CN112678794A - Method for preparing multi-element doped lithium iron phosphate from phosphorized slag - Google Patents
Method for preparing multi-element doped lithium iron phosphate from phosphorized slag Download PDFInfo
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- CN112678794A CN112678794A CN202110123541.3A CN202110123541A CN112678794A CN 112678794 A CN112678794 A CN 112678794A CN 202110123541 A CN202110123541 A CN 202110123541A CN 112678794 A CN112678794 A CN 112678794A
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Abstract
The invention discloses a method for preparing multi-element doped lithium iron phosphate from phosphorized slag. The method for preparing the multi-element doped lithium iron phosphate by the phosphorization slag comprises the following steps: step A: mixing the phosphated residue with hydrochloric acid, stirring for dissolving, adding ferric salt and iron oxide or phosphoric acid according to the iron-phosphorus ratio in the solution to adjust the iron-phosphorus ratio, performing suction filtration, and collecting filtrate; and B: distilling the filtrate, adding a surfactant solution in the distillation process, leaching after the ferric phosphate is separated out from the solution, washing a filter cake, drying and calcining to obtain finished anhydrous ferric phosphate; and C: and C, adding a lithium source and a carbon source into the iron phosphate obtained in the step B, mixing and grinding the mixture by taking water as a medium, and spray-drying the obtained slurry to obtain sintered precursor powder. The method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag has relatively simple reaction conditions, and the residual amount of metal element impurities in the iron phosphate is relatively small, so that the preparation of the subsequent lithium iron phosphate is facilitated.
Description
Technical Field
The invention relates to a method for preparing multi-element doped lithium iron phosphate from phosphorized slag.
Background
Chinese patent CN102593450A discloses a method for preparing multi-element doped lithium iron phosphate by using phosphated waste residues as main raw materials. Firstly, acid cleaning is carried out on the phosphorization slag to prepare crude iron phosphate containing metal elements such as Zn, Ca, Ni and the like. Then the crude ferric phosphate is used as a raw material, and a carbothermic reduction high-temperature solid phase method is adopted to prepare the lithium iron phosphate. The method has the advantages that the process for preparing the crude iron phosphate is too simple, the residual amount of metal element impurities in the iron phosphate is large, and the subsequent preparation of the lithium iron phosphate is not utilized.
Chinese patent CN105810943A discloses a method for preparing zinc-doped lithium iron phosphate by using phosphated slag. And (3) washing and removing impurities from the phosphorization slag by using two inorganic acids to obtain the iron phosphate containing trace zinc. Then preparing the lithium iron phosphate by the iron phosphate by adopting a carbothermic high-temperature solid phase method. The method needs to adopt high-temperature high-pressure reaction in an acidic medium system, and the reaction conditions are relatively harsh.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing multi-element doped lithium iron phosphate from phosphated slag.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing multi-element doped lithium iron phosphate from phosphorized slag comprises the following steps:
step A: mixing the phosphated residue with hydrochloric acid, stirring for dissolving, adding ferric salt and iron oxide or phosphoric acid according to the iron-phosphorus ratio in the solution to adjust the iron-phosphorus ratio, performing suction filtration, and collecting filtrate;
and B: distilling the filtrate, adding a surfactant solution in the distillation process, leaching after the ferric phosphate is separated out from the solution, washing a filter cake, drying and calcining to obtain finished anhydrous ferric phosphate;
and C: adding a lithium source and a carbon source into the iron phosphate obtained in the step B, mixing and grinding the mixture by taking water as a medium, and spray-drying the obtained slurry to obtain sintered precursor powder;
step D: and D, roasting the precursor powder obtained in the step C for 6-12 hours at the temperature of 600-800 ℃ under the protection of inert gas to obtain trace metal element doped lithium iron phosphate.
Further, the concentration of the hydrochloric acid in the step A is 10-38%.
Further, the heating temperature of the distillation in the step B is 80-200 ℃.
Further, in the step B, the surfactant is at least one of a sulfonate surfactant or a sulfate surfactant.
Further, the drying temperature of the ferric phosphate in the step B is 80-150 ℃.
Further, the calcining temperature of the ferric phosphate in the step B is 400-700 ℃.
Compared with the prior art, the method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag has the advantages that the reaction conditions are relatively simple, the residual amount of metal element impurities in the iron phosphate is small, and the subsequent preparation of the lithium iron phosphate is utilized.
Detailed Description
The invention provides a method for preparing multi-element doped lithium iron phosphate from phosphorization slag, which is characterized by comprising the following steps of:
step A: mixing the phosphated residue with hydrochloric acid, stirring for dissolving, adding ferric salt and iron oxide or phosphoric acid according to the iron-phosphorus ratio in the solution to adjust the iron-phosphorus ratio, performing suction filtration, and collecting filtrate;
and B: distilling the filtrate, adding a surfactant solution in the distillation process, leaching after the ferric phosphate is separated out from the solution, washing a filter cake, drying and calcining to obtain finished anhydrous ferric phosphate, wherein the ferric phosphate contains trace elements such as Zn, Al, Cr, Ti and the like;
and C: adding a lithium source and a carbon source into the iron phosphate obtained in the step B, mixing and grinding the mixture by taking water as a medium, and spray-drying the obtained slurry to obtain sintered precursor powder;
step D: and D, roasting the precursor powder obtained in the step C for 6-12 hours at the temperature of 600-800 ℃ under the protection of inert gas to obtain trace metal element doped lithium iron phosphate.
Further, the concentration of the hydrochloric acid in the step A is 10-38%.
Further, the heating temperature of the distillation in the step B is 80-200 ℃.
Further, in the step B, the surfactant is at least one of a sulfonate surfactant or a sulfate surfactant.
Further, the drying temperature of the ferric phosphate in the step B is 80-150 ℃.
Further, the calcining temperature of the ferric phosphate in the step B is 400-700 ℃.
Compared with the prior art, the method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag has the advantages that the reaction conditions are relatively simple, the residual amount of metal element impurities in the iron phosphate is small, and the subsequent preparation of the lithium iron phosphate is utilized.
Example 1
20 g of dry phosphated residue is taken and added with 100 ml of 15 percent hydrochloric acid, and stirred and dissolved for 12 hours. After the molar ratio of phosphorus to iron in the solution is measured, adding ferric trichloride, and adjusting the molar ratio of phosphorus to iron in the solution to 1.1: and 1, carrying out suction filtration and collecting filtrate. Adding the filtrate into a distillation flask, heating to 150 deg.C while stirring, and adding 0.2% sodium dodecyl sulfate into the distillation flask, if foam appears, removing in time. And after the ferric phosphate is separated out, stopping heating, performing suction filtration, and washing the filter cake for multiple times by using deionized water. The filter cake is dried at 90 ℃ and then is burnt at 500 ℃ for 2 hours to obtain the multielement doped anhydrous iron phosphate.
Grinding anhydrous iron phosphate into powder, adding lithium carbonate according to the molar ratio of lithium to iron of 1.02:1, adding glucose according to 10% of the weight of the iron phosphate, and stirring with deionized water to prepare slurry with the solid content of 30%. Adding the slurry into a small-sized nanometer grinding machine, grinding the slurry to a micro-nanometer level in particle size, and then carrying out spray drying. And (3) calcining the dried powder in a box-type atmosphere furnace under the protection of nitrogen, and calcining for 8 hours at 730 ℃ to obtain the lithium iron phosphate material. The obtained lithium iron phosphate is made into a button cell, and the 0.1C first discharge capacity of the button cell is 158.2 mAh/g.
Example 2
20 g of dry phosphated residue is taken and added with 100 ml of 25 percent hydrochloric acid, and stirred and dissolved for 12 hours. After the molar ratio of phosphorus to iron in the solution is measured, adding ferric oxide, adjusting the molar ratio of phosphorus to iron in the solution to 1:1, performing suction filtration, and collecting filtrate. Adding the filtrate into a distillation flask, heating to 130 deg.C under stirring, and adding 0.2% sodium lauryl sulfate into the distillation flask, if foam appears, removing in time. And after the ferric phosphate is separated out, stopping heating, performing suction filtration, and washing the filter cake for multiple times by using deionized water. The filter cake is dried at 90 ℃ and then calcined at 500 ℃ for 2 hours to obtain the multielement doped anhydrous iron phosphate.
Grinding anhydrous iron phosphate into powder, adding lithium carbonate according to the molar ratio of lithium to iron of 1.02:1, adding glucose according to 10% of the weight of the iron phosphate, and stirring with deionized water to prepare slurry with the solid content of 30%. Adding the slurry into a small-sized nanometer grinding machine, grinding the slurry to a micro-nanometer level in particle size, and then carrying out spray drying. And calcining the dried powder in a box-type atmosphere furnace under the protection of nitrogen, and calcining at 730 ℃ for 8 hours to obtain the lithium iron phosphate material. The obtained lithium iron phosphate is made into a button cell, and the 0.1C first discharge capacity of the button cell is 157.5 mAh/g.
The above description is only for the purpose of illustrating specific embodiments of the present invention, and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made in accordance with the spirit of the present invention should be considered as falling within the scope of the present invention.
Claims (6)
1. A method for preparing multi-element doped lithium iron phosphate from phosphorized slag is characterized by comprising the following steps: the method comprises the following steps:
step A: mixing the phosphated residue with hydrochloric acid, stirring for dissolving, adding ferric salt and iron oxide or phosphoric acid according to the iron-phosphorus ratio in the solution to adjust the iron-phosphorus ratio, performing suction filtration, and collecting filtrate;
and B: distilling the filtrate, adding a surfactant solution in the distillation process, leaching after the ferric phosphate is separated out from the solution, washing a filter cake, drying and calcining to obtain finished anhydrous ferric phosphate;
and C: adding a lithium source and a carbon source into the iron phosphate obtained in the step B, mixing and grinding the mixture by taking water as a medium, and spray-drying the obtained slurry to obtain sintered precursor powder;
step D: and D, roasting the precursor powder obtained in the step C for 6-12 hours at the temperature of 600-800 ℃ under the protection of inert gas to obtain trace metal element doped lithium iron phosphate.
2. The method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag as claimed in claim 1, which is characterized in that: the concentration of the hydrochloric acid in the step A is 10-38%.
3. The method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag as claimed in claim 1, which is characterized in that: and the heating temperature of the distillation in the step B is 80-200 ℃.
4. The method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag as claimed in claim 1, which is characterized in that: and in the step B, the surfactant is at least one of sulfonate surfactant or sulfate surfactant.
5. The method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag as claimed in claim 1, which is characterized in that: and the drying temperature of the ferric phosphate in the step B is 80-150 ℃.
6. The method for preparing the multi-element doped lithium iron phosphate by using the phosphorization slag as claimed in claim 1, which is characterized in that: and the calcining temperature of the ferric phosphate in the step B is 400-700 ℃.
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| CN202110123541.3A CN112678794A (en) | 2021-01-29 | 2021-01-29 | Method for preparing multi-element doped lithium iron phosphate from phosphorized slag |
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| CN202110123541.3A CN112678794A (en) | 2021-01-29 | 2021-01-29 | Method for preparing multi-element doped lithium iron phosphate from phosphorized slag |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810943A (en) * | 2016-05-16 | 2016-07-27 | 上海第二工业大学 | Method for preparing zinc-doped lithium iron phosphate from phosphated residue |
| CN106495122A (en) * | 2016-11-03 | 2017-03-15 | 王坚 | A kind of method that waste lithium iron phosphate positive plate reclaims iron phosphate presoma |
| CN107473195A (en) * | 2017-09-11 | 2017-12-15 | 上海第二工业大学 | A kind of method that superfine iron phosphate micro mist is prepared using phosphatization slag as raw material |
| CN107512710A (en) * | 2017-06-30 | 2017-12-26 | 南通玛盛环保科技有限公司 | A kind of method for purifying phosphatization slag and preparing lithium iron phosphate positive material |
| CN107720715A (en) * | 2017-09-28 | 2018-02-23 | 湖南华菱节能环保科技有限公司 | A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material |
-
2021
- 2021-01-29 CN CN202110123541.3A patent/CN112678794A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810943A (en) * | 2016-05-16 | 2016-07-27 | 上海第二工业大学 | Method for preparing zinc-doped lithium iron phosphate from phosphated residue |
| CN106495122A (en) * | 2016-11-03 | 2017-03-15 | 王坚 | A kind of method that waste lithium iron phosphate positive plate reclaims iron phosphate presoma |
| CN107512710A (en) * | 2017-06-30 | 2017-12-26 | 南通玛盛环保科技有限公司 | A kind of method for purifying phosphatization slag and preparing lithium iron phosphate positive material |
| CN107473195A (en) * | 2017-09-11 | 2017-12-15 | 上海第二工业大学 | A kind of method that superfine iron phosphate micro mist is prepared using phosphatization slag as raw material |
| CN107720715A (en) * | 2017-09-28 | 2018-02-23 | 湖南华菱节能环保科技有限公司 | A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material |
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