CN103864044A - Method for converting ferrophosphorus into battery grade ferric phosphate by using microwave method - Google Patents
Method for converting ferrophosphorus into battery grade ferric phosphate by using microwave method Download PDFInfo
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- CN103864044A CN103864044A CN201410083977.4A CN201410083977A CN103864044A CN 103864044 A CN103864044 A CN 103864044A CN 201410083977 A CN201410083977 A CN 201410083977A CN 103864044 A CN103864044 A CN 103864044A
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- ferrophosphorus
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Abstract
The invention discloses a method for converting ferrophosphorus into battery grade ferric phosphate by using a microwave method. The method comprises the following steps: grinding ferrophosphorus into 200-300 meshes, adding a mixed solution of phosphoric acid and nitric acid, placing in a microwave reactor, and performing microwave reaction for 20-50min under the pressure of 0.2-0.9 Mpa at the temperature of 110-140 DEG C to dissolve ferrophosphorus powder thoroughly; further carrying out the microwave reaction for 30-50min under the pressure of 0.2-0.9Mpa at the temperature of 110-140 DEG C under the condition that impurity ions are not separated; filtering, washing and drying a precipitate by relieving pressure of the microwave reactor to prepare the white battery grade ferric phosphate. When the method is adopted, the impurity ions are not needed to be separated, the prepared ferric phosphate is few in impurities, even in particle size distribution, and is applicable to further prepare battery grade lithium iron phosphate.
Description
Technical field
The present invention relates to phosphoric acid salt, be particularly converted into the method for battery-grade iron phosphate by ferrophosphorus.
Background technology
Iron lithium phosphate, owing to having heavy body, high-voltage, good cycle and eco-friendly advantage, is expected to become the important materials of the required large-scale energy-storage batteries such as electromobile.
Solid reaction process is widely used method in current iron lithium phosphate production and research process, and tertiary iron phosphate becomes the important presoma of making iron lithium phosphate in carbothermic method gradually.In numerous documents and patent, all provide source of iron and phosphorus source to make the battery-grade iron phosphate lithium of excellent property with tertiary iron phosphate.
Pertinent literature and experimental study show, the preparation of tertiary iron phosphate mixes with phosphoric acid or soluble phosphoric acid salts solution with trivalent iron salt conventionally, utilizes ammoniacal liquor or alkali lye control pH value in 1.8 left and right, and under 85 DEG C of left and right heating conditions, crystallization forms; Tertiary iron phosphate also can, with divalent iron salt and phosphoric acid or soluble phosphate formation mixing solutions, by oxygenant and alkali lye control reaction conditions, obtain form iron phosphate crystal.But in commercial process, be difficult to effectively reach uniform pH value by all conversion zones of alkali lye control on the one hand, can bring ferric hydrolysis, thereby produce impurity; On the other hand, the use of ammoniacal liquor or other alkali lye increases the production cost of iron lithium phosphate, may introduce impurity simultaneously, simultaneously because molysite cost in raw material is higher, makes tertiary iron phosphate cost higher.Applicant, for the present Research of current tertiary iron phosphate, has developed taking phosphorus production byproduct ferrophosphorus as raw material, dissolves and crystallization, and do not need, on the basis of Physical or chemical method removal of impurities, directly to prepare battery-grade iron phosphate by microwave method.
Summary of the invention
The object of the invention is to provide a kind of taking ferrophosphorus as raw material, dissolves and crystallization by microwave method in acidic medium, is not needing Physical or chemical method removal of impurities and is not needing ammoniacal liquor or other alkali lye control pH value in the situation that, prepare the method for battery-grade iron phosphate.
Technical scheme of the present invention: it comprises the steps:
Step 1: ferrophosphorus being ground to 200 order-300 orders, adding phosphoric acid and nitric acid mix acid liquor, be placed in microwave reactor, is 0.2MPa-0.9MPa at pressure, temperature is under the condition of 110 DEG C-140 DEG C, microwave reaction 20min-50min, ferrophosphorus powder fully dissolves;
Step 2: ferrophosphorus, on above-mentioned Microwave Dissolution basis, does not need in the situation of separating impurity ion, continues microwave reaction 30min-50min; Pressure is 0.2MPa-0.9MPa, and temperature is 110 DEG C-140 DEG C;
Step 3: microwave reactor is by pressure release, by sedimentation and filtration, washing, the dry white cell level tertiary iron phosphate of preparing.
Mix acid liquor described in step 1 refers to that concentration is 0.2molL
-1-1 molL
-1phosphoric acid and concentration be 0.2molL
-1-1 molL
-1nitric acid form mixing solutions, in dissolution system, phosphoric and ferro element mol ratio are controlled to 3:1-6:1.
Described microwave reactor refers to that utilizing wavelength is the radiowave of 0.001～1 meter, and the hertzian wave that frequency is 300MHz-3000GHz is converted into the reactor of heat energy after being absorbed by polar material.
Advantage of the present invention: use raw material ferrophosphorus price low; The present invention is by Microwave Dissolution and crystallization, and process is simple, does not need impurity to separate; The tertiary iron phosphate foreign matter content of preparing is few, and Orthophosphoric acid Ferrum purity is high, and even particle size distribution is applicable to further prepare battery-grade iron phosphate lithium.
Embodiment
Embodiment 1:
Take and be ground to 3 grams of 200 object ferrophosphorus, adding concentration is 0.8 molL
-1phosphoric acid solution 50ml, concentration is 0.5 molL
-1salpeter solution 50ml, stirs and is placed in microwave reactor sealed vessel, and it is 0.7MPa that the first stage arranges voltage-controlled, and the reaction times is 30min, and it is 0.3MPa that subordinate phase arranges voltage-controlled, and the reaction times is 40min.
After pressure release, by sedimentation and filtration, washing, dry, prepare battery-grade iron phosphate.
Embodiment 2:
Take and be ground to 3 grams of 300 object ferrophosphorus, adding concentration is 0.8 molL
-150 milliliters of phosphoric acid solutions, concentration is 0.5 molL
-150 milliliters of salpeter solutions, are placed in microwave reactor sealed vessel, and it is 0.6MPa that the first stage arranges voltage-controlled, and the reaction times is 40min, and it is 0.4MPa that subordinate phase arranges voltage-controlled, and the reaction times is 50min.
After pressure release, by sedimentation and filtration, washing, dry, prepare battery-grade iron phosphate.
Embodiment 3:
Take and be ground to 3 grams of 300 object ferrophosphorus, adding concentration is 0.8 molL
-150 milliliters of phosphoric acid solutions, concentration is 0.9 molL
-150 milliliters of salpeter solutions, are placed in microwave reactor sealed vessel, and it is 0.6MPa that the first stage arranges voltage-controlled, and the reaction times is 35min, and it is 0.4MPa that subordinate phase arranges voltage-controlled, and the reaction times is 50min.
After pressure release, by sedimentation and filtration, washing, dry, prepare battery-grade iron phosphate.
Claims (3)
1. utilize microwave method ferrophosphorus to be converted into the method for battery-grade iron phosphate, it is characterized in that: it comprises the steps:
Step 1: ferrophosphorus being ground to 200 order-300 orders, adding phosphoric acid and nitric acid mix acid liquor, be placed in microwave reactor, is 0.2MPa-0.9MPa at pressure, temperature is under the condition of 110 DEG C-140 DEG C, microwave reaction 20min-50min, ferrophosphorus powder fully dissolves;
Step 2: ferrophosphorus, on above-mentioned Microwave Dissolution basis, does not need in the situation of separating impurity ion, continues microwave reaction 30min-50min; Pressure is 0.2MPa-0.9MPa, and temperature is 110 DEG C-140 DEG C;
Step 3: microwave reactor is by pressure release, by sedimentation and filtration, washing, the dry white cell level tertiary iron phosphate of preparing.
2. method according to claim 1, is characterized in that: described mix acid liquor refers to that concentration is 0.2molL
-1-1 molL
-1phosphoric acid and concentration be 0.2molL
-1-1 molL
-1the mixing solutions that forms of nitric acid, in dissolution system, phosphoric and ferro element mol ratio are controlled to 3:1-6:1.
3. method according to claim 1, is characterized in that: described microwave reactor refers to that utilizing wavelength is the radiowave of 0.001 meter～1 meter, and the hertzian wave that frequency is 300MHz-3000GHz is converted into the reactor of heat energy after being absorbed by polar material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410083977.4A CN103864044B (en) | 2014-03-10 | 2014-03-10 | Microwave method is utilized ferrophosphorus to be converted into the method for battery-grade iron phosphate |
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| CN201410083977.4A CN103864044B (en) | 2014-03-10 | 2014-03-10 | Microwave method is utilized ferrophosphorus to be converted into the method for battery-grade iron phosphate |
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| CN103864044A true CN103864044A (en) | 2014-06-18 |
| CN103864044B CN103864044B (en) | 2015-08-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107792840A (en) * | 2017-10-27 | 2018-03-13 | 昆明理工大学 | A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate |
| CN107986252A (en) * | 2017-10-27 | 2018-05-04 | 昆明理工大学 | A kind of method that ferric phosphate is prepared using accessory substance ferrophosphorus |
| CN108767197A (en) * | 2018-06-05 | 2018-11-06 | 贵州大学 | A kind of preparation method of optimization based lithium-ion battery positive plate |
| CN115432683A (en) * | 2022-10-09 | 2022-12-06 | 铜陵安伟宁新能源科技有限公司 | Method for preparing high-compaction battery-grade iron phosphate under low-temperature condition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011030786A1 (en) * | 2009-09-09 | 2011-03-17 | 戸田工業株式会社 | Ferric phosphate hydrate particle powder and process for production thereof, olivine-type lithium iron phosphate particle powder and process for production thereof, and non-aqueous electrolyte secondary battery |
| CN102167303A (en) * | 2011-04-30 | 2011-08-31 | 云南省化工研究院 | Method for preparing anhydrous ferric orthophosphate by microwave spouting |
| WO2013099409A1 (en) * | 2011-12-26 | 2013-07-04 | 株式会社村田製作所 | Method for producing iron phosphate, lithium iron phosphate, electrode active material, and secondary battery |
-
2014
- 2014-03-10 CN CN201410083977.4A patent/CN103864044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011030786A1 (en) * | 2009-09-09 | 2011-03-17 | 戸田工業株式会社 | Ferric phosphate hydrate particle powder and process for production thereof, olivine-type lithium iron phosphate particle powder and process for production thereof, and non-aqueous electrolyte secondary battery |
| CN102167303A (en) * | 2011-04-30 | 2011-08-31 | 云南省化工研究院 | Method for preparing anhydrous ferric orthophosphate by microwave spouting |
| WO2013099409A1 (en) * | 2011-12-26 | 2013-07-04 | 株式会社村田製作所 | Method for producing iron phosphate, lithium iron phosphate, electrode active material, and secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107792840A (en) * | 2017-10-27 | 2018-03-13 | 昆明理工大学 | A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate |
| CN107986252A (en) * | 2017-10-27 | 2018-05-04 | 昆明理工大学 | A kind of method that ferric phosphate is prepared using accessory substance ferrophosphorus |
| CN108767197A (en) * | 2018-06-05 | 2018-11-06 | 贵州大学 | A kind of preparation method of optimization based lithium-ion battery positive plate |
| CN108767197B (en) * | 2018-06-05 | 2021-07-13 | 贵州大学 | Preparation method for optimizing lithium ion battery positive plate |
| CN115432683A (en) * | 2022-10-09 | 2022-12-06 | 铜陵安伟宁新能源科技有限公司 | Method for preparing high-compaction battery-grade iron phosphate under low-temperature condition |
| CN115432683B (en) * | 2022-10-09 | 2024-04-26 | 铜陵安伟宁新能源科技有限公司 | Method for preparing high-compaction battery-level ferric phosphate under low-temperature condition |
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| CN103864044B (en) | 2015-08-26 |
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