CN112938922B - Method for preparing battery-grade ferric phosphate from titanium white byproduct ferrous sulfate - Google Patents
Method for preparing battery-grade ferric phosphate from titanium white byproduct ferrous sulfate Download PDFInfo
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Abstract
The invention discloses a method for preparing battery-grade ferric phosphate from titanium white byproduct ferrous sulfate, which belongs to the technical field of battery material preparation, and comprises the following steps: dissolving phosphate in water, adding titanium white by-product ferrous sulfate, carrying out suction filtration after the heating reaction is finished, adding an oxidant into the obtained filtrate, heating, and carrying out filter pressing, washing, drying and sintering after the reaction is finished to obtain the battery-grade ferric phosphate; the invention realizes the high added value recycling of the titanium white byproduct ferrous sulfate, and the prepared ferric phosphate has high purity, low impurity content, small and uniform granularity and high tap density, and meets the requirements of battery-level ferric phosphate; the invention has simple process, higher yields of intermediate products and final products, mature and reliable technology and easy realization of industrialized production; the invention has the advantages of easily obtained raw materials, low cost, no pollution in the reaction process and meeting the green environmental protection requirement.
Description
Technical Field
The invention belongs to the technical field of battery material preparation, and particularly relates to a method for preparing battery-grade ferric phosphate from titanium white by-product ferrous sulfate.
Background
The lithium iron phosphate anode material is the most rapidly developed lithium battery anode material at present, the purity, the structure and the morphology of the ferric phosphate serving as a precursor of the lithium iron phosphate have great influence on the performance of the lithium iron phosphate, and the electrochemical performance of the lithium iron phosphate synthesized from different ferric phosphate raw materials has great difference, so that the prepared ferric phosphate with excellent quality has great significance for popularization and application of the lithium iron phosphate anode material.
The existing preparation process of ferric phosphate mainly comprises a hydrothermal method, a sol-gel method and the like. The hydrothermal method is an effective method for inorganic synthesis and material treatment by adopting an aqueous solution as a reaction system in a specially-made closed reactor, and creating a relatively high-temperature and high-pressure reaction environment by heating and pressurizing the reaction system, so that substances which are generally insoluble or insoluble are dissolved and recrystallized. The hydrothermal method is one of the wet chemical methods for preparing the ultra-fine powder. Nanjing Dada in 2000The chemical Guo Xuefeng adopts a hydrothermal method to uniformly mix iron powder, sodium hydroxide, water and the like, then reacts for one week at the normal pressure of 120 ℃, and the lamellar crystal ferric phosphate is obtained through centrifugation, washing and drying. In 2006 Mal et al, ferric chloride and disodium phosphate were uniformly mixed, and sodium dodecyl sulfate was used as a surfactant, and the mixture was subjected to hydrothermal reaction at 180℃for 15 hours to thereby prepare an organic and inorganic combined composite mesoporous ferric phosphate for the first time. Kandori et al have controlled the reactant Fe (ClO) by stringent 4 ) 3 And the concentration of phosphoric acid, and carrying out hydrothermal reaction for 16 hours to obtain spherical ferric phosphate. Compared with other powder preparation methods, the hydrothermal method has the advantages of simple reaction process, but the disadvantage of one-time feeding, uncontrollable whole growth process, limited crystal growth size and number by the size of the container, long reaction time and difficulty in industrial production.
The sol-gel method is generally to prepare a uniform solution by using a chemical reagent of metal alkoxide or inorganic salt and a solvent, uniformly mix the solution with a reactant in a liquid phase, react with water in a certain solvent to generate a stable sol system, then convert the sol into gel through standing or drying treatment, and calcine the gel at a temperature lower than the conventional sintering temperature to form the metal oxide ultrafine powder. The sol-gel process requires a relatively low temperature for chemical reactions, and can achieve uniformity at the molecular level. But the time required for the whole sol-gel process is longer; the gel has a plurality of micropores, and the dried product is easy to shrink.
At present, most enterprises generally adopt Fe 2+ Or Fe (Fe) 3+ An aqueous solution of ions selected from the group consisting of hydroxides, oxides, oxyhydroxides, hydrous oxides, carbonates and hydroxycarbonates in the oxidized state of iron (II), iron (III) or mixed iron (II, III) compounds is introduced into an aqueous medium containing phosphoric acid, and an oxidizing agent is added to the aqueous Fe phosphate 2+ Oxidizing iron (II) in the solution to obtain FePO of the general formula 4 ·nH 2 Ferric (iii) orthophosphate precipitate of O. The research on preparing ferric sulfate by using the titanium white byproduct ferrous sulfate is less, and complicated impurity removal and purification steps are usually required, so that the research on preparing battery-grade ferric phosphate by using the titanium white byproduct ferrous sulfate as a raw material with simple process is carried outThe method has important significance for reasonable utilization of the titanium white byproduct ferrous sulfate and development of the lithium iron phosphate anode material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing battery grade ferric phosphate from titanium white byproduct ferrous sulfate.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a method for preparing battery-grade ferric phosphate from titanium white byproduct ferrous sulfate, which comprises the following steps:
(1) Dissolving phosphate in water, adding titanium white byproduct ferrous sulfate, and carrying out suction filtration after the heating reaction is finished to obtain filtrate and precipitate;
(2) And (3) adding an oxidant into the filtrate obtained in the step (1), heating, and after the reaction, performing filter pressing, washing, drying and sintering to obtain the battery-grade ferric phosphate.
Further, in the step (1), the phosphate is diammonium hydrogen phosphate.
Further, in the step (1), the temperature is heated to 50-60 ℃, and the reaction time is 12-24 hours.
Further, in the step (2), the oxidant is 30-35 wt% of hydrogen peroxide.
Further, in the step (2), the heating is carried out to 130-140 ℃, and the reaction time is 24-36 h.
Further, the amount of the oxidizing agent in the step (2) is 1.5 to 2 times the theoretical molar amount of the oxidizing agent required for converting all ferrous ions in the filtrate into ferric ions.
The reaction equation of the invention is:
2FeSO 4 +H 2 O 2 +2H 2 O+2(NH 4 ) 2 HPO 4 →2(NH 4 )SO 4 +2FePO 4 ·2H 2 O↓
2FePO 4 ·2H 2 O→2FePO 4 +2H 2 O。
compared with the prior art, the invention has the following beneficial effects:
(1) The battery grade ferric phosphate is prepared by taking the titanium white byproduct ferrous sulfate as a raw material, so that the high added value recycling of the titanium white byproduct ferrous sulfate is realized, the prepared ferric phosphate has high purity, less impurity content, small and uniform granularity and high tap density, and meets the requirements of the battery grade ferric phosphate;
(2) The invention has simple process, higher yields of intermediate products and final products, mature and reliable technology and easy realization of industrialized production;
(3) The invention has the advantages of easily obtained raw materials, low cost, no pollution in the reaction process and meeting the green environmental protection requirement.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "parts" in the present invention are parts by weight unless otherwise specified.
In the following examples, feSO was produced as a titanium white byproduct in ferrous sulfate 4 The content of (2) is 16.98%; the H is 2 O 2 The theoretical amount of (2) refers to H required for converting ferrous ions in the filtrate into ferric ions 2 O 2 Theoretical molar amount of (a).
Example 1
The preparation of the battery-grade ferric phosphate comprises the following steps:
(1) 9.26 parts of diammonium hydrogen phosphate is dissolved in water, placed in a stainless steel reaction kettle, and titanium white byproduct ferrous sulfate is added to enable FeSO to be generated 4 18.34 parts of the mixture is heated to 50 ℃, stirred and reacted for 24 hours, and filtered by suction to obtain filtrate and precipitate;
(2) Adding 30wt% hydrogen peroxide into the filtrate obtained in the step (1) to ensure that H contained in the hydrogen peroxide 2 O 2 The molar weight of the iron phosphate is 2 times of the theoretical dosage, the iron phosphate is heated to 130 ℃, a large amount of white precipitate appears after the reaction is carried out for 36 hours, then the iron phosphate is subjected to filter pressing by a filter press, other wastes such as salts are removed by washing with pure water, then the iron phosphate is put into a dryer for drying, so as to obtain ferric orthophosphate dihydrate, then the ferric orthophosphate is sintered and dehydrated, and then the ferric orthophosphate is sent to a grinding system for grinding and crushing, and packaging, so as to obtain 10 parts of battery-grade ferric phosphate.
Example 2
The preparation method of the battery-grade ferric phosphate comprises the following steps:
(1) 9.26 parts of diammonium hydrogen phosphate is dissolved in water, placed in a stainless steel reaction kettle, and titanium white byproduct ferrous sulfate is added to enable FeSO to be generated 4 18.34 parts of the mixture is heated to 60 ℃, stirred and reacted for 12 hours, and filtered by suction to obtain filtrate and precipitate;
(2) Adding 35wt% hydrogen peroxide into the filtrate obtained in the step (1) to ensure that H contained in the hydrogen peroxide 2 O 2 The molar weight of the iron phosphate is 1.5 times of the theoretical dosage, the iron phosphate is heated to 140 ℃, a large amount of white precipitate appears after the reaction for 24 hours, then the iron phosphate is subjected to filter pressing by a filter press, other wastes such as salts are removed by washing with pure water, then the iron phosphate is put into a dryer for drying, so as to obtain dihydrate iron orthophosphate, then the dihydrate iron phosphate is sintered and dehydrated, and is sent to a grinding system for grinding and crushing, and is packaged, so that the battery-grade iron phosphate is obtained.
Example 3
The preparation of the battery-grade ferric phosphate comprises the following steps:
(1) 9.26 parts of diammonium hydrogen phosphate is dissolved in water, placed in a stainless steel reaction kettle, and titanium white byproduct ferrous sulfate is added to enable FeSO to be generated 4 18.34 parts of the mixture is heated to 55 ℃, stirred and reacted for 18 hours, and filtered by suction to obtain filtrate and precipitate;
(2) Adding hydrogen peroxide with the concentration of 33wt% into the filtrate obtained in the step (1) to ensure that H contained in the hydrogen peroxide 2 O 2 The molar weight of the iron phosphate is 1.8 times of the theoretical dosage, the iron phosphate is heated to 135 ℃, a large amount of white precipitate appears after reaction for 30 hours, then the iron phosphate is subjected to filter pressing by a filter press, other wastes such as salts are removed by washing with pure water, then the iron phosphate is put into a dryer for drying, so as to obtain dihydrate iron orthophosphate, then the dihydrate iron phosphate is sintered and dehydrated, and the dihydrate iron phosphate is sent to a grinding system for grinding and crushing, and packaging, so that the battery-grade iron phosphate is obtained.
Comparative example 1
The difference is that in step (1) the heating is to 80℃as in example 1.
Comparative example 2
9.26 parts of diammonium hydrogen phosphate is dissolved in water, placed in a stainless steel reaction kettle, and titanium white byproduct ferrous sulfate is added to enable FeSO to be generated 4 18.34 parts by weight, stirring uniformly, and adding 30wt% hydrogen peroxide to obtain H contained in hydrogen peroxide 2 O 2 The molar weight of the catalyst is 2 times of the theoretical dosage, the catalyst is heated to 130 ℃ and reacts for 36 hours, and a large amount of catalyst appearsWhite precipitate, press-filtering with press filter, washing with pure water to remove other salt and other waste, drying in drier to obtain ferric orthophosphate dihydrate, sintering for dewatering, grinding with grinding system, and packaging to obtain ferric phosphate.
Effect verification
The iron phosphates prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to IPC total composition measurement, fe/P was calculated, tap density was measured, and the results were compared with commercially available iron sulfate, and are shown in Table 1.
TABLE 1
As can be seen from Table 1, the iron phosphate prepared by the method has high purity, low impurity content, small and uniform granularity and high tap density, meets the requirements of battery-grade iron phosphate, and is superior to commercial iron phosphate.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (4)
1. The method for preparing the battery-grade ferric phosphate by using the titanium white byproduct ferrous sulfate is characterized by comprising the following steps of:
(1) Dissolving phosphate in water, adding titanium white byproduct ferrous sulfate, and carrying out suction filtration after the heating reaction is finished to obtain filtrate and precipitate;
(2) Adding an oxidant into the filtrate obtained in the step (1), heating, and after the reaction, performing filter pressing, washing, drying and sintering to obtain the battery-grade ferric phosphate;
heating to 50-60 ℃ in the step (1), wherein the reaction time is 12-24 hours;
and (3) heating to 130-140 ℃ in the step (2), wherein the reaction time is 24-36 h.
2. The method of claim 1, wherein the phosphate in step (1) is diammonium phosphate.
3. The method of claim 1, wherein the oxidant in step (2) is 30-35 wt% hydrogen peroxide.
4. The method of claim 1, wherein the amount of the oxidizing agent used in step (2) is 1.5 to 2 times the theoretical molar amount of the oxidizing agent required to convert all of the ferrous ions in the filtrate to ferric ions.
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| CN115701828A (en) * | 2022-11-25 | 2023-02-14 | 宁波新福钛白粉有限公司 | Quasi-continuous method for preparing battery-grade anhydrous iron phosphate by using ferrous sulfate |
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