CN112811405A - Preparation method of ferric phosphate with controllable morphology - Google Patents
Preparation method of ferric phosphate with controllable morphology Download PDFInfo
- Publication number
- CN112811405A CN112811405A CN202110384792.7A CN202110384792A CN112811405A CN 112811405 A CN112811405 A CN 112811405A CN 202110384792 A CN202110384792 A CN 202110384792A CN 112811405 A CN112811405 A CN 112811405A
- Authority
- CN
- China
- Prior art keywords
- solution
- phosphate
- amount
- iron
- ferrous sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of ferric phosphate with controllable morphology, which comprises the following steps: dissolving pure iron in concentrated sulfuric acid to prepare ferrous sulfate, diluting 80g/L high-concentration ferrous sulfate solution, adding concentrated phosphoric acid for acidification, wherein the acidification amount is 10-20% of the molar amount of iron ions, adding industrial-grade hydrogen peroxide solution into the acidified solution for oxidation, stirring the solution at a certain speed in the process, adding 2.0mol/L of phosphate salt into the obtained solution, wherein the phosphate salt is 92.5-100% of the molar amount of the iron ions, and heating and aging the solution along with the stirring process. The preparation method of the shape-controllable iron phosphate has the advantages of simple process, mild reaction conditions, low cost, controllable shape and easy realization of large-scale production.
Description
Technical Field
The invention relates to a preparation method of ferric phosphate with controllable morphology, belonging to the technical field of synthesis process control.
Background
In recent years, the problems of energy and environment are becoming more serious, the development of clean energy is urgently needed, and the large-scale use of various clean energy puts higher requirements on energy storage elements, so that the service life of an energy storage battery is also put higher requirements.
The iron phosphate is called ferric orthophosphate, anhydrous iron phosphate (FePO)4) Is one of ferric orthophosphates, can be used as a battery anode material, and can also be used as a good raw material for preparing a lithium iron phosphate battery material. At present, the method for synthesizing the iron phosphate is more, wherein the most used raw materials are soluble iron salts, but the cost of the raw materials is higher, the technical process for producing the iron phosphate is complex, the appearance of the product is uncontrollable, and the prepared product cannot be used as a battery anode material and a precursor of lithium iron phosphate.
Aiming at the defects of high production cost, complex process engineering and uncontrollable product appearance, the invention provides the method which has low cost and simple process and is suitable for large-scale industrial production.
Disclosure of Invention
In view of this, the technical problems to be solved by the present invention are: the defects of the prior art are overcome, the preparation method of the shape-controllable iron phosphate is provided, and the prepared battery-grade iron phosphate is simple in process, mild in reaction conditions, low in cost, controllable in shape and easy to realize large-scale production.
A preparation method of ferric phosphate with controllable morphology comprises the following steps:
1) the invention is that pure iron reacts with diluted concentrated sulfuric acid to prepare ferrous sulfate, 75g/L-85g/L high concentration ferrous sulfate solution is diluted, and added with concentrated phosphoric acid for acidification, the acidification amount is 10% -20% of the amount of iron ion matter, industrial grade hydrogen peroxide solution is added with the acidified solution for oxidation, and the solution is stirred at a certain speed in the process;
2) adding 1-2.0mol/l of phosphate into the obtained solution, wherein the amount of the phosphate is 92.5% -100% of that of the iron ion substances, and heating and aging the solution along with the stirring process.
In the technical scheme, the mass ratio of pure iron and concentrated sulfuric acid participating in the reaction is as follows: (1.5-1.2) 1.
In the technical scheme, the concentration of the diluted ferrous sulfate is 50-60 g/l.
In the technical scheme, the amount of the added industrial-grade hydrogen peroxide is 125-155% of the amount of the iron ion substances, the stirring speed is 740-760rpm, and the feeding time is 10-20 min.
In the technical scheme, the added phosphorus salt is one or a mixture of several of sodium dihydrogen phosphate, disodium hydrogen phosphate and trisodium phosphate which are reaction products of sodium hydroxide and phosphoric acid.
In the technical scheme, the heating temperature of the solution in the process of adding the phosphorus salt is 85-90 ℃, and the stirring speed is 300-900 rpm.
In the technical scheme, the aging time of the solution in the process is 1-3h, and the stirring speed is 250-350 rpm.
The invention has the beneficial effects that: the preparation method of the shape-controllable iron phosphate has the advantages that the prepared battery-grade iron phosphate is simple in process, mild in reaction condition, low in cost, controllable in shape and easy to realize large-scale production.
Drawings
FIG. 1 is an SEM of granular iron phosphate dihydrate.
FIG. 2 is an SEM of flaky iron phosphate dihydrate.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Reacting pure iron with diluted concentrated sulfuric acid to prepare ferrous sulfate, diluting 80g/l of high-concentration ferrous sulfate solution, adding concentrated phosphoric acid for acidification, wherein the acidification amount is 5% of the amount of iron ion substances, adding industrial-grade hydrogen peroxide solution into the acidified iron salt solution for oxidation, wherein the added industrial-grade hydrogen peroxide solution is 150% of the amount of iron ion substances, and stirring at the speed of 750rpm in the process;
adding 1.8mol/l of sodium monohydrogen phosphate with nearly neutral pH value of a liquid alkali adjusting system into the obtained solution, wherein the phosphate amount is 92.5-100% of the amount of iron ion substances, heating the reaction system at 85-90 ℃ for 2-2.5h, and aging for 1-3h, filtering, pulping and washing the obtained yellowish slurry to obtain a yellowish material filter cake with a spheroid shape, ensuring that the conductivity of the filtrate is less than 80 mu m/cm, and ventilating and drying the filter cake. Finally, dehydrating the spheroid yellowish material at the constant temperature of 600 ℃ for 4 hours to obtain slightly yellow spheroid ferric phosphate FePO4，The particle size of the particles is about 20 μm.
Example 2
Reacting pure iron with diluted concentrated sulfuric acid to prepare ferrous sulfate, diluting 90g/l of high-concentration ferrous sulfate solution, adding concentrated phosphoric acid for acidification, wherein the acidification amount is 15% of the amount of iron ions, adding industrial-grade hydrogen peroxide solution into the acidified solution for oxidation, wherein the added industrial-grade hydrogen peroxide solution is 150% of the molar amount of the iron ions, and stirring at the speed of 750rpm in the process;
2.0mol/l of sodium dihydrogen phosphate is added into the obtained solution, the phosphate amount is 92.5-100% of the amount of iron ion substances, the heating temperature of the reaction system is 85-90 ℃, the aging time is 1-2h, the obtained white slurry is filtered, pulped and washed to obtain a petal-shaped white material filter cake, the conductivity of the filtrate is ensured to be less than 80 mu m/cm, and meanwhile, the filter cake is ventilated and dried. Finally, dehydrating the petal-shaped white material at the constant temperature of 550 ℃ for 4h to obtain yellowish flaky ferric phosphate FePO4The particle size of the particles is6-9μm。
Claims (7)
1. A preparation method of ferric phosphate with controllable morphology is characterized by comprising the following steps: the method comprises the following steps:
1) the invention is that pure iron reacts with diluted concentrated sulfuric acid to prepare ferrous sulfate, 75g/L-85g/L high concentration ferrous sulfate solution is diluted, and added with concentrated phosphoric acid for acidification, the acidification amount is 10% -20% of the amount of iron ion matter, industrial grade hydrogen peroxide solution is added with the acidified solution for oxidation, and the solution is stirred at a certain speed in the process;
2) adding 1-2.0mol/l of phosphate into the obtained solution, wherein the amount of the phosphate is 92.5% -100% of that of the iron ion substances, and heating and aging the solution along with the stirring process.
2. The method of claim 1, wherein: the molar ratio of pure iron and concentrated sulfuric acid participating in the reaction is (1.5-1.2): 1.
3. The method of claim 1, wherein: the concentration of ferrous sulfate after dilution is 50-60 g/l.
4. The method of claim 1, wherein: the amount of the technical grade hydrogen peroxide added is 125-155% of the amount of the iron ion substance, the stirring speed is 740-760rpm, and the feeding time is 10-20 min.
5. The method of claim 2, wherein: the added phosphorus salt is one or a mixture of sodium dihydrogen phosphate, disodium hydrogen phosphate and trisodium phosphate which are reaction products of sodium hydroxide and phosphoric acid.
6. The method of claim 2, wherein: the temperature of the solution during the process of adding the phosphorus salt is 85-90 ℃, and the stirring speed is 300-900 rpm.
7. The method of claim 2, wherein: the aging time of the process for the solution is 1h-3h, and the stirring speed is 250-350 rpm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011612832 | 2020-12-30 | ||
| CN2020116128320 | 2020-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112811405A true CN112811405A (en) | 2021-05-18 |
Family
ID=75863572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110384792.7A Pending CN112811405A (en) | 2020-12-30 | 2021-04-09 | Preparation method of ferric phosphate with controllable morphology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112811405A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117509583A (en) * | 2023-11-23 | 2024-02-06 | 新洋丰农业科技股份有限公司 | Preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102255078A (en) * | 2011-05-27 | 2011-11-23 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
| KR20150007104A (en) * | 2013-07-10 | 2015-01-20 | 한국화학연구원 | The preparing method of lithium iron phosphate cathode active materials, the lithium iron phosphate cathod acive materials thereby and the secondary battery using the same |
| CN106044737A (en) * | 2016-08-15 | 2016-10-26 | 河北安耐哲新能源技术有限公司 | Preparation method of high-purity battery-grade anhydrous iron phosphate |
| CN106384822A (en) * | 2016-12-06 | 2017-02-08 | 中钢集团安徽天源科技股份有限公司 | Preparation method of amorphous battery-grade iron phosphate, lithium iron phosphate, battery positive electrode material and secondary battery |
| CN109326777A (en) * | 2018-08-28 | 2019-02-12 | 北京泰丰先行新能源科技有限公司 | A kind of preparation method of lithium iron phosphate cell material |
| CN110436428A (en) * | 2019-07-08 | 2019-11-12 | 湖南雅城新材料有限公司 | A kind of preparation method of sheet-form iron phosphate, sheet-form iron phosphate obtained and its application |
-
2021
- 2021-04-09 CN CN202110384792.7A patent/CN112811405A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102255078A (en) * | 2011-05-27 | 2011-11-23 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
| KR20150007104A (en) * | 2013-07-10 | 2015-01-20 | 한국화학연구원 | The preparing method of lithium iron phosphate cathode active materials, the lithium iron phosphate cathod acive materials thereby and the secondary battery using the same |
| CN106044737A (en) * | 2016-08-15 | 2016-10-26 | 河北安耐哲新能源技术有限公司 | Preparation method of high-purity battery-grade anhydrous iron phosphate |
| CN106384822A (en) * | 2016-12-06 | 2017-02-08 | 中钢集团安徽天源科技股份有限公司 | Preparation method of amorphous battery-grade iron phosphate, lithium iron phosphate, battery positive electrode material and secondary battery |
| CN109326777A (en) * | 2018-08-28 | 2019-02-12 | 北京泰丰先行新能源科技有限公司 | A kind of preparation method of lithium iron phosphate cell material |
| CN110436428A (en) * | 2019-07-08 | 2019-11-12 | 湖南雅城新材料有限公司 | A kind of preparation method of sheet-form iron phosphate, sheet-form iron phosphate obtained and its application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117509583A (en) * | 2023-11-23 | 2024-02-06 | 新洋丰农业科技股份有限公司 | Preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101708834B (en) | Wafer-like ferric phosphate, preparation method and application thereof | |
| KR101547137B1 (en) | Iron (III) orthophosphate for Li ion accumulators | |
| US20230322558A1 (en) | Preparation method and application of iron phosphate | |
| EP3029762A1 (en) | Method for synthesizing nano-lithium iron phosphate without water of crystallization in aqueous phase at normal pressure | |
| KR20110139190A (en) | Production of iron orthophosphate | |
| CN102126713B (en) | High-purity iron phosphate used for producing lithium ion battery positive-pole material and preparation method thereof | |
| CN111377426B (en) | Preparation method of anhydrous iron phosphate nanoparticles | |
| WO2024055467A1 (en) | Method for preparing iron phosphate by using phosphorite and ferrous sulfate | |
| CN101920948A (en) | Method for preparing granularity controllable ferric orthophosphate powder | |
| CN108862226A (en) | Preparation method of high-purity battery-grade iron phosphate | |
| CN107344715A (en) | The production method of feed-level calcium biphosphate | |
| CN109928375A (en) | A method of ferric phosphate is prepared using calcium dihydrogen phosphate | |
| CN115477293A (en) | Preparation method of anhydrous iron phosphate with low impurity and high specific surface area | |
| CN112811405A (en) | Preparation method of ferric phosphate with controllable morphology | |
| CN104733709A (en) | Preparation method of lithium manganese iron phosphate or lithium manganese iron phosphate composite material in controllable crystal form | |
| CN117263153B (en) | Porous spherical ferric phosphate, preparation method thereof and metal phosphate | |
| CN102153061B (en) | Method for synthesizing ferric phosphate material | |
| CN101913585A (en) | Synthesizing method of battery-level ultra-thin iron phosphate | |
| CN103832991A (en) | Preparation method of iron phosphate nano material | |
| CN113353908A (en) | Preparation method of rod-shaped nano iron phosphate material | |
| CN111792635A (en) | Preparation method of anhydrous iron phosphate | |
| CN113213445A (en) | Preparation method of battery-grade lithium phosphate | |
| CN111377425A (en) | Preparation method of low-cost iron phosphate particles | |
| CN114084878B (en) | Preparation method for synthesizing ferric phosphate by using double iron sources | |
| CN118495499B (en) | Preparation method of carbonless phosphate positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210518 |
|
| WD01 | Invention patent application deemed withdrawn after publication |