CN113897490B - Defluorination method and application of lithium ion battery anode material leaching solution - Google Patents

Defluorination method and application of lithium ion battery anode material leaching solution Download PDF

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CN113897490B
CN113897490B CN202111514165.7A CN202111514165A CN113897490B CN 113897490 B CN113897490 B CN 113897490B CN 202111514165 A CN202111514165 A CN 202111514165A CN 113897490 B CN113897490 B CN 113897490B
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defluorination
carbonate
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CN113897490A (en
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王海北
邓超群
李诗丽
秦树辰
郑朝振
李强
邹小平
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BGRIMM Technology Group Co Ltd
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
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    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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    • Y02P10/20—Recycling

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Abstract

The invention relates to the field of purification and impurity removal of waste power battery leachate, in particular to a defluorination method and application of the leachate of a lithium ion battery anode material. The defluorination method comprises the following steps: mixing the positive electrode material, an acid solution and a reducing agent, carrying out reduction acid leaching reaction, and carrying out solid-liquid separation to obtain a positive electrode leaching solution; mixing the positive electrode leaching solution with carbonate, performing flocculation precipitation, and then performing solid-liquid separation to obtain a first defluorination solution; uniformly mixing the first defluorination solution with a flocculating agent, adding carbonate into the first defluorination solution, performing flocculation precipitation, and then performing solid-liquid separation to obtain a second defluorination solution; in the step (b) and the step (c), the pH value of the mixed material is 4-6 in the flocculation precipitation process. The invention can realize deep defluorination and simultaneously reduce the dosage of flocculating agent and carbonate to the utmost extent; greatly reduces the loss rate of Ni and/or Co and/or Mn; simple operation, short period and low cost.

Description

Defluorination method and application of lithium ion battery anode material leaching solution
Technical Field
The invention relates to the field of purification and impurity removal of waste power battery leachate, in particular to a method for removing fluorine from lithium ion battery anode material leachate and application thereof, and more particularly relates to a method for removing fluorine from lithium ion battery anode material leachate and a method for recovering nickel, cobalt and manganese from a lithium ion battery anode material.
Background
The power lithium battery is composed of positive and negative electrode materials, current collectors and electrolyte (generally LiPF)6) And PVDF as a binder, and the like, and the fluoride used for modifying the electrolyte, PVDF as a binder, or the positive electrode material contains a certain amount of F element. After the anode material is subjected to acid leaching, a large amount of impurity F elements enter the leachate, and when valuable metals in the leachate are recovered, the corrosion performance of F seriously affects the normal operation of equipment and the quality of a precursor prepared by a precursor solution obtained by purifying and removing impurities subsequently. Therefore, it is necessary to deeply remove fluorine from the leachate of the waste power battery.
Patent CN110669933A discloses a method for removing fluorine in a nickel-cobalt-manganese solution, in which an aluminum sulfate solution obtained by acid leaching of a lithium battery current collector is added into the nickel-cobalt-manganese solution, and the pH of the solution is adjusted to a certain pH value by using alkali, so that the deep impurity removal of F is realized.
Patent CN106745343A discloses a method for removing fluorine and silicon ions from a nickel sulfate cobalt manganese solution, which utilizes P507 as an extracting agent, Ni, Co and Mn are extracted to an organic phase, and fluorine, silicon and sodium are left in a water phase, so that the purpose of removing impurities from fluorine and silicon is achieved.
The patent CN102586804A discloses a method for removing fluoride ions in a manganese sulfate solution for electrolytic manganese metal production, and the method is characterized in that calcium carbonate serving as a defluorinating agent and diatomite are added into the manganese sulfate solution to remove the fluoride ions in the solution, so that the content of the fluoride ions can be reduced to below 60 mu g/g, and manganese loss in the solution is not caused.
The patent CN108118152A discloses a method for efficiently removing fluoride ions in a manganese sulfate solution, which is characterized in that a certain amount of solid cerium hydroxide is added into the fluorine-containing manganese sulfate solution, the mixture is stirred and kept stand for 12-18 hours at a certain temperature and pH, the content of F ions is reduced from 3200ppm to 87ppm, and the fluorine removal rate is about 97%.
However, the above method can achieve F removal, but has many disadvantages. For example, the CN106745343A patent adopts an extraction method to remove fluorine, and has the disadvantages of complicated process and higher costThe prepared solution has a certain amount of residual organic matters, which is not good for preparing a precursor; the patent CN102586804A introduces diatomite, which causes the solution system to be complicated; the CN108118152A patent realizes the removal of fluorine, and the fluorine removal period is too long; in patent CN110669933A, sodium hydroxide or ammonia water is used as neutralizer, when the concentration of Ni/Co/Mn contained in leachate is too high or the concentration of Fe/Al contained in leachate is too high, the loss rate of Ni/Co/Mn is too high due to local over-alkaling or entrainment and the like, and a large amount of Na exists in the solution after defluorination+Or NH4 +This can seriously degrade the performance of the precursor.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for removing fluorine from a lithium ion battery anode material leaching solution, which is characterized in that carbonate is used as a neutralizer, a mixed material is adjusted to a specific pH value, and a two-step flocculation precipitation fluorine removal method is adopted, so that the use amounts of a flocculating agent and the carbonate are reduced to the maximum extent while deep fluorine removal is realized; and the loss rate of Ni and/or Co and/or Mn is greatly reduced during the defluorination process. Meanwhile, the method has the advantages of simple operation, short period, low cost, no sodium ions, ammonium ions, organic matters and the like after fluorine removal, and solves the problem of serious loss of Ni, Co and Mn in the prior art.
The second purpose of the invention is to provide an application, in particular to a method for recovering nickel, cobalt and manganese from a lithium ion battery positive electrode material, wherein the loss rate of Ni and/or Co and/or Mn is low, and sodium ions, ammonium ions, organic matters and the like are not remained in the recovery process.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the defluorination method of the lithium ion battery anode material leaching solution comprises the following steps:
(a) mixing the positive electrode material, an acid solution and a reducing agent, carrying out reduction acid leaching reaction, and carrying out solid-liquid separation to obtain a positive electrode leaching solution;
(b) mixing the positive electrode leaching solution with carbonate, performing flocculation precipitation, and then performing solid-liquid separation to obtain a first defluorination solution;
(c) uniformly mixing the first defluorination solution and a flocculating agent, adding carbonate into the first defluorination solution, performing flocculation precipitation, and then performing solid-liquid separation to obtain a second defluorination solution;
wherein, in the step (b) and the step (c), the pH value of the mixed material is 4-6 in the flocculation precipitation process, including but not limited to the value of any one of 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6 and 5.8 or the range value between any two.
According to the method for removing fluorine from the lithium ion battery anode material leaching solution, provided by the invention, the carbonate is used as a neutralizer, the mixed material is adjusted to a specific pH value, and a two-step flocculation precipitation fluorine removal means is adopted, so that the dosage of a flocculating agent and the carbonate is reduced to the maximum extent while deep fluorine removal is realized; and the loss rate of Ni and/or Co and/or Mn is greatly reduced during the defluorination process. Meanwhile, the method has the advantages of simple operation, short period, low cost, no sodium ions, ammonium ions, organic matters and the like after fluorine removal, and solves the problem of serious loss of Ni, Co and Mn in the prior art.
The positive electrode material is from a waste lithium ion power battery, and the positive electrode material is separated for recycling after the battery is disassembled. The positive electrode material comprises at least one of a lithium nickelate positive electrode material, a lithium cobaltate positive electrode material, a lithium manganate positive electrode material, a nickel-cobalt-manganese ternary positive electrode material and a nickel-cobalt-aluminum ternary positive electrode material.
The invention relates to the following principle: defluorination is carried out by flocculation precipitation. Specifically, the flocculation precipitation method is to utilize the flocculating agent to complex fluoride to generate precipitation or the flocculating agent to generate the adsorption effect of alum blossom after hydrolysis reaction, so that the fluoride is coagulated or precipitated, and the impurities of the fluoride are removed through filtration and separation.
According to the invention, the positive electrode leachate obtained by carrying out reduction acid leaching reaction on the positive electrode material comprises impurity elements such as Fe, Al, Cu, F and the like, wherein the content of Al is higher. The method fully utilizes the Al salt and the Fe salt of the pickle liquor, and adds a certain amount of carbonate to adjust the pH value of the solution, so that the Al salt and the Fe salt are hydrolyzed to generate hydroxide, and the preliminary flocculation precipitation defluorination is realized, namely the step (b), wherein a large amount of F can be removed. But at the moment, a small amount of F element still remains in the primary defluorination solution, so that deep flocculation precipitation defluorination needs to be carried out, namely step (c), and only a small amount of Al salt needs to be added in the step, so that the content of F is qualified, and the requirement of ternary precursor preparation is met.
Namely, the invention achieves the aim of deep fluorine removal on one hand by adopting a two-step fluorine removal method. On the other hand, the addition amount of the flocculating agent is obviously reduced, and the aim of saving cost is fulfilled.
The method provided by the invention takes carbonate as a neutralizer and adopts two-step flocculation precipitation for fluorine removal, so that the method is not only suitable for a low-concentration system containing Ni, Co and Mn salts, but also suitable for a high-concentration system containing Ni, Co and Mn salts, and the method can greatly reduce the loss rate of Ni, Co and Mn.
In some specific embodiments of the present invention, in the process of mixing the leachate with the carbonate, the carbonate powder is first uniformly mixed with water to prepare a carbonate dispersion liquid with a mass concentration of 10 to 30%, and then the dispersion liquid is mixed with the leachate, which is more favorable for uniform dispersion. Because if the carbonate powder is directly mixed with the leaching solution, the phenomenon of lumping is easy to occur and the carbonate powder is not easy to disperse uniformly.
Preferably, in step (a), the acid solution comprises an organic acid solution and/or an inorganic acid solution.
Preferably, the organic acid comprises citric acid and/or acetic acid;
and/or; the inorganic acid includes at least one of sulfuric acid, hydrochloric acid, and nitric acid.
In some specific embodiments of the invention, the inorganic acid solution comprises at least one of concentrated sulfuric acid, concentrated hydrochloric acid, and concentrated nitric acid.
By adopting a specific type of acid solution, the full reaction is facilitated, and the anode leaching solution with high nickel, cobalt and manganese contents is extracted and obtained.
Preferably, in step (a), the reducing agent comprises at least one of hydrogen peroxide, sodium thiosulfate, sodium sulfite and hydrazine sulfate.
The reducing agent is used for reducing the valuable metal Co/Mn of the positive electrode material, so that the efficient leaching of the valuable metal Co/Mn is promoted.
In some specific embodiments of the present invention, the reducing agent is more preferably hydrogen peroxide, which can reduce the valuable metal Co/Mn of the positive electrode material to promote efficient leaching thereof, and at the same time, can also function as an oxidizing agent to oxidize Fe from +2 to + 3.
Preferably, in step (b), the carbonate includes at least one of calcium carbonate, aluminum carbonate, nickel carbonate, cobalt carbonate, and manganese carbonate.
In the prior art, sodium hydroxide or ammonia water is often used as a neutralizing agent, but the neutralizing agent is easily over-alkalified locally, so that the loss of nickel, cobalt and manganese is serious. According to the invention, the specific carbonate is used as a neutralizer to adjust the pH value, so that the loss rate of nickel, cobalt and manganese can be effectively reduced.
Preferably, in step (c), the flocculant comprises at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, polyaluminum sulfate, aluminum citrate, and aluminum acetate.
In some specific embodiments of the invention, the anion of the flocculant used in step (c) is the same as the anion of the acid solution in step (a).
Preferably, in the step (c), in the mixed material of the first defluorination solution and the flocculant, the molar ratio of the fluorine ions in the first defluorination solution to the aluminum element in the flocculant is 1: 2-6, including but not limited to any one of the point values of 1:3, 1:4 and 1:5 or the range value between any two.
By adopting the molar ratio, the dosage of the flocculating agent can be reduced while deep fluorine removal is carried out, and the cost is saved.
Preferably, in the step (b) and the step (c), the temperature of the mixed material is 40-60 ℃ in the flocculation precipitation process, including but not limited to the point value of any one of 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ and 58 ℃ or the range value between any two of the points;
and/or the flocculation settling time is 0.5-2 h, including but not limited to the point value of any one of 1h and 1.5h or the range value between any two.
The use of the above range of temperature and time is advantageous for flocculation or precipitation and thus for improving the removal rate of fluorine.
The invention also provides a method for recovering nickel, cobalt and manganese from the lithium ion battery anode material, which comprises the above method for removing fluorine from the lithium ion battery anode material leachate.
According to the method for recovering nickel, cobalt and manganese from the lithium ion battery cathode material, in the recovery process, the loss rate of Ni and/or Co and/or Mn is low, and sodium ions, ammonium ions, organic matters and the like are not left.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for removing fluorine from the lithium ion battery anode material leaching solution, provided by the invention, the carbonate is used as a neutralizer, the mixed material is adjusted to a specific pH value, and a two-step flocculation precipitation fluorine removal means is adopted, so that the dosage of a flocculating agent and the carbonate is reduced to the maximum extent while deep fluorine removal is realized; and the loss rate of Ni and/or Co and/or Mn is greatly reduced in the defluorination process, and the loss rate of Ni, Co and Mn is below 0.05 percent in the defluorination process. Meanwhile, the method has the advantages of simple operation, short period, low cost, no sodium ions, ammonium ions, organic matters and the like after fluorine removal, and solves the problem of serious loss of Ni, Co and Mn in the prior art.
(2) The defluorination method of the lithium ion battery anode material leaching solution provided by the invention adopts the flocculation precipitation method to defluorinate, and adopts a two-step defluorination method, so that the deep defluorination purpose is achieved, the defluorination rate is as high as about 99.8%, and the addition amount of a flocculating agent is obviously reduced and the cost is saved by utilizing iron ions and aluminum ions in the anode leaching solution.
(3) According to the method for recovering nickel, cobalt and manganese from the lithium ion battery anode material, the loss rate of Ni and/or Co and/or Mn is low in the recovery process, and sodium ions, ammonium ions, organic matters and the like are not left.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a method for removing fluorine from a leaching solution of a lithium ion battery positive electrode material according to embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within 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 not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The method for removing fluorine from the leachate of the lithium ion battery positive electrode material provided in this embodiment is shown in fig. 1, and specifically includes the following steps:
(a) mixing water and waste LiNi in a mass ratio of 4:1xCoyMnzO2Mixing the positive electrode materials of the lithium battery to obtain ore pulp; adding concentrated sulfuric acid into the ore pulp, mixing uniformly, then slowly adding hydrogen peroxide into the ore pulp, carrying out reduction acid leaching reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a leaching solution;
(b) taking 500mL of the leaching solution obtained in the step (a), and slowly adding 20 mass percent of CaCO into the leaching solution3Dispersing liquid, adjusting the pH value of the mixed material to 5, performing flocculation precipitation at 55 ℃, reacting for 1h, and performing solid-liquid separation to obtain 506mL of first defluorination solution;
(c) taking 250mL of the first defluorination solution obtained in the step (b) and 3.77g of Al2(SO4)3∙18H2Mixing and uniformly stirring O, and performing deep flocculation precipitation for fluorine removal, wherein the molar ratio of fluorine ions in the first fluorine removal solution to aluminum in the flocculating agent is 1: 4; then adding 20 percent CaCO by mass concentration3And (3) dispersing the solution, adjusting the pH value of the mixed material to 5, reacting for 1h at 55 ℃, and carrying out solid-liquid separation to obtain 248mL of second defluorination solution.
Wherein, the contents of each element in the leaching solution obtained in the step (a), the first defluorination solution obtained in the step (b) and the second defluorination solution obtained in the step (c) are shown in the following table 1.
TABLE 1 contents of respective elements in the leach liquor, the first defluorination solution and the second defluorination solution
Element(s) Ni Co Mn Al Fe F
Leach liquor 72.15g/L 23.19g/L 67.64g/L 8.51g/L 0.30g/L 1.59g/L
First defluorination solution 71.89g/L 23.05g/L 67.49g/L 30.58mg/L 0.38mg/L 106.32mg/L
Second defluorination solution 71.45g/L 22.89g/L 67.28g/L 28.16mg/L 0.26mg/L 3.06mg/L
As can be seen from Table 1, the F content was reduced from 1.59g/L to 3.06mg/L or less, the fluorine removal rate was 99.8% or more, and the Ni, Co and Mn loss rates during the fluorine removal process were all 0.05% or less. The contents of Ni, Co and Mn in the filter residue after solid-liquid separation are all below 0.05 percent, and the values of Ni, Co and Mn are not recovered.
Example 2
The method for removing fluorine from the lithium ion battery anode material leaching solution provided by the embodiment comprises the following steps of:
(a) mixing water and the waste lithium nickelate battery positive electrode material in a mass ratio of 2:1 to obtain ore pulp; adding concentrated hydrochloric acid into the ore pulp, mixing uniformly, then slowly adding hydrogen peroxide into the ore pulp, carrying out reduction acid leaching reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a leaching solution;
(b) taking 500mL of the leaching solution obtained in the step (a), and slowly adding NiCO with the mass concentration of 15 percent into the leaching solution3Dispersing liquid, adjusting the pH value of the mixed material to 4, performing flocculation precipitation at 550 ℃, reacting for 1h, and performing solid-liquid separation to obtain 498mL of first defluorination solution;
(c) taking 250mL of the first defluorination solution obtained in the step (b) and 0.81g of AlCl3Mixing and stirring uniformly, and performing deep flocculation precipitation for removing fluorine, wherein the molar ratio of fluorine ions in the first fluorine removal solution to aluminum in the flocculating agent is 1: 2; then adding NiCO with the mass concentration of 15 percent into the mixture3And (3) dispersing the solution, adjusting the pH value of the mixed material to 4, reacting for 1h at 55 ℃, and carrying out solid-liquid separation to obtain 253mL of second defluorination solution.
Wherein, the contents of each element in the leaching solution obtained in the step (a), the first defluorination solution obtained in the step (b) and the second defluorination solution obtained in the step (c) are shown in the following table 2.
TABLE 2 contents of respective elements in the leach solution, the first defluorination solution and the second defluorination solution
Element(s) Ni Al Fe F
Leach liquor 105.29g/L 9.28g/L 0.51g/L 1.62g/L
First defluorination solution 105.18g/L 105.89mg/L 0.85mg/L 115.20mg/L
Second defluorination solution 104.59g/L 85.59mg/L 0.59mg/L 4.16mg/L
As can be seen from Table 2, the F content was reduced from 1.62g/L to 4.16mg/L or less, the fluorine removal rate was 99.8% or more, and the Ni, Co and Mn loss rates during the fluorine removal process were all 0.05% or less. The contents of Ni, Co and Mn in the filter residue after solid-liquid separation are all below 0.05 percent, and the values of Ni, Co and Mn are not recovered.
Example 3
The method for removing fluorine from the lithium ion battery anode material leaching solution provided by the embodiment comprises the following steps of:
(a) mixing water and waste LiNi in a mass ratio of 4:1xCoyMnzO2Mixing the positive electrode materials of the lithium battery to obtain ore pulp; adding acetic acid into the ore pulp, mixing uniformly, then slowly adding hydrogen peroxide into the ore pulp, carrying out reduction acid leaching reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a leaching solution;
(b) taking 500mL of the leaching solution obtained in the step (a), and slowly adding 20 mass percent of MnCO into the leaching solution3Dispersing liquid, adjusting the pH value of the mixed material to 5, performing flocculation precipitation at 55 ℃, reacting for 1h, and performing solid-liquid separation to obtain 502mL of first defluorination solution;
(c) take 250mLMixing the first defluorination solution obtained in the step (b) with 1.09g of aluminum acetate, uniformly stirring, and performing deep flocculation precipitation defluorination, wherein the molar ratio of fluoride ions in the first defluorination solution to aluminum elements in a flocculating agent is 1: 3; then adding 20% MnCO by mass concentration into the mixture3And (3) dispersing the solution, adjusting the pH value of the mixed material to 5, reacting for 1h at 55 ℃, and carrying out solid-liquid separation to obtain 246mL of second defluorination solution.
Wherein, the contents of each element in the leaching solution obtained in the step (a), the first defluorination solution obtained in the step (b) and the second defluorination solution obtained in the step (c) are shown in the following table 3.
TABLE 3 contents of the respective elements in the leach solution, the first defluorination solution and the second defluorination solution
Element(s) Ni Co Mn Al Fe F
Leach liquor 71.09g/L 22.89g/L 66.82g/L 8.18g/L 0.35g/L 1.61g/L
First defluorination solution 70.79g/L 22.78g/L 66.42g/L 35.24mg/L 0.31mg/L 101.25mg/L
Second defluorination solution 70.29g/L 22.34g/L 66.22g/L 26.24mg/L 0.26mg/L 3.69mg/L
As can be seen from Table 3, the F content was reduced from 1.61g/L to 3.69mg/L or less, the fluorine removal rate was 99.8% or more, and the Ni, Co, and Mn loss rates during the fluorine removal process were all 0.05% or less. The contents of Ni, Co and Mn in the filter residue after solid-liquid separation are all below 0.05 percent, and the values of Ni, Co and Mn are not recovered.
Comparative example 1
The method for removing fluorine from the lithium ion battery positive electrode material leachate provided by the present comparative example is substantially the same as that of example 1, except that 20% by mass CaCO is added in step (b)3The dispersion was replaced with a 20% sodium hydroxide solution by mass.
Wherein, the contents of each element in the leaching solution, the first defluorination solution and the second defluorination solution are shown in the following table 4.
TABLE 4 contents of respective elements in the leach solution, the first defluorination solution and the second defluorination solution
Element(s) Ni Co Mn Al Fe F
Leach liquor 72.15g/L 23.19g/L 67.64g/L 8.51g/L 0.30g/L 1.59g/L
First defluorination solution 65.29g/L 20.89g/L 62.64g/L 32.28mg/L 0.54mg/L 107.32mg/L
Second defluorination solution 62.14g/L 19.49g/L 60.37g/L 27.39mg/L 0.37mg/L 3.89mg/L
As can be seen from Table 4, the loss rates of nickel, cobalt and manganese were about 15%, 17% and 12%, respectively. It can be seen that the removal of fluorine by using a sodium hydroxide solution as a neutralizing agent can be achieved, but a large amount of loss of nickel, cobalt and manganese is caused.
Comparative example 2
The method for removing fluorine from the lithium ion battery positive electrode material leachate provided by the present comparative example is substantially the same as that of example 1, except that 20% by mass CaCO is added in step (b)3And replacing the dispersion liquid with a sodium carbonate solution with the mass fraction of 20%.
Wherein, the contents of each element in the leaching solution, the first defluorination solution and the second defluorination solution are shown in the following table 5.
TABLE 5 contents of respective elements in the leach solution, the first defluorination solution and the second defluorination solution
Element(s) Ni Co Mn Al Fe F
Leach liquor 72.15g/L 23.19g/L 67.64g/L 8.51g/L 0.30g/L 1.59g/L
First defluorination solution 56.30g/L 18.27g/L 50.38g/L 34.15mg/L 0.50mg/L 99.39mg/L
Second defluorination solution 48.34g/L 16.58g/L 42.29g/L 29.12mg/L 0.24mg/L 2.83mg/L
As can be seen from Table 5, the fluorine removal was carried out using a sodium carbonate solution as a neutralizing agent, but due to CO3 2-The reaction with nickel, cobalt and manganese can cause the nickel, cobalt and manganese to be deposited in the slag in a large quantity, and the loss is caused. The contents of Ni, Co and Mn in the filter residue after solid-liquid separation are respectively 25.85%, 21.18% and 24.67%.
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 make the essence of the corresponding technical solutions 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 alternatives and modifications that are within the scope of the invention.

Claims (9)

1. The method for removing fluorine from the lithium ion battery anode material leaching solution is characterized by comprising the following steps of:
(a) mixing the positive electrode material, an acid solution and a reducing agent, carrying out reduction acid leaching reaction, and carrying out solid-liquid separation to obtain a positive electrode leaching solution;
(b) mixing the positive electrode leaching solution with carbonate, performing flocculation precipitation, and then performing solid-liquid separation to obtain a first defluorination solution;
(c) uniformly mixing the first defluorination solution and a flocculating agent, adding carbonate into the first defluorination solution, performing flocculation precipitation, and then performing solid-liquid separation to obtain a second defluorination solution;
in the step (b) and the step (c), the pH value of the mixed material is 4-6 in the flocculation precipitation process;
in step (c), the flocculant comprises at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, polyaluminum sulfate, aluminum citrate, and aluminum acetate.
2. The method according to claim 1, wherein in the step (a), the acid solution comprises an organic acid solution and/or an inorganic acid solution.
3. The fluorine removal method according to claim 2, wherein the organic acid comprises citric acid and/or acetic acid;
and/or; the inorganic acid includes at least one of sulfuric acid, hydrochloric acid, and nitric acid.
4. The fluorine removal method according to claim 1, wherein in the step (a), the reducing agent comprises at least one of hydrogen peroxide, sodium thiosulfate, sodium sulfite and hydrazine sulfate.
5. The defluorination method of claim 1, wherein in step (b), said carbonate comprises at least one of calcium carbonate, aluminum carbonate, nickel carbonate, cobalt carbonate and manganese carbonate.
6. The method according to claim 1, wherein in the step (c), the molar ratio of the fluorine ions in the first defluorination solution to the aluminum element in the flocculant in the mixed material of the first defluorination solution and the flocculant is 1: 2-6.
7. The method for removing fluorine according to any one of claims 1 to 6, wherein the temperature of the mixed material during the flocculation precipitation in the steps (b) and (c) is 40 to 60 ℃.
8. The defluorination method according to any one of claims 1 to 6, wherein in the steps (b) and (c), the flocculation time is 0.5 to 2 hours.
9. A method for recovering nickel, cobalt and manganese from a lithium ion battery cathode material, which comprises the method for removing fluorine from the lithium ion battery cathode material leachate according to any one of claims 1 to 8.
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