CN115893351A - Method for preparing battery-grade iron phosphate by using waste ferrous chloride solution and application thereof - Google Patents
Method for preparing battery-grade iron phosphate by using waste ferrous chloride solution and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of waste liquid treatment, in particular to a method for preparing battery-grade iron phosphate by using a waste by-product ferrous chloride solution and application thereof. The method comprises the following steps: adding a metallic iron material into the waste ferrous chloride solution to perform a first impurity removal reaction to obtain a first impurity removal feed liquid; adding a solution containing phosphate ions and an alkali liquor into the first impurity-removed feed liquid, and then carrying out solid-liquid separation to obtain a ferrous chloride solution; mixing a ferrous chloride solution, a phosphate solution and an oxidant, carrying out a synthetic reaction, and then carrying out solid-liquid separation to obtain an iron phosphate dihydrate; in the process of the synthesis reaction, the pH value of the mixed material is 1.5-2.5; and calcining the iron phosphate dihydrate to obtain the battery-grade iron phosphate. According to the method, the battery-grade iron phosphate is prepared by taking the waste and side ferrous chloride solution as a raw material, so that the waste and side ferrous chloride solution is recycled at a high value, the pollution of waste liquid to the environment is avoided, and the treatment cost is reduced.
Description
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for preparing battery-grade iron phosphate by using a waste by-product ferrous chloride solution and application thereof.
Background
In the process of producing titanium dioxide by chlorination process, a large amount of waste liquid with ferrous chloride as main component is generated, and the waste liquid also contains a large amount of impurity ions such as hydrogen ions, manganese ions, aluminum ions and the like. If the waste liquid is not treated and directly discharged, environmental pollution is easily caused. The treatment agent is used for treatment and then discharged, so that the treatment cost is increased, and the waste of resources is caused.
At present, a waste and secondary ferrous chloride solution generated in the production process of titanium dioxide by a chlorination method is treated by the following method: the lime milk is used for neutralizing the waste liquid to obtain the precipitate of which the main component is ferric hydroxide, the waste residue after separation and washing is directly conveyed to a slag yard for concentrated stacking, and the stacking needs to occupy a large amount of land, so that the stacking cost of enterprises can be increased, and the environment is influenced. Therefore, how to provide a method for recycling the titanium dioxide waste liquid in the chlorination process is of great significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for preparing battery-grade iron phosphate by using waste and secondary ferrous chloride solution, which takes the waste and secondary ferrous chloride solution as a raw material to prepare the battery-grade iron phosphate with high added value, avoids the pollution of waste liquid to the environment while recycling the waste and secondary ferrous chloride solution with high value, and reduces the treatment cost.
The second objective of the present invention is to provide an application of the battery grade ferric phosphate prepared by the method for preparing the battery grade ferric phosphate by using the waste ferrous chloride solution as described above in a lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for preparing battery-grade iron phosphate by using a waste secondary ferrous chloride solution, which comprises the following steps:
adding a metallic iron material into the waste ferrous chloride solution to perform a first impurity removal reaction, and removing iron ions, chromium ions and vanadium ions to obtain a first impurity removal feed liquid; the waste secondary ferrous chloride solution comprises waste liquid generated in the production process of titanium dioxide by a chlorination method, and the main components of the waste secondary ferrous chloride solution comprise ferrous ions, ferric ions, chloride ions, aluminum ions, chromium ions and vanadium ions;
adding a solution containing phosphate ions and an alkali liquor into the first impurity-removed feed liquid, and carrying out a second impurity-removed reaction to remove aluminum ions, chromium ions and vanadium ions to obtain a second impurity-removed feed liquid; carrying out solid-liquid separation on the second impurity-removed feed liquid to obtain a ferrous chloride solution;
mixing the ferrous chloride solution, phosphate solution and oxidant, carrying out synthetic reaction, and then carrying out solid-liquid separation to obtain iron phosphate dihydrate; wherein, in the process of the synthesis reaction, the pH value of the mixed material is 1.5-2.5;
and calcining the iron phosphate dihydrate to obtain the battery-grade iron phosphate.
Preferably, the metallic iron material comprises elemental iron and/or reduced ilmenite;
preferably, in the first impurity removal reaction process, the temperature of the mixed material is 20-90 ℃;
preferably, the time of the first impurity removal reaction is 0.5-2 h;
preferably, the first impurity removal reaction is carried out until the pH value of the mixed material is 2-3.
Preferably, the phosphate ion-containing solution comprises a phosphoric acid solution and/or a phosphate solution; preferably, the phosphate solution comprises at least one of a sodium phosphate solution, a sodium monohydrogen phosphate solution, and a disodium hydrogen phosphate solution;
preferably, the volume of the solution containing phosphate ions is 0.1-0.5% of the volume of the waste secondary ferrous chloride solution.
Preferably, the alkali solution comprises at least one of an ammonia water solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium bicarbonate solution and a sodium carbonate solution;
preferably, the alkali liquor is added to the mixed material until the pH value is 4.0-4.5.
Preferably, in the second impurity removal reaction process, the temperature of the mixed material is 20-90 ℃;
preferably, the time of the second impurity removal reaction is 0.5 to 2 hours.
Preferably, the phosphate solution used during the synthesis reaction comprises a sodium monohydrogen phosphate solution and/or a disodium hydrogen phosphate solution;
preferably, the phosphate solution used in the synthesis reaction process is 8-15% by mass.
Preferably, the oxidant comprises hydrogen peroxide;
preferably, the iron element in the ferrous chloride solution, the phosphorus element in the phosphate and the H in the hydrogen peroxide solution 2 O 2 In a molar ratio of 1:1:1.1 to 2.
Preferably, in the process of the synthesis reaction, the temperature of the mixed materials is 20-95 ℃;
preferably, the time of the synthesis reaction is 2 to 5 hours.
Preferably, the calcining temperature is 480-580 ℃, and the calcining time is 1-4 h.
The invention also provides application of the battery grade iron phosphate prepared by the method for preparing the battery grade iron phosphate by using the waste ferrous chloride solution as a by-product in lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for preparing the battery-grade iron phosphate by using the waste and secondary ferrous chloride solution, the prepared iron phosphate can meet the index requirement of the battery-grade iron phosphate, so that the waste and secondary ferrous chloride solution is recycled with high value, the pollution of waste liquid to the environment is reduced, and the environmental protection pressure of a chlorination process production line is reduced.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
In a first aspect, the invention provides a method for preparing battery-grade iron phosphate by using a waste ferrous chloride solution as a by-product, which comprises the following steps:
adding a metallic iron material into the waste ferrous chloride solution to perform a first impurity removal reaction, and removing iron ions, chromium ions and vanadium ions to obtain a first impurity removal feed liquid.
The waste secondary ferrous chloride solution comprises waste liquid generated in the production process of titanium dioxide by a chlorination method, and the main components of the waste secondary ferrous chloride solution comprise ferrous ions (ferrous ions), ferric ions, chloride ions, aluminum ions, chromium ions, vanadium ions and a large amount of hydrogen ions.
The reaction occurring in the first impurity removal reaction process comprises:
Fe 3+ +Fe＝Fe 2+ ；
H + +Fe＝H 2 ↑+Fe 2+ ；
2Cr 6+ +3Fe＝3Fe 2+ +2Cr 3+ ；
V 5+ +Fe＝Fe 2+ +V 3+ 。
and adding a solution containing phosphate radical ions and alkali liquor into the first impurity-removed feed liquid, and performing a second impurity-removed reaction to remove aluminum ions, chromium ions and vanadium ions to obtain a second impurity-removed feed liquid. And carrying out solid-liquid separation on the second impurity-removed feed liquid to obtain a ferrous chloride solution.
According to the invention, the solution containing phosphate ions is added, so that the impurity removal effect can be achieved, the filter pressing speed can be increased, the separation efficiency can be improved, and the yield can be further improved. Solves the problems that in the prior art, only alkali liquor is added to generate aluminum hydroxide colloid, so that the filtering is difficult and the separation efficiency is low.
In addition, the concentration of the iron element has certain influence on the performance of the prepared battery-grade iron phosphate. The solution containing phosphate ions can also play a role in diluting the concentration of the iron element.
The reaction occurring in the second impurity removal reaction process comprises:
Al 3+ +PO 4 3- ＝AlPO 4 ↓；
Cr 3+ +3OH - ＝Cr(OH) 3 ↓；
V 3+ +3OH - ＝V(OH) 3 ↓。
and mixing the ferrous chloride solution, phosphate solution and oxidant, carrying out synthesis reaction, and then carrying out solid-liquid separation to obtain the iron phosphate dihydrate. Wherein, in the process of the synthesis reaction, the pH value of the mixed material is 1.5-2.5; including but not limited to, a point value of any one of 1.7, 1.9, 2.0, 2.2, 2.4, or a range value between any two.
The reactions that occur during the synthesis reaction include:
2Fe 2+ +2PO 4 3- +4H + +H 2 O 2 +2OH-＝2FePO 4 ·2H 2 O。
in some embodiments of the invention, after the synthesis reaction is carried out and then the solid-liquid separation is carried out, a water washing step is further included. And washing with water until the conductivity is less than 500ms/cm.
And calcining the iron phosphate dihydrate to obtain the battery grade iron phosphate.
The reactions that occur during the calcination include: fePO 4 ·2H 2 O＝FePO 4 +2H 2 O。
In some embodiments of the present invention, after the calcining, a crushing (pulverizing) step is further included.
According to the method for preparing the battery-grade iron phosphate by using the waste and secondary ferrous chloride solution, the prepared iron phosphate can meet the index requirement of the battery-grade iron phosphate, so that the waste and secondary ferrous chloride solution is recycled with high value, the pollution of waste liquid to the environment is reduced, and the environmental protection pressure of a chlorination process production line is reduced.
Moreover, the method has the advantages of simplicity, easiness in implementation, short flow, easiness in realization of batch production and the like.
In some specific embodiments of the invention, the mass fraction of HCl in the waste secondary ferrous chloride solution is 2% to 5%, the mass concentration of Fe element is 60 to 100g/L, the mass concentration of Al element is 6 to 10g/L, the mass concentration of Cr element is 1 to 2g/L, and the mass concentration of V element is 1 to 2g/L.
Preferably, the metallic iron material comprises elemental iron and/or reduced ilmenite.
In some embodiments of the invention, the elemental iron comprises at least one of iron powder, iron filings, and iron sheet.
Preferably, in the first impurity removal reaction process, the temperature of the mixed material is 20-90 ℃; including but not limited to the values of any one of 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or ranges between any two.
Preferably, the time of the first impurity removal reaction is 0.5-2 h; including but not limited to point values of any of 1h, 1.5h, or range values between any two.
Preferably, the first impurity removal reaction is carried out until the pH of the mixed material is 2 to 3, including but not limited to the values of any one of 2.1, 2.2, 2.3, 2.5, 2.7, 2.8, 2.9 or the range between any two.
Preferably, the phosphate ion-containing solution comprises a phosphoric acid solution and/or a phosphate solution; wherein the phosphate solution comprises at least one of a sodium phosphate solution, a sodium monohydrogen phosphate solution, and a disodium hydrogen phosphate solution.
Preferably, the volume of the phosphate ion-containing solution is between 0.1% and 0.5% of the volume of the waste secondary ferrous chloride solution, including but not limited to the point of any one of 0.2%, 0.3%, 0.4%, or a range between any two.
Preferably, the alkali solution includes at least one of an aqueous ammonia solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium bicarbonate solution, and a sodium carbonate solution.
Preferably, the lye is added in an amount to provide a pH of the combined materials of 4.0 to 4.5, including but not limited to values of any one of 4.1, 4.2, 4.3, 4.4 or ranges therebetween.
In some specific embodiments of the present invention, the molar concentration of the alkali solution is 0.5 to 2mol/L, including but not limited to any one of the values of 0.8mol/L, 1.0mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L or a range between any two.
In some embodiments of the present invention, the alkali solution is added at a constant rate.
Preferably, in the second impurity removal reaction process, the temperature of the mixed material is 20-90 ℃; including but not limited to, the point value of any one of 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, or the range value between any two.
Preferably, the time of the second impurity removal reaction is 0.5-2 h, including but not limited to the point value of any one of 1h, 1.5h or the range value between any two.
Preferably, the phosphate solution used during the synthesis reaction comprises a sodium monohydrogen phosphate solution and/or a disodium hydrogen phosphate solution.
In some embodiments of the present invention, the phosphate solution used in the synthesis reaction may be a solution obtained by reacting phosphoric acid with sodium hydroxide.
Preferably, the mass fraction of the phosphate solution used during the synthesis reaction is between 8% and 15%, including but not limited to the values of any one of 9%, 10%, 11%, 12%, 13%, 14%, or ranges between any two.
Preferably, the oxidant comprises hydrogen peroxide. Wherein the hydrogen peroxide is hydrogen peroxide solution.
In some specific embodiments of the present invention, the mass fraction of the hydrogen peroxide is 20% to 30%.
Preferably, the iron element in the ferrous chloride solution, the phosphorus element in the phosphate and the H in the hydrogen peroxide solution 2 O 2 In a molar ratio of 1:1: 1.1-2, including but not limited to 1:1:1.2, 1:1:1.4, 1:1:1.5, 1:1:1.7, 1:1:1.9, or a range between any two.
Preferably, in the process of the synthesis reaction, the temperature of the mixed materials is 20-95 ℃; including but not limited to, a point value of any one of 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or a range value between any two.
Preferably, the time of the synthesis reaction is between 2 and 5 hours, including but not limited to the point of any one of 3 hours, 4 hours, or a range between any two. .
In some embodiments of the invention, the synthesis reaction comprises: firstly reacting for 1-2 h under the conditions of pH = 1.8-2.5 and normal temperature (15-30 ℃), then adjusting pH = 1.5-1.8 and heating to 80-95 ℃ for reacting for 1-3 h. This enables battery grade iron phosphate with even better performance to be produced.
In some specific embodiments of the present invention, the ferric phosphate dihydrate is obtained, and at the same time, a filtrate containing phosphate ions is obtained, and the filtrate can be used as a solution containing phosphate ions for performing a second impurity removal reaction.
Preferably, the temperature of the calcination is between 480 and 580 ℃, including but not limited to the values of any one of 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 550 ℃, 570 ℃, or the values of a range between any two.
The calcination time is 1 to 4 hours, including but not limited to the point of any one of 2 hours, 3 hours, or a range between any two.
In a second aspect, the invention also provides application of the battery grade iron phosphate prepared by the method for preparing the battery grade iron phosphate by using the waste byproduct ferrous chloride solution in a lithium ion battery.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
The waste and secondary ferrous chloride solution adopted in the following embodiments and various proportions of the invention is waste liquid (same batch) generated in the production process of titanium dioxide by a chlorination method, and the content of impurity elements in the waste liquid is shown in table 1.
Example 1
The method for preparing battery-grade iron phosphate by using the waste secondary ferrous chloride solution provided by the embodiment comprises the following steps:
(1) Adding iron powder into a waste and side-product ferrous chloride solution generated in the production process of titanium dioxide by a chlorination method, removing iron ions, chromium ions and vanadium ions, and reacting at 60 ℃ for 0.5h until the pH value of the mixed material is 2. Obtaining a first impurity-removed feed liquid.
(2) And adding a sodium phosphate solution (namely a solution containing phosphate ions) with the volume of 0.1 percent of that of the waste ferrous chloride solution into the first impurity-removed feed liquid, pumping 0.5mol/L of sodium hydroxide solution into the first impurity-removed feed liquid by using a peristaltic pump to adjust the pH to be =4.0, reacting at 60 ℃ for 0.5h, and performing filter pressing to obtain the purified ferrous chloride solution. Through detection and calculation, the yield of the iron element (the mass of the iron element in the purified ferrous chloride solution/the mass of the iron element in the waste ferrous chloride solution multiplied by 100%) is 96%.
(3) Adding the iron element in the ferrous chloride solution, the phosphorus element in the phosphate and the H in the hydrogen peroxide into the purified ferrous chloride solution 2 O 2 Adding 10% by mass of a sodium monohydrogen phosphate solution and 27% by mass of hydrogen peroxide, simultaneously adopting 8% by mass of a sodium hydroxide solution to control the pH =2.0 in the synthesis reaction process, adding phosphoric acid after reacting for 1.5h, adjusting the pH =1.7 of the solution, heating to 85 ℃, carrying out pressure filtration after reacting for 1h, washing with water, calcining a filter cake (namely iron phosphate dihydrate) after washing with water until the conductivity is less than 500ms/cm, wherein the calcining temperature is 480 ℃, the calcining time is 4h, and crushing is carried out after calcining to obtain the iron phosphate.
Example 2
The method for preparing battery-grade iron phosphate by using the waste secondary ferrous chloride solution provided by the embodiment comprises the following steps:
(1) Adding reduced titanium into a waste by-product ferrous chloride solution generated in the production process of titanium dioxide by a chlorination method, reacting for 1h at 50 ℃, removing iron ions, chromium ions and vanadium ions until the pH value of the mixed material is 3, and obtaining a first impurity-removed feed liquid.
(2) Adding a disodium hydrogen phosphate solution (namely a solution containing phosphate ions) with the volume of 0.2 percent of that of the waste and side ferrous chloride solution into the first impurity-removed feed liquid, pumping 1mol/L of a sodium hydroxide solution into the solution by using a peristaltic pump to adjust the pH to be =4.0, reacting at 50 ℃ for 1h, and then performing filter pressing to obtain a purified ferrous chloride solution, wherein the yield of the iron element (the mass of the iron element in the purified ferrous chloride solution/the mass of the iron element in the waste and side ferrous chloride solution multiplied by 100%) is 95% through detection and calculation.
(3) Adding iron element in the ferrous chloride solution, phosphorus element in phosphate and H in hydrogen peroxide into the purified ferrous chloride solution 2 O 2 The molar ratio of (1)Controlling the pH =2.2 in the reaction process by using a sodium hydroxide solution with the mass fraction of 8%, adding phosphoric acid after reacting for 1h, adjusting the pH =1.9 of the solution, heating to 90 ℃, performing pressure filtration and water washing after reacting for 1h until the conductivity is less than 500ms/cm, calcining the filter cake at the calcining temperature of 500 ℃ for 3h, and crushing after calcining to obtain the iron phosphate.
Example 3
The method for preparing battery-grade iron phosphate by using the waste secondary ferrous chloride solution provided by the embodiment comprises the following steps:
(1) Adding iron sheet into a waste by-product ferrous chloride solution generated in the production process of titanium dioxide by a chlorination method, reacting for 2 hours at 70 ℃, removing iron ions, chromium ions and vanadium ions until the pH value of the mixed material is 2.5, and obtaining a first impurity-removed feed liquid.
(2) Adding a sodium phosphate solution (namely a solution containing phosphate ions) with the volume of 0.1 percent of that of the waste and side ferrous chloride solution into the first impurity-removed feed liquid, pumping 2mol/L of a sodium hydroxide solution into the first impurity-removed feed liquid by using a peristaltic pump to adjust the pH to be =4.5, reacting at 70 ℃ for 0.5h, and then performing pressure filtration to obtain a purified ferrous chloride solution, wherein the yield of the iron element (the mass of the iron element in the purified ferrous chloride solution/the mass of the iron element in the waste and side ferrous chloride solution multiplied by 100%) is 95% by detection and calculation.
(3) Adding the iron element in the ferrous chloride solution, the phosphorus element in the phosphate and the H in the hydrogen peroxide into the purified ferrous chloride solution 2 O 2 Adding a 15% disodium hydrogen phosphate solution and 25% hydrogen peroxide by mass percentage into the mixture according to a molar ratio of 1.
Comparative example 1
The method for preparing battery-grade iron phosphate by using the waste and by-product ferrous chloride solution provided by the comparative example is basically the same as that in example 1, except that the steps (1) and (2) are not performed, and a monosodium phosphate solution and hydrogen peroxide are directly added into the waste and by-product ferrous chloride solution generated in the production process of titanium dioxide by a chlorination method to perform a synthesis reaction.
Comparative example 2
The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as a side product is basically the same as that in example 1, except that no sodium phosphate solution is added in the step (2).
Through detection and calculation, the yield of the iron element (the mass of the iron element in the purified ferrous chloride solution/the mass of the iron element in the waste ferrous chloride solution multiplied by 100%) in the comparative example is 85%.
Comparative example 3
The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as the secondary part is basically the same as that in example 1, except that in the step (3), a sodium hydroxide solution with the mass fraction of 8% is used for controlling the pH =3.0 in the synthesis reaction process.
Experimental example 1
The impurity element content in the waste by-product ferrous chloride solution generated in the production process of titanium dioxide by chlorination method is detected, the impurity element content in the purified ferrous chloride solution prepared in the step (2) of the embodiments 1-3 and the comparative examples 2-3 is respectively detected, and the detection results are shown in table 1.
TABLE 1 impurity element content in purified ferrous chloride solution of each group
As can be seen from Table 1, in comparative example 2, the efficiency of removing impurities was lowered without adding the sodium phosphate solution in step (2).
Experimental example 2
The element contents of the battery grade iron phosphate prepared in each of the above examples and comparative examples were measured, and the results are shown in table 2.
Table 2 element content in battery grade iron phosphate
As can be seen from table 2, the iron phosphate prepared according to the examples of the present invention can satisfy the index requirements of battery grade iron phosphate.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. The method for preparing battery grade iron phosphate by using the waste secondary ferrous chloride solution is characterized by comprising the following steps:
adding a metallic iron material into the waste ferrous chloride solution to perform a first impurity removal reaction, and removing iron ions, chromium ions and vanadium ions to obtain a first impurity removal feed liquid; the waste secondary ferrous chloride solution comprises waste liquid generated in the production process of titanium dioxide by a chlorination method, and the main components of the waste secondary ferrous chloride solution comprise ferrous ions, ferric ions, chloride ions, aluminum ions, chromium ions and vanadium ions;
adding a solution containing phosphate ions and an alkali liquor into the first impurity-removed feed liquid, and carrying out a second impurity-removed reaction to remove aluminum ions, chromium ions and vanadium ions to obtain a second impurity-removed feed liquid; carrying out solid-liquid separation on the second impurity-removed feed liquid to obtain a ferrous chloride solution;
mixing the ferrous chloride solution, phosphate solution and oxidant, carrying out synthetic reaction, and then carrying out solid-liquid separation to obtain iron phosphate dihydrate; wherein, in the process of the synthesis reaction, the pH value of the mixed material is 1.5-2.5;
and calcining the iron phosphate dihydrate to obtain the battery-grade iron phosphate.
2. The method for preparing battery-grade iron phosphate by using the waste secondary ferrous chloride solution according to claim 1, wherein the metallic iron material comprises elemental iron and/or reduced ilmenite;
preferably, in the first impurity removal reaction process, the temperature of the mixed material is 20-90 ℃;
preferably, the time of the first impurity removal reaction is 0.5-2 h;
preferably, the first impurity removal reaction is carried out until the pH value of the mixed material is 2-3.
3. The method for preparing battery grade iron phosphate by using the waste ferrous chloride by-product solution according to claim 1, wherein the solution containing phosphate ions comprises a phosphoric acid solution and/or a phosphate solution; preferably, the phosphate solution comprises at least one of a sodium phosphate solution, a sodium monohydrogen phosphate solution, and a disodium hydrogen phosphate solution;
preferably, the volume of the solution containing phosphate ions is 0.1-0.5% of the volume of the waste secondary ferrous chloride solution.
4. The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as the auxiliary material, according to claim 1, wherein the alkali solution comprises at least one of an ammonia water solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium bicarbonate solution and a sodium carbonate solution;
preferably, the alkali liquor is added to the mixed material until the pH value is 4.0-4.5.
5. The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as claimed in claim 1, wherein the temperature of the mixed materials is 20-90 ℃ in the second impurity removal reaction process;
preferably, the time of the second impurity removal reaction is 0.5-2 h.
6. The method for preparing battery-grade iron phosphate by using the waste ferrous chloride by-product solution as claimed in claim 1, wherein the phosphate solution used in the synthesis reaction process comprises sodium monohydrogen phosphate solution and/or disodium hydrogen phosphate solution;
preferably, the phosphate solution used in the synthesis reaction process is 8-15% by mass.
7. The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as the secondary raw material as claimed in claim 1, wherein the oxidant comprises hydrogen peroxide;
preferably, the iron element in the ferrous chloride solution, the phosphorus element in the phosphate and the H in the hydrogen peroxide 2 O 2 In a molar ratio of 1:1:1.1 to 2.
8. The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as the secondary raw material according to claim 1, wherein the temperature of the mixed materials is 20-95 ℃ in the synthesis reaction process;
preferably, the time of the synthesis reaction is 2 to 5 hours.
9. The method for preparing battery-grade iron phosphate by using the waste ferrous chloride solution as claimed in claim 1, wherein the calcining temperature is 480-580 ℃ and the calcining time is 1-4 h.
10. Use of battery grade iron phosphate prepared by the method for preparing battery grade iron phosphate from waste ferrous chloride solution according to any one of claims 1 to 9 in lithium ion batteries.
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