit, and tap density is high.
The present invention solves above-mentioned technical problem by following technological means:
A kind of preparation method of manganese phosphate, is following steps:
(1) pure water being added in manganese salt, adds complexing agent and Macrogol 4000, stirring and dissolving is complete, manganese solution is obtained,
Pure water is added in urea and MAP, dissolution obtains precipitant solution completely, dilutes phosphoric acid addition pure water to obtain phosphoric acid solution；
(2) bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, and the pH of mixed solution is 2.5-3,
Then heating to temperature is 90-95 DEG C, opens stirring, so that mixing speed is 200-300r/min, then by manganese solution, precipitating
Agent solution and phosphoric acid solution cocurrent are added in the liquid of bottom, and maintaining the pH of reaction process is 2.5-3, and reaction temperature is 90-95 DEG C, on
Manganese ion content in clear liquid is 100-300mg/L, residence time 7-10h, continuous overflow discharging；
(3) continuous overflow is discharged and is aged 1-2h in transfer tank, while continuous overflow being discharged using cooling coil and is cooled down
It is lower than 50 DEG C to temperature, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.
The manganese salt is at least one of LITHIUM BATTERY manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, the complexing agent
For DETA, manganese ion concentration is 1-1.5mol/L, complexing agent concentration 0.01-0.05mol/L, poly- second two in obtained manganese solution
The mass fraction of alcohol 4000 is 0.1-0.5%.
The concentration of urea in the precipitant solution is 2-3mol/L, and the concentration of MAP is 1-1.5mol/L.
The concentration of the phosphoric acid solution is 1-2mol/L.
The bottom liquid product being added in the step (2) is 0.15-0.2 times of reactor volume.
It is 150-200r/min that step (3) ageing process, which maintains mixing speed, in cooling coil using cold pure water into
Row cooling, the hot pure water after exchanging heat wash manganese phosphate.
Screening is sieved using 150-200 mesh ultrasonic activation, except iron uses electric magnetic iron remover.
Calcium oxide is added in the mother liquor that the step (3) is obtained by filtration, and the pH for adjusting solution is 8-8.5, then filters, obtains
Filtrate obtain nitrogenous fertilizer by condensing crystallizing, sulfuric acid is added in obtained precipitation slag, and being warming up to temperature is 50-70 DEG C, then filter,
Calcium sulfate slag and phosphorous acid solution are obtained, after TBP extraction is added in phosphorous acid solution, pure water back extraction obtains phosphoric acid solution, returns to step
Suddenly (1) uses.
The present invention prepares manganese phosphate using control crystalline deposit method, by the complexing of EDTA and manganese, while poly- second is added
Glycol 4000 can play the role of complexing and dispersion, then prepare the mixed solution of urea and MAP, effect that there are two urea,
Complexing can be played, while at high temperature, urea can decompose to obtain carbon dioxide and ammonia, ammonia very soluble in water,
And carbon dioxide can come out in loss from solution, so that urea is provided with the control precipitating reagent of control precipitated crystal, simultaneously
Phosphoric acid is added, plays the role of adjusting and stablizing solution pH.
The present invention produces manganese phosphate by continuity method, and by control and the stable state of maintenance process, process pH is 2.5-3,
Reaction temperature is 90-95 DEG C, and the manganese ion content in supernatant is 100-300mg/L, residence time 7-10h, available
Even particle size distribution, better crystallinity degree, primary particle size is small and grows closely knit, the high product of tap density.
Continuity method produces manganese phosphate, and automated feeding may be implemented in high production efficiency, artificial few.
And the recycling of Phosphorus From Wastewater acid group and ammonium root may be implemented in the present invention, oxygen is added in the mother liquor that step (3) is obtained by filtration
Change calcium, the pH for adjusting solution is 8-8.5, is then filtered, and obtained filtrate obtains nitrogenous fertilizer by condensing crystallizing, obtained precipitation slag
Sulfuric acid is added, being warming up to temperature is 50-70 DEG C, is then filtered, and calcium sulfate slag and phosphorous acid solution are obtained, and phosphorous acid solution is added
After TBP extraction, pure water back extraction obtains phosphoric acid solution, and return step (1) uses, specific that following reaction occurs:
2PO4 3-+3Ca2+----Ca3(PO4)2
Ca3(PO4)2+3H2SO4----3CaSO4↓+2H3PO4
For obtained phosphorous acid solution in addition to phosphoric acid, there are also the impurity such as sulfuric acid, calcium ion, are separated by extraction, and obtain purity
High phosphoric acid is returned and is used.
The beneficial effects of the present invention are: simple process and low cost, obtained manganese phosphate even particle size distribution, better crystallinity degree,
Primary particle size is small and growth is closely knit, and tap density is high.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail, a kind of preparation side of manganese phosphate of the present embodiment
Method is following steps:
(1) pure water being added in manganese salt, adds complexing agent and Macrogol 4000, stirring and dissolving is complete, manganese solution is obtained,
Pure water is added in urea and MAP, dissolution obtains precipitant solution completely, dilutes phosphoric acid addition pure water to obtain phosphoric acid solution；
(2) bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, and the pH of mixed solution is 2.5-3,
Then heating to temperature is 90-95 DEG C, opens stirring, so that mixing speed is 200-300r/min, then by manganese solution, precipitating
Agent solution and phosphoric acid solution cocurrent are added in the liquid of bottom, and maintaining the pH of reaction process is 2.5-3, and reaction temperature is 90-95 DEG C, on
Manganese ion content in clear liquid is 100-300mg/L, residence time 7-10h, continuous overflow discharging；
(3) continuous overflow is discharged and is aged 1-2h in transfer tank, while continuous overflow being discharged using cooling coil and is cooled down
It is lower than 50 DEG C to temperature, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.
The manganese salt is at least one of LITHIUM BATTERY manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, the complexing agent
For DETA, manganese ion concentration is 1-1.5mol/L, complexing agent concentration 0.01-0.05mol/L, poly- second two in obtained manganese solution
The mass fraction of alcohol 4000 is 0.1-0.5%.
The concentration of urea in the precipitant solution is 2-3mol/L, and the concentration of MAP is 1-1.5mol/L.
The concentration of the phosphoric acid solution is 1-2mol/L.
The bottom liquid product being added in the step (2) is 0.15-0.2 times of reactor volume.
It is 150-200r/min that step (3) ageing process, which maintains mixing speed, in cooling coil using cold pure water into
Row cooling, the hot pure water after exchanging heat wash manganese phosphate.
Screening is sieved using 150-200 mesh ultrasonic activation, except iron uses electric magnetic iron remover.
Calcium oxide is added in the mother liquor that the step (3) is obtained by filtration, and the pH for adjusting solution is 8-8.5, then filters, obtains
Filtrate obtain nitrogenous fertilizer by condensing crystallizing, sulfuric acid is added in obtained precipitation slag, and being warming up to temperature is 50-70 DEG C, then filter,
Calcium sulfate slag and phosphorous acid solution are obtained, after TBP extraction is added in phosphorous acid solution, pure water back extraction obtains phosphoric acid solution, returns to step
Suddenly (1) uses.
Embodiment 1
A kind of preparation method of manganese phosphate, is following steps:
(1) pure water is added in LITHIUM BATTERY manganese chloride, adds complexing agent DETA and Macrogol 4000, stirring and dissolving is complete
Entirely, manganese solution is obtained, pure water is added in urea and MAP, dissolution obtains precipitant solution completely, and phosphoric acid addition pure water is diluted
To phosphoric acid solution, manganese ion concentration is 1.3mol/L, complexing agent concentration 0.04mol/L, polyethylene glycol in obtained manganese solution
4000 mass fraction is 0.3%.
The concentration of urea in the precipitant solution is 2.4mol/L, and the concentration of MAP is 1.3mol/L.
The concentration of the phosphoric acid solution is 1.5mol/L.
(2) bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, and the pH of mixed solution is 2.8, so
After be warming up to temperature be 93 DEG C, open stirring so that mixing speed be 250r/min, then by manganese solution, precipitant solution and
Phosphoric acid solution cocurrent is added in the liquid of bottom, and maintaining the pH of reaction process is 2.8, and reaction temperature is 93 DEG C, manganese in supernatant from
Sub- content is 180mg/L, residence time 8h, continuous overflow discharging；The bottom liquid product being added in the step (2) is reaction kettle
0.18 times of volume；By bottom liquid it is deployed after, sample detection is as a result as follows:
| Project | 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 material overflowed, solid content 12.5%, partial size is surveyed in sampling, as a result as follows:
| Laser particle size | Dmin | D10 | D50 | D90 | Dmax |
| Data | 1.48μm | 3.19μm | 4.52μm | 5.91μm | 6.87μm |
Filtering and sampling surveys supernatant simultaneously, and detection data is as follows:
| Project | 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) continuous overflow is discharged and is aged 2h in transfer tank, while being cooled to continuous overflow discharging using cooling coil
Temperature is lower than 50 DEG C, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.Step (3) ageing process
Maintenance mixing speed is 180r/min, is cooled down in cooling coil using cold pure water, the hot pure water after exchanging heat washs phosphorus
Sour manganese.Screening is sieved using 150 mesh ultrasonic activations, except iron uses electric magnetic iron remover.The data for obtaining manganese phosphate are as follows:
Calcium oxide is added in the mother liquor that the step (3) is obtained by filtration, and the pH for adjusting solution is 8.4, then filters, obtains
Filtrate obtains nitrogenous fertilizer by condensing crystallizing, and sulfuric acid is added in obtained precipitation slag, and being warming up to temperature is 65 DEG C, then filters, obtains
Calcium sulfate slag and phosphorous acid solution, after TBP extraction is added in phosphorous acid solution, pure water back extraction obtains phosphoric acid solution, return step
(1) it uses.
Embodiment 2
A kind of preparation method of manganese phosphate, is following steps:
(1) pure water being added in manganese salt, adds complexing agent and Macrogol 4000, stirring and dissolving is complete, manganese solution is obtained,
Pure water is added in urea and MAP, dissolution obtains precipitant solution completely, dilutes phosphoric acid addition pure water to obtain phosphoric acid solution；
(2) bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, and the pH of mixed solution is 2.7, so
After be warming up to temperature be 90 DEG C, open stirring so that mixing speed be 280r/min, then by manganese solution, precipitant solution and
Phosphoric acid solution cocurrent is added in the liquid of bottom, and maintaining the pH of reaction process is 2.7, and reaction temperature is 90 DEG C, manganese in supernatant from
Sub- content is 250mg/L, residence time 9h, continuous overflow discharging；
(3) continuous overflow is discharged and is aged 1.5h in transfer tank, while continuous overflow being discharged using cooling coil and is cooled down
It is lower than 50 DEG C to temperature, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.
The manganese salt is LITHIUM BATTERY manganese sulfate, and the complexing agent is DETA, and manganese ion concentration is in obtained manganese solution
1.4mol/L, complexing agent concentration 0.035mol/L, the mass fraction of Macrogol 4000 are 0.4%.
The concentration of urea in the precipitant solution is 2.8mol/L, and the concentration of MAP is 1.45mol/L.
The concentration of the phosphoric acid solution is 1.8mol/L.
The bottom liquid product being added in the step (2) is 0.16 times of reactor volume.
It is 185r/min that step (3) ageing process, which maintains mixing speed, is carried out in cooling coil using cold pure water cold
But, the hot pure water after exchanging heat washs manganese phosphate.
Screening is sieved using 200 mesh ultrasonic activations, except iron uses electric magnetic iron remover.
Calcium oxide is added in the mother liquor that the step (3) is obtained by filtration, and the pH for adjusting solution is 8.4, then filters, obtains
Filtrate obtains nitrogenous fertilizer by condensing crystallizing, and sulfuric acid is added in obtained precipitation slag, and being warming up to temperature is 65 DEG C, then filters, obtains
Calcium sulfate slag and phosphorous acid solution, after TBP extraction is added in phosphorous acid solution, pure water back extraction obtains phosphoric acid solution, return step
(1) it uses.
The data for obtaining manganese phosphate are as follows:
| Index | Mn | Moisture | 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 body | Primary particle size |
| 1.89g/mL | 46.8ppm | 11.9ppm | 5.3m2/g | 0.39ppm | 42nm |
Embodiment 3
A kind of preparation method of manganese phosphate, is following steps:
(1) pure water being added in manganese salt, adds complexing agent and Macrogol 4000, stirring and dissolving is complete, manganese solution is obtained,
Pure water is added in urea and MAP, dissolution obtains precipitant solution completely, dilutes phosphoric acid addition pure water to obtain phosphoric acid solution；
(2) bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, and the pH of mixed solution is 3, then
Being warming up to temperature is 95 DEG C, opens stirring, so that mixing speed is 260r/min, then by manganese solution, precipitant solution and phosphorus
Acid solution cocurrent is added in the liquid of bottom, and maintaining the pH of reaction process is 3, and reaction temperature is 95 DEG C, and the manganese ion in supernatant contains
Amount is 135mg/L, residence time 9h, continuous overflow discharging；
(3) continuous overflow is discharged and is aged 1.8h in transfer tank, while continuous overflow being discharged using cooling coil and is cooled down
It is lower than 50 DEG C to temperature, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.
The manganese salt is LITHIUM BATTERY manganese acetate, and the complexing agent is DETA, and manganese ion concentration is in obtained manganese solution
1.5mol/L, complexing agent concentration 0.05mol/L, the mass fraction of Macrogol 4000 are 0.25%.
The concentration of urea in the precipitant solution is 2.8mol/L, and the concentration of MAP is 1.2mol/L.
The concentration of the phosphoric acid solution is 2mol/L.
The bottom liquid product being added in the step (2) is 0.16 times of reactor volume.
It is 165r/min that step (3) ageing process, which maintains mixing speed, is carried out in cooling coil using cold pure water cold
But, the hot pure water after exchanging heat washs manganese phosphate.
Screening is sieved using 150 mesh ultrasonic activations, except iron uses electric magnetic iron remover.
Calcium oxide is added in the mother liquor that the step (3) is obtained by filtration, and the pH for adjusting solution is 8.3, then filters, obtains
Filtrate obtains nitrogenous fertilizer by condensing crystallizing, and sulfuric acid is added in obtained precipitation slag, and being warming up to temperature is 65 DEG C, then filters, obtains
Calcium sulfate slag and phosphorous acid solution, after TBP extraction is added in phosphorous acid solution, pure water back extraction obtains phosphoric acid solution, return step
(1) it uses.
The data for obtaining manganese phosphate are as follows:
| Index | Mn | Moisture | 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 body | Primary particle size |
| 1.78g/mL | 14.7ppm | 10.3ppm | 5.7m2/g | 0.32ppm | 45nm |
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (8)
1. a kind of preparation method of manganese phosphate, which is characterized in that be following steps:
(1) pure water is added in manganese salt, adds complexing agent and Macrogol 4000, stirring and dissolving is complete, obtains manganese solution, will urinate
Pure water is added in element and MAP, and dissolution obtains precipitant solution completely, dilutes phosphoric acid addition pure water to obtain phosphoric acid solution；
(2) bottom liquid will be added in reaction kettle, bottom liquid is the mixed solution of ammonium hydroxide and phosphoric acid, and the pH of mixed solution is 2.5-3, then
Being warming up to temperature is 90-95 DEG C, opens stirring, so that mixing speed is 200-300r/min, it is then that manganese solution, precipitating reagent is molten
Liquid and phosphoric acid solution cocurrent are added in the liquid of bottom, and maintaining the pH of reaction process is 2.5-3, and reaction temperature is 90-95 DEG C, supernatant
In manganese ion content be 100-300mg/L, residence time 7-10h, continuous overflow discharging；
(3) continuous overflow is discharged and is aged 1-2h in transfer tank, while continuous overflow discharging is cooled to by temperature using cooling coil
Degree is lower than 50 DEG C, is then filtered, washed, dries, sieves and removes iron, obtain manganese phosphate.
2. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: the manganese salt is LITHIUM BATTERY sulfuric acid
At least one of manganese, manganese chloride, manganese nitrate or manganese acetate, the complexing agent are DETA, manganese ion in obtained manganese solution
Concentration is 1-1.5mol/L, and complexing agent concentration 0.01-0.05mol/L, the mass fraction of Macrogol 4000 is 0.1-
0.5%.
3. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: the urine in the precipitant solution
The concentration of element is 2-3mol/L, and the concentration of MAP is 1-1.5mol/L.
4. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: the concentration of the phosphoric acid solution is
1-2mol/L。
5. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: be added in the step (2)
Liquid product in bottom is 0.15-0.2 times of reactor volume.
6. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: step (3) ageing process
Maintenance mixing speed is 150-200r/min, is cooled down in cooling coil using cold pure water, the hot pure water after exchanging heat is washed
Wash manganese phosphate.
7. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: screening is super using 150-200 mesh
Acoustic vibration sieve, except iron uses electric magnetic iron remover.
8. a kind of preparation method of manganese phosphate according to claim 1, it is characterised in that: the step (3) is obtained by filtration
Mother liquor calcium oxide is added, the pH for adjusting solution is 8-8.5, is then filtered, and obtained filtrate obtains nitrogenous fertilizer by condensing crystallizing,
Sulfuric acid is added in obtained precipitation slag, and being warming up to temperature is 50-70 DEG C, then filters, obtains calcium sulfate slag and phosphorous acid solution, contain
After TBP extraction is added in phosphoric acid solution, pure water back extraction obtains phosphoric acid solution, and return step (1) uses.
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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110898782A (en) * | 2019-10-31 | 2020-03-24 | 乳源东阳光磁性材料有限公司 | Automatic preparation facilities of ternary precursor |
| CN110898782B (en) * | 2019-10-31 | 2023-10-27 | 乳源东阳光新能源材料有限公司 | Automatic preparation facilities of ternary precursor |
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