CN111924817A - Method for comprehensively utilizing waste lithium iron phosphate anode material - Google Patents
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Abstract
The invention discloses a method for comprehensively utilizing waste lithium iron phosphate positive electrode materials, which comprises the steps of leaching the waste lithium iron phosphate positive electrode materials by using acid liquor, converting ferrous ions into iron ions through oxidation reaction after adjusting iron-phosphorus ratio and pH value of leachate to strong acidity, generating ferric phosphate precipitate, and carrying out liquid-solid separation to obtain hydrated ferric phosphate and a lithium-containing solution; removing heavy metal ions from the lithium-containing solution by a precipitation method, and then carrying out liquid-solid separation to obtain heavy metal precipitation slag and lithium-containing purified liquid; adding a lithium ion precipitator into the lithium-containing purified liquid, adjusting the pH value to be weakly acidic or alkaline to perform lithium ion precipitation reaction, and then performing liquid-solid separation to obtain a lithium salt product. The method can recover iron, phosphorus and lithium in the waste lithium iron phosphate cathode material at a high recovery rate, and simultaneously obtain the iron phosphate and lithium salt products with high purity and high tap density, and the method has the advantages of simple recovery process, mild conditions and low cost, and meets the requirements of industrial production.
Description
Technical Field
The invention relates to a recycling method of waste lithium iron phosphate anode materials, in particular to a method for comprehensively utilizing waste lithium iron phosphate anode materials, and belongs to the technical field of waste new energy material treatment and resource utilization.
Background
In recent years, the electric automobile industry in China is developing at a high speed, and the sales volume of electric automobiles will continue to increase at a high speed in a future period. At present, lithium ion secondary batteries using lithium iron phosphate as a positive electrode material have been widely used in power batteries of electric vehicles due to their characteristics of low cost, good safety performance, and the like. In the process of promoting the high-speed growth of power batteries by the rapid development of the electric automobile industry, the number of waste lithium ion batteries is rapidly increased year by year. Therefore, in order to recycle materials, save cost and protect environment, when the large-scale abandonment age of electric automobiles in China comes, the recycling of waste lithium iron phosphate cathode materials becomes urgent.
The recovery method of the waste lithium iron phosphate anode material can be roughly divided into two types: the first type is a pyrogenic process technique, i.e., regeneration of lithium iron phosphate by high temperature treatment. The method comprises the specific steps of utilizing a lithium source and a waste lithium iron phosphate anode material to carry out hydrothermal reaction or solvothermal reaction to generate lithium iron phosphate, or carrying out ball milling and calcination on the recovered waste lithium iron phosphate anode material and a lithium source solid phase to carry out liquid phase or solid phase direct lithium supplement repair on the waste lithium iron phosphate in a lithium-deficient state, and then coating a conductive agent or coating the conductive agent and doping metal ions to carry out targeted repair and regeneration. The method has the main advantages that the process flow is very simple, but the problems of carrying partial binder, electrolyte impurities, incomplete repair of the damaged lithium iron phosphate structure and the like still exist. The second type is a wet processing technique, i.e., iron phosphate and lithium carbonate are produced after wet chemical process treatment, and then lithium iron phosphate is prepared again by a carbothermic method. The method comprises the steps of crushing waste lithium iron phosphate positive electrode materials, dissolving the crushed materials with acid, adding alkali liquor to adjust the pH value to precipitate iron and phosphorus, and carrying out solid-liquid separation to obtain iron phosphate and a lithium-containing solution. And adding sodium carbonate or sodium bicarbonate into the lithium solution to obtain a lithium carbonate product, and then mixing and calcining the obtained iron phosphate, lithium carbonate and a carbon source reducing agent to obtain the lithium iron phosphate cathode material. The method realizes high added value recovery and utilization of the waste lithium iron phosphate anode material, and has the defect that impurities such as aluminum, copper and the like inevitably exist in the waste lithium iron phosphate anode material, so that the technical bottleneck restricting the method is always how to improve the quality of the iron phosphate product.
Disclosure of Invention
Aiming at the defects of the method for recovering the resources of the waste lithium iron phosphate positive electrode material by a wet method in the prior art, the invention aims to provide the method for comprehensively utilizing the waste lithium iron phosphate positive electrode material, the method can recover iron, phosphorus and lithium in the waste lithium iron phosphate positive electrode material at a high recovery rate, simultaneously obtain high-purity and high-tap-density iron phosphate and high-purity lithium salt, and has the advantages of simple recovery process, mild conditions and low cost, thereby meeting the requirements of industrial production.
In order to achieve the technical purpose, the invention provides a method for comprehensively utilizing a waste lithium iron phosphate anode material, which comprises the following steps of:
1) leaching the waste lithium iron phosphate anode material by using acid liquor to obtain leachate containing iron, phosphorus and lithium;
2) adjusting the iron-phosphorus ratio and the pH value of the leachate to 0.01-1.2, adding an oxidant to perform an oxidation reaction to convert ferrous ions into iron ions, heating to 80-120 ℃ to react for 8.0-48.0 h, and performing liquid-solid separation after the reaction is finished to obtain a hydrated iron phosphate product and a lithium-containing solution;
3) adjusting the pH value of the lithium-containing solution to 2.0-5.0, adding a heavy metal precipitator to perform heavy metal ion precipitation reaction, and performing liquid-solid separation to obtain heavy metal precipitation slag and lithium-containing purification solution;
4) and adding a lithium precipitator into the lithium-containing purified liquid, adjusting the pH value of the lithium-containing purified liquid to be weakly acidic or alkaline, performing lithium ion precipitation reaction, and performing liquid-solid separation to obtain a lithium salt product.
The main reaction process of the technical scheme of the comprehensive utilization of the waste lithium iron phosphate anode material comprises the reaction steps of leaching, generating ferric phosphate, removing impurities, precipitating lithium and the like: the first step reaction is a leaching process, and the acid solution is adopted in the leaching process, so that iron, phosphate radical, lithium and the like can be efficiently dissolved out, and the subsequent recovery process is facilitated; the second step reaction is the synthesis of hydrated ferric phosphate and the crystal growth process, and the process can effectively prevent Al by strictly and synergistically controlling the acidity of a reaction system, the reaction temperature, the reaction time and other conditions3+、Cu2+Controlling the metal impurities in a solution system in a cocrystallization process so that the metal impurities are not coprecipitated with iron ions to obtain high-purity hydrated iron phosphate, and effectively regulating and controlling the growth process of hydrated iron phosphate crystals to obtain a hydrated iron phosphate product with high tap density, wherein the tap density reaches 1.2g/cm3Left and right; the third step is a process of removing impurities of heavy metal ions, mainly comprising precipitation separation of the heavy metal ions by a precipitation method, the fourth step is a process of lithium ion precipitation reaction, and lithium is recovered in a lithium salt form by using a lithium precipitator.
In the technical scheme of the invention, the acidity of the reaction system, the reaction temperature, the reaction time and other conditions are controlledThe principle of the generation and growth of crystals of hydrated iron phosphate is as follows: by utilizing reaction conditions such as high acidity and the like, the phosphorus source is ensured to exist mainly in the form of phosphoric acid molecules or dihydrogen phosphate ions, and the phosphoric acid molecules or hydrogen phosphate ions and slow phosphate ions are promoted to be ionized at a high rate by combining the cooperative control of reaction temperature and reaction time, so that the low-concentration phosphate ions are released, the nucleation rate of iron phosphate precipitation is greatly reduced, and iron phosphate grains can be controlled to grow into high-density hydrated iron phosphate with high crystallinity. Solubility product constant Ksp of iron phosphate (1.3X 10)-22) Very small, in the initial stage of the reaction, in Fe3+Under the condition of higher concentration (more than or equal to 1.5mol/L), even if phosphoric acid molecules or dihydrogen phosphate ions ionize a very small amount of phosphate ions, hydrated iron phosphate precipitates can be continuously formed; when the reaction is near the end of the reaction (setting Fe)3+Initial concentration of 0.5g/L, i.e., approximately 0.001mol/L), Fe is also due to the very low solubility product constant of iron phosphate3+]*[PO4 3-]Is also easily equal to or greater than 1.3X 10-22Thereby forming a hydrated ferric phosphate precipitate and ensuring the completion of the precipitation reaction. Because the phosphate radical with extremely low concentration is slowly ionized under the conditions of extremely low solubility product constant and high acidity of the iron phosphate, the continuous growth of the crystal grains of the hydrated iron phosphate is ensured, and the hydrated iron phosphate product with high tap density is obtained. At the same concentration, the phosphate solubility product constant of metal ions such as copper is large, and the metal ions still exist in the solution system in the form of metal ions.
As a preferred technical solution, the leaching conditions are as follows: the solid-to-solid ratio of the leaching solution is 2-8 mL:1g, the temperature is 40-90 ℃, and the time is 1.0-5.0 h. Under the preferable leaching condition, iron, lithium, phosphate radical and the like in the waste lithium iron phosphate anode material can be leached to the maximum extent, so that the recovery rate of the useful elements is improved. The using amount of the acid solution is 0.5-1.5 times (preferably 0.8-1.2 times) of the theoretical using amount, and the theoretical amount refers to the theoretical molar amount of the acid required for forming corresponding salts from Fe, Li, Al and the like in the waste lithium iron phosphate anode material. The preferable solid-to-solid ratio of the leaching solution is 3-5 mL:1 g. The leaching temperature is preferably 50-80 ℃, and the time is preferably 1.5-3.0 h. The acid solution is sulfuric acid solution, hydrochloric acid solution or mixed solution of sulfuric acid and hydrochloric acid.
As a preferable technical scheme, the iron-phosphorus ratio of the leaching solution is adjusted to 1: 1.1-1.5. And supplementing an iron source or a phosphorus source to meet the proportion, so that the iron source or the phosphorus source is favorable for generating iron phosphate precipitation in an optimal proportion range, and the iron conversion rate is improved. The iron supplementing reagent is ferrous sulfate heptahydrate or ferrous sulfate solution dissolved by iron sheet/iron scrap sulfuric acid, and the phosphorus supplementing reagent is one or more of phosphoric acid, sodium, potassium or ammonium monohydrogen phosphate or dihydrogen phosphate or phosphate, and the reagents are well known in the industry.
As a preferable technical solution, the oxidizing agent is at least one of hydrogen peroxide, potassium peroxide, sodium peroxide, and persulfate. The persulfate is one or more of sodium persulfate, potassium persulfate or ammonium persulfate.
As a preferable technical scheme, the dosage of the oxidant is 1-2 times of the theoretical molar quantity of the oxidant required for converting all ferrous ions in the leachate into iron ions.
As a preferable technical solution, in the preparation process of converting phosphorus and iron into iron phosphate hydrate in step 2), the pH of the leachate is preferably adjusted to 0.01 to 1.2 (more preferably 0.1 to 0.8). The technological parameters for preparing the hydrated iron phosphate by precipitating Fe and P are as follows: the preferable precipitation reaction temperature is 90-115 ℃, and the preferable precipitation reaction time is 10.0-36.0 h. The reagent for adjusting the pH of the solution is one or more than one of sulfuric acid, ammonia water or lithium hydroxide solution with the concentration of 1:1.
As a preferred technical solution, the oxidation reaction conditions are: the temperature is 30-80 ℃ and the time is 1.0-2.0 h. The temperature of the oxidation reaction is preferably 40-60 ℃, and the time is preferably 1.2-1.5 h.
As a preferred technical solution, the precipitation reaction conditions are: the temperature is 30-80 ℃, the time is 1.5-5.0 h, and the dosage of the heavy metal precipitator is 0.8-2.5 times of the theoretical molar quantity of the heavy metal precipitator required for completely converting heavy metal ions in the lithium-containing solution into precipitates. The preferable pH value in the heavy metal ion precipitation reaction process is 3.0-4.0. The preferable reaction temperature is 40-60 ℃. Preference is given toThe reaction time of (a) is 2.0 to 3.0 hours. The preferable dosage of the heavy metal precipitator is 1-2 times of the theoretical amount. In the process of heavy metal ion precipitation reaction, the reagent for adjusting the pH of the solution is one or more than one of 1:1 diluted ammonia water or lithium hydroxide solution. The heavy metal precipitant is one or more of water soluble hydroxide (such as common sodium hydroxide, potassium hydroxide, etc.), water soluble sulfide salt (such as sodium sulfide, etc.), water soluble hydrosulfide (such as sodium hydrosulfide, etc.), insoluble active ferrous compound (such as active ferrous sulfide, etc.), and its theoretical dosage is based on MS or M (OH)2(M represents Cu)2+Equal heavy metal ions).
As a preferred technical solution, the conditions of the lithium ion precipitation reaction are as follows: the temperature is 30-80 ℃, the time is 1.5-3.0 h, and the dosage of the lithium precipitator is 1-1.5 times of the theoretical molar quantity of the lithium precipitator required for completely converting lithium ions in the lithium-containing purification liquid into corresponding precipitates. In the lithium ion precipitation reaction process: the preferable pH value is 7.0-10.0, the preferable reaction temperature is 40-60 ℃, and the preferable reaction time is 2-2.5 h; the preferable dosage of the lithium precipitator is 1.1-1.3 times of the theoretical amount. And in the process of preparing the lithium salt by lithium ion precipitation reaction, the pH reagent of the solution is adjusted to be one or more than one of 1:1 diluted ammonia water or lithium hydroxide solution. The precipitation reagent for precipitating lithium ions is one or more of water-soluble carbonate (such as sodium carbonate/ammonium, etc.), water-soluble hydrogen carbonate (such as sodium hydrogen carbonate/ammonium, etc.), water-soluble phosphate (sodium phosphate/ammonium), water-soluble hydrogen phosphate (sodium hydrogen phosphate/ammonium), water-soluble dihydrogen phosphate (sodium dihydrogen phosphate/ammonium, etc.), and the theoretical amount of the precipitation reagent is calculated according to the lithium salt.
The waste lithium iron phosphate anode material is powder produced by crushing and sorting waste lithium iron phosphate batteries, and mainly comprises a lithium iron phosphate anode active substance.
The invention provides a method for comprehensively utilizing waste lithium iron phosphate anode materials, which comprises the following specific steps of:
(1) the controllable leaching process of the waste lithium iron phosphate anode material comprises the following steps: mixing the waste lithium iron phosphate positive electrode material with an acid solution leaching agent with a certain concentration and volume, wherein the using amount of the acid leaching agent is 0.5-1.5 times of the theoretical using amount, the liquid-solid ratio is 2-8: 1, the reaction is carried out for 1.0-5.0 h under the condition that the temperature is controlled to be 40-90 ℃, Fe, P and Li in the waste lithium iron phosphate positive electrode material are transferred into a solution, and a leaching solution and a leaching residue are obtained after liquid-solid separation, wherein the leaching solution is used for preparing hydrated iron phosphate and lithium carbonate, and the leaching residue is used for recovering Al and graphite powder.
(2) The preparation process of the selective precipitation Fe/P or hydrated ferric phosphate comprises the following steps: including Fe2+Oxidation to Fe3+And two processes for preparing hydrated iron phosphate by precipitating Fe and P: analyzing the content of Fe and P in the leachate obtained in the step (1), supplementing a lacking iron source or phosphorus source based on the Fe/P ratio of 1: 1.1-1.5, adjusting the pH value of the solution to 0.01-1.2 (preferably 0.1-0.8), adding an oxidant to enable Fe in the solution to be in the range of 0.01-1.22+Oxidation to Fe3+The oxidant is used in the amount of Fe oxide2+1.1-2.0 times of theoretical amount, the oxidation reaction temperature is 30-80 ℃, the oxidation reaction time is 1.0-2.0 h, the temperature is increased to 80-120 ℃, the precipitation reaction time is 6.0-48.0 h, hydrated iron phosphate is generated, after the reflux reaction is finished, liquid-solid separation is carried out to obtain the Li-containing iron phosphate+Filtrate and crude hydrated iron phosphate; containing Li+And (3) using the filtrate to prepare a lithium carbonate product, washing the crude hydrated iron phosphate with water until no sulfate ions or chloride ions are detected in a barium chloride solution or a silver nitrate solution, and drying to obtain the high-purity hydrated iron phosphate.
(3) Preparation process of lithium ion or lithium carbonate: the method comprises two processes of removing heavy metal ions and preparing lithium salt products by a precipitation method: the heavy metal ion removing process by the precipitation method is to the process containing the Li in the step (2)+Adding an alkali reagent into the filtrate, adjusting the pH value of the solution to 2.0-5.0, adding a heavy metal precipitator to remove Li+Small amount of Cu in filtrate2+The dosage of heavy metal precipitator is 0.8-2.5 times of theoretical amount, the precipitation reaction temperature is 30-80 ℃, the reaction time is 1.5-5.0 h, and the heavy metal precipitation slag and Li-containing slag are obtained through liquid-solid separation+Purifying the liquid; the lithium salt is prepared by precipitation method by adding lithium precipitant into Li+In the purified solution, adjusting the pH value of the system to 6.0-12.0, reacting at a constant temperature of 30-80 ℃ for 1.5-3.0 h, carrying out liquid-solid separation to obtain a lithium precipitation filtrate and a crude lithium salt product, wherein the lithium precipitation filtrate is used for precipitating lithium saltConcentrating and evaporating to recover sodium, potassium or ammonium salt, washing the crude lithium salt product with water until no sulfate ions or chloride ions are detected in a barium chloride solution or a silver nitrate solution, and drying to obtain a high-purity lithium salt product.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the method comprehensively recovers the main components such as phosphorus, iron and lithium elements in the waste lithium iron phosphate anode material, also recovers the entrained aluminum, copper and the like and the graphite powder cathode material, and has higher recovery rate of each component which can reach more than 90 percent.
2. The controlled leaching process for leaching the waste lithium iron phosphate anode material divides aluminum and graphite powder and iron, lithium and phosphorus into two groups, thereby greatly reducing the Fe content2+、Li+And PO4 3-The purification burden of the solution is realized by preparing the hydrated ferric phosphate under the condition of high acidity, so that Al is avoided3+、Cu2+And the like, and the high-purity and high-tap density ferric phosphate can be obtained by adding the impurity components into the hydrated ferric phosphate product, and the synthesis process of the hydrated ferric phosphate is simplified.
3. The invention adopts ammonium salt or lithium salt or ammonia water or lithium hydroxide as the pH adjusting reagent and the precipitating reagent of the solution, avoids the introduction of other cation components in the solution, and obtains the high-purity lithium salt product after heavy metal ion precipitation and impurity removal.
Drawings
FIG. 1 is a process flow of comprehensive utilization of waste lithium iron phosphate anode materials;
FIG. 2 is an SEM photograph of hydrated iron phosphate of example 1;
FIG. 3 is the XRD pattern of the hydrated iron phosphate product of example 1;
FIG. 4 is an SEM photograph of hydrated iron phosphate of example 2;
FIG. 5 is the XRD pattern of the hydrated iron phosphate product of example 2;
FIG. 6 is an SEM photograph of hydrated iron phosphate of example 3;
FIG. 7 is the XRD pattern of the hydrated iron phosphate product of example 3;
FIG. 8 is an SEM photograph of hydrated iron phosphate of example 4;
FIG. 9 is the XRD pattern of the hydrated iron phosphate product of example 4;
FIG. 10 is an SEM photograph of hydrated iron phosphate of example 5;
figure 11 is the XRD pattern of the hydrated iron phosphate product of example 5.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
(1) The controllable leaching process of the waste lithium iron phosphate anode material comprises the following steps: weighing 100g of the waste lithium iron phosphate battery positive electrode material, calculating according to the chemical calculation of iron/phosphorus/lithium in the raw materials, adding sulfuric acid with the theoretical quantity multiple of 0.8, controlling the liquid-solid ratio to be 3:1, the leaching temperature to be 50 ℃, and leaching for 2.0h to obtain a suspension, and performing vacuum filtration to perform liquid-solid separation to obtain a lithium/phosphorus/iron-containing leachate and aluminum/graphite powder-containing leaching residues. Analyzing and measuring the contents of Fe, Li, P and Al in the leaching solution, and calculating the leaching rate.
(2) The preparation process of the selective precipitation Fe/P or hydrated ferric phosphate comprises the following steps: adding ferrous sulfate heptahydrate according to the measured values of Fe and P in the leaching solution obtained in the step (1) and according to the mass ratio of Fe to P of 1:1.15, stirring until ferrous sulfate solid is completely dissolved, adjusting the pH value of the solution to be 0.20 by using dilute sulfuric acid of 1:1, adding 30% of hydrogen peroxide to oxidize the ferrous ions, wherein the dosage of the hydrogen peroxide is 1.2 times of the theoretical dosage, the oxidation temperature is 40 ℃, the oxidation reaction time is 1.0h, then raising the temperature of the reaction system to 100 ℃, carrying out constant-temperature reflux reaction for 18.0h, carrying out vacuum filtration and liquid-solid separation after the reaction reaches the end point to obtain filtrate containing lithium ions, washing filter residues until sulfate ions do not exist, and drying to obtain a hydrated iron phosphate product. The filtrate was analyzed for Fe, P and Li content and the precipitation rate was calculated. And (4) feeding the hydrated iron phosphate product to perform ICP full-component measurement, and calculating Fe/P in the hydrated iron phosphate product. And sampling the hydrated iron phosphate product to perform tap density measurement and SEM and XRD detection.
(3) Preparation process of lithium ion or lithium carbonate: analytical determination of Li content in step (2)+Cu in filtrate2+The content of (A) is that the solution pH value is adjusted to 3.5 by using LiOH solution with the ratio of 1:1, ammonium sulfide solution with the theoretical amount of 1.2 times is added, andcarrying out sulfurization precipitation to remove heavy metal ions, controlling the reaction temperature at 40 ℃ and the reaction time at 2.0h to reach the reaction end point, and carrying out vacuum filtration to obtain the Li-containing material+Purifying the liquid; determination of Li in purification liquid+And (3) adding ammonium bicarbonate with the theoretical dosage of 1.5 times to precipitate lithium ions, adjusting the pH value of the solution to 8 by adopting 1:1 diluted ammonia water, keeping the reaction temperature of a constant system at 60 ℃, keeping the reaction time at 2.0h, after the reaction is finished, carrying out vacuum filtration, washing and drying to obtain a lithium carbonate product, and sampling to carry out ICP full-component content determination.
The leaching rate of the main elements in the step (1) and the precipitation rate of the main elements in the step (2) are shown in table 1, the ICP detection result of the hydrated iron phosphate, the Fe/P and tap density are shown in table 2, the ICP detection result of the lithium carbonate is shown in table 3, and the SEM and XRD detection results of the hydrated iron phosphate product are shown in table 1 and fig. 2.
Example 2
(1) The controllable leaching process of the waste lithium iron phosphate anode material comprises the following steps: weighing 100g of waste lithium iron phosphate battery positive electrode material, adding hydrochloric acid with the theoretical quantity multiple of 1.2 times according to the stoichiometric quantity of iron/phosphorus/lithium in the raw materials, controlling the liquid-solid ratio to be 4:1, the leaching temperature to be 80 ℃, and the leaching time to be 3.0h to obtain suspension, and performing vacuum filtration and liquid-solid separation to obtain leachate containing lithium/phosphorus/iron and leaching slag containing aluminum/graphite powder. Analyzing the contents of Fe, Li, P and Al in the leaching solution, and calculating the leaching rate.
(2) The preparation process of the selective precipitation Fe/P or hydrated ferric phosphate comprises the following steps: adding ammonium dihydrogen phosphate according to the measured value of Fe and P in the leaching solution in the step (1) according to the mass ratio of Fe to P of 1:1.2, stirring until ammonium dihydrogen phosphate solid is completely dissolved, adjusting the pH value of the solution to be 0.30 by using 1:1 dilute sulfuric acid, adding 30% hydrogen peroxide to oxidize ferrous ions, wherein the dosage of the hydrogen peroxide is 1.3 times of the theoretical dosage, the oxidation temperature is 60 ℃, the oxidation reaction time is 1.5h, raising the temperature of the reaction system to 1005 ℃, carrying out constant-temperature reflux reaction for 24.0h, carrying out vacuum filtration and liquid-solid separation after the reaction reaches the end point to obtain filtrate containing lithium ions, washing filter residues until no chloride ions exist, and drying to obtain a hydrated iron phosphate product. The filtrate was analyzed for Fe, P and Li content and the precipitation rate was calculated. And (4) feeding the hydrated iron phosphate product to perform ICP full-component measurement, and calculating Fe/P in the hydrated iron phosphate product. And sampling the hydrated iron phosphate product to perform tap density measurement and SEM and XRD detection.
(3) Preparation process of lithium ion or lithium carbonate: analytical determination of Li content in step (2)+Cu in filtrate2Adjusting the pH value of the solution to 4.0 by using a LiOH solution with the ratio of 1:1, adding ammonium sulfide with the theoretical amount of 1.15 times, carrying out vulcanization precipitation to remove heavy metal ions, controlling the reaction temperature to be 60 ℃, the reaction time to be 1.50h, carrying out vacuum filtration at the end of the reaction, and obtaining the Li-containing solution+Purifying the liquid; determination of Li in purification liquid+And (3) adding ammonium bicarbonate with the theoretical dosage of 1.3 times to precipitate lithium ions, adjusting the pH value of the solution to 9 by adopting 1:1 diluted ammonia water, keeping the reaction temperature of a constant system at 60 ℃, keeping the reaction time at 1.5h, after the reaction is finished, carrying out vacuum filtration, washing and drying to obtain a lithium carbonate product, and sampling to carry out ICP full-component content determination.
The leaching rate of the main elements in the step (1) and the precipitation rate of the main elements in the step (2) are shown in table 1, the ICP detection result of the hydrated iron phosphate, the Fe/P and tap density are shown in table 2, the ICP detection result of the lithium carbonate is shown in table 3, and the SEM and XRD detection results of the hydrated iron phosphate product are shown in table 3 and fig. 4.
Example 3
(1) The controllable leaching process of the waste lithium iron phosphate anode material comprises the following steps: weighing 100g of waste lithium iron phosphate battery positive electrode material, adding sulfuric acid with the theoretical quantity multiple of 1.0 time according to the chemical calculation of iron/phosphorus/lithium in the raw materials, controlling the liquid-solid ratio to be 5:1, the leaching temperature to be 70 ℃, and the leaching time to be 3.0h to obtain suspension, and performing vacuum filtration to perform liquid-solid separation to obtain leachate containing lithium/phosphorus/iron and leaching slag containing aluminum/graphite powder. Analyzing the contents of Fe, Li, P and Al in the leaching solution, and calculating the leaching rate.
(2) The preparation process of the selective precipitation Fe/P or hydrated ferric phosphate comprises the following steps: adding solid-phase ammonium dihydrogen phosphate according to the measured values of Fe and P in the leaching solution obtained in the step (1) and according to the mass ratio of Fe to P of 1:1.2, stirring until ammonium dihydrogen phosphate solids are completely dissolved, adjusting the pH value of the solution to be 0.30 by using 1:1 dilute sulfuric acid, adding 30% hydrogen peroxide to oxidize ferrous ions, wherein the dosage of the ferrous ions is 1.15 times of the theoretical dosage, the oxidation temperature is 50 ℃, the oxidation reaction time is 2.0 hours, raising the temperature of the reaction system to 95 ℃, carrying out constant-temperature reflux reaction for 30.0 hours, carrying out vacuum filtration and liquid-solid separation after the reaction reaches the end point to obtain filtrate containing lithium ions, washing filter residues until sulfate ions do not exist, and drying to obtain a hydrated iron phosphate product. The filtrate was analyzed for Fe, P and Li content and the precipitation rate was calculated. And (4) feeding the hydrated iron phosphate product to perform ICP full-component measurement, and calculating Fe/P in the hydrated iron phosphate product. And sampling the hydrated iron phosphate product to perform tap density measurement and SEM and XRD detection.
(3) Preparation process of lithium ion or lithium carbonate: analytical determination of Li content in step (2)+Cu in filtrate2+In the content of 1:1 NH3∙H2Adjusting the pH value of the solution to 4.0 by using O solution, adding ammonium bisulfide with the theoretical amount of 2.0 times, carrying out vulcanization precipitation to remove heavy metal ions, controlling the reaction temperature to be 60 ℃, the reaction time to be 2.0h, carrying out vacuum filtration at the end point of the reaction, and obtaining the Li-containing solution+Purifying the liquid; determination of Li in purification liquid+And (3) adding ammonium bicarbonate with the theoretical dosage of 1.25 times to precipitate lithium ions, adjusting the pH value of the solution to 10 by adopting 1:1 diluted ammonia water, keeping the temperature of the system at 50 ℃, reacting for 3.0h, after the reaction is finished, carrying out vacuum filtration, washing and drying to obtain a lithium carbonate product, and sampling to carry out ICP full-component content determination.
The leaching rate of the main elements in the step (1) and the precipitation rate of the main elements in the step (2) are shown in table 1, the ICP detection result of the hydrated iron phosphate, the Fe/P and tap density are shown in table 2, the ICP detection result of the lithium carbonate is shown in table 3, and the SEM and XRD detection results of the hydrated iron phosphate product are shown in fig. 5 and fig. 6.
Example 4
(1) The controllable leaching process of the waste lithium iron phosphate anode material comprises the following steps: weighing 100g of waste lithium iron phosphate battery positive electrode material, adding sulfuric acid with 0.9 times of theoretical quantity according to the stoichiometric quantity of iron/phosphorus/lithium in the raw materials, controlling the liquid-solid ratio to be 4:1, the leaching temperature to be 80 ℃, and the leaching time to be 2.5h to obtain suspension, and performing vacuum filtration to perform liquid-solid separation to obtain leachate containing lithium/phosphorus/iron and leaching slag containing aluminum/graphite powder. Analyzing the contents of Fe, Li, P and Al in the leaching solution, and calculating the leaching rate.
(2) The preparation process of the selective precipitation Fe/P or hydrated ferric phosphate comprises the following steps: according to the measured values of Fe and P in the leaching solution in the step (1), supplementing the lacking ferrous sulfate heptahydrate according to the mass ratio of Fe to P of 1:1.15, stirring until the solid phase of the ferrous sulfate is completely dissolved, adjusting the pH value of the solution to be 0.50 by using 1:1 dilute sulfuric acid, adding 30% hydrogen peroxide to oxidize the ferrous ions, wherein the dosage of the hydrogen peroxide is 1.2 times of the theoretical dosage, the oxidation temperature is 50 ℃, the oxidation reaction time is 2.0 hours, raising the temperature of the reaction system to 115 ℃, carrying out constant-temperature reflux reaction for 18.0 hours, after the reaction reaches the end point, carrying out vacuum filtration liquid-solid separation to obtain filtrate containing lithium ions, washing filter residues until no sulfate ions exist, and drying to obtain a hydrated iron phosphate product. The filtrate was analyzed for Fe, P and Li content and the precipitation rate was calculated. And (4) feeding the hydrated iron phosphate product to perform ICP full-component measurement, and calculating Fe/P in the hydrated iron phosphate product. And sampling the hydrated iron phosphate product to perform tap density measurement and SEM and XRD detection.
(3) Preparation process of lithium ion or lithium carbonate: analytical determination of Li content in step (2)+Cu in solution2+Adjusting the pH value of the solution to 4.5 by using a LiOH solution with the ratio of 1:1, adding ammonium sulfide with the theoretical amount of 1.20 times, carrying out vulcanization precipitation to remove heavy metal ions, controlling the reaction temperature to be 50 ℃, the reaction time to be 2.0h, carrying out vacuum filtration at the end of the reaction, and obtaining the Li-containing solution+Purifying the liquid; determination of Li in purification liquid+Adding ammonium phosphate with the concentration of 2.0 times of the theoretical dosage to precipitate lithium ions, adjusting the pH value of the solution to 9 by adopting 1:1 dilute ammonia water, keeping the reaction temperature of the system at 50 ℃, keeping the reaction time at 2.5h, after the reaction is finished, carrying out vacuum filtration, washing and drying to obtain a lithium phosphate product, and sampling to carry out ICP full-component content determination.
The leaching rate of the main elements in the step (1) and the precipitation rate of the main elements in the step (2) are shown in table 1, the ICP detection result, Fe/P and tap density of the hydrated iron phosphate are shown in table 2, the ICP detection result of the lithium phosphate is shown in table 3, and the SEM and XRD detection results of the hydrated iron phosphate product are shown in fig. 7 and fig. 8.
Example 5
(1) The controllable leaching process of the waste lithium iron phosphate anode material comprises the following steps: weighing 100g of waste lithium iron phosphate battery positive electrode material, adding sulfuric acid with the theoretical quantity multiple of 1.2 times according to the stoichiometric quantity of iron/phosphorus/lithium in the raw materials, controlling the liquid-solid ratio to be 4:1, the leaching temperature to be 80 ℃, and the leaching time to be 1.5h to obtain suspension, and performing vacuum filtration and liquid-solid separation to obtain leachate containing lithium/phosphorus/iron and leaching slag containing aluminum/graphite powder. Analyzing the contents of Fe, Li, P and Al in the leaching solution, and calculating the leaching rate.
(2) The preparation process of the selective precipitation Fe/P or hydrated ferric phosphate comprises the following steps: supplementing the lacking ammonium dihydrogen phosphate solid according to the measured values of Fe and P in the leaching solution obtained in the step (1) and the ratio of Fe to P of 1:1.2, stirring until the solid phase of the ammonium dihydrogen phosphate is completely dissolved, adjusting the pH value of the solution to be 0.6 by using 1:1 dilute sulfuric acid, adding 30% of hydrogen peroxide to oxidize ferrous ions, wherein the dosage is 1.5 of the theoretical dosage, the oxidation temperature is 60 ℃, the oxidation reaction time is 1.5h, raising the temperature of the reaction system to 110 ℃, carrying out constant-temperature reflux reaction for 36.0h, carrying out vacuum filtration liquid-solid separation after the reaction reaches the end point to obtain filtrate containing lithium ions, washing filter residues until sulfate ions do not exist, and drying to obtain a hydrated iron phosphate product. The filtrate was analyzed for Fe, P and Li content and the precipitation rate was calculated. And (4) feeding the hydrated iron phosphate product to perform ICP full-component measurement, and calculating Fe/P in the hydrated iron phosphate product. And sampling the hydrated iron phosphate product to perform tap density measurement and SEM and XRD detection.
(3) Preparation process of lithium ion or lithium carbonate: analytical determination of Li content in step (2)+Cu in solution2+Adjusting the pH value of the solution to 3.5 by using a LiOH solution with the ratio of 1:1, adding ammonium sulfide with the theoretical amount of 1.5 times, carrying out vulcanization precipitation to remove heavy metal ions, controlling the reaction temperature to be 60 ℃, the reaction time to be 1.5h, carrying out vacuum filtration at the end of the reaction, and obtaining the Li-containing solution+Purifying the liquid; determination of Li in purification liquid+Adding ammonium dihydrogen phosphate with the theoretical dosage of 2.0 times to precipitate lithium ions, adjusting the pH value of the solution to 9 by adopting 1:1 diluted ammonia water, keeping the reaction temperature of the system at 60 ℃, keeping the reaction time at 3.0h, after the reaction is finished, carrying out vacuum filtration, washing and drying to obtain a lithium phosphate product, and sampling to carry out ICP full-component content determination.
The leaching rate of the main elements in the step (1) and the precipitation rate of the main elements in the step (2) are shown in table 1, the ICP detection result, Fe/P and tap density of the hydrated iron phosphate are shown in table 2, the ICP detection result of the lithium phosphate is shown in table 3, and the SEM and XRD detection results of the hydrated iron phosphate product are shown in fig. 9 and fig. 10.
Comparative example 1
The pH of the solution is adjusted to 2.0 by using 1:1 dilute sulfuric acid in the step (2), and the rest of the process is the same as that of the example 1. The leaching rate of the main elements in the step (1) and the precipitation rate of the main elements in the step (2) are shown in Table 1. The tap density of the hydrated iron phosphate is measured to be only 0.8702g/cm3。
As can be seen from the results in table 1, although the precipitation rates of Fe, P, and Li in step (2) are improved, the nucleation rate of iron ions and phosphate ions is high due to the high pH in the preparation process of hydrated iron phosphate, so that the grain growth rate of the hydrated iron phosphate is relatively reduced, and the tap density of the hydrated iron phosphate product is significantly low.
Comparative example 2
The reflux isothermal reaction temperature in step (2) was 70 ℃ and the rest of the procedure was the same as in example 1. After liquid-solid separation of the synthesized hydrated iron phosphate product, the concentrations of the remaining iron ions and phosphate ions in the precipitated iron/phosphorus filtrate were measured, and the precipitation rates of the iron ions and the phosphate ions were calculated to be only 69.3% and 67.8%. Obviously, the temperature is too low to facilitate the precipitation of iron ions and phosphate ions.
Table 1: leaching rate of main elements in the step (1) and precipitation rate of main elements in the step (2)
Table 2: ICP (inductively coupled plasma) detection result of hydrated iron phosphate, Fe/P (iron phosphate) and tap density
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Tap density (g/cm)3) | 1.2013 | 1.2562 | 1.1878 | 1.2137 | 1.1905 |
| P(％) | 16.08 | 15.98 | 16.67 | 16.70 | 16.36 |
| Fe(％) | 29.03 | 28.87 | 30.09 | 30.15 | 29.52 |
| Fe/P | 0.9994 | 1.0001 | 0.9986 | 0.9994 | 0.9989 |
| Ca(ppm) | 5.3 | 8.7 | 2.8 | 3.5 | 7.1 |
| Mg(ppm) | 1.1 | 3.9 | 2.5 | 1.9 | 4.2 |
| Na(ppm) | 5.1 | 6.7 | 3.6 | 2.3 | 1.9 |
| Ni(ppm) | 0.1 | 0.9 | 0.6 | 0.8 | 0.2 |
| Zn(ppm) | 0.8 | 0.4 | 0.2 | 0.6 | 0.3 |
| Cu(ppm) | 0.3 | 0.5 | 0.2 | 0.6 | 0.4 |
| Mn(ppm) | 4.1 | 3.9 | 7.2 | 5.7 | 6.3 |
| Pb(ppm) | 1.3 | 2.8 | 1.9 | 1.6 | 2.5 |
| Cr(ppm) | 0.9 | 0.4 | 0.6 | 0.2 | 0.7 |
| K(ppm) | 1.3 | 2.8 | 1.7 | 3.0 | 1.9 |
| Co(ppm) | 0.2 | 0.7 | 0.6 | 0.3 | 0.5 |
| Al(ppm) | 99 | 87 | 103 | 92 | 101 |
| S(ppm) | 110 | 108 | 127 | 93 | 105 |
Table 3: ICP detection result of lithium carbonate or lithium phosphate
Claims (9)
1. A method for comprehensively utilizing waste lithium iron phosphate anode materials is characterized by comprising the following steps: the method comprises the following steps:
1) leaching the waste lithium iron phosphate anode material by using acid liquor to obtain leachate containing iron, phosphorus and lithium;
2) adjusting the iron-phosphorus ratio and the pH value of the leachate to 0.01-1.2, adding an oxidant to perform an oxidation reaction to convert ferrous ions into iron ions, heating to 80-120 ℃ to react for 8.0-48.0 h, and performing liquid-solid separation after the reaction is finished to obtain a hydrated iron phosphate product and a lithium-containing solution;
3) adjusting the pH value of the lithium-containing solution to 2.0-5.0, adding a heavy metal precipitator to perform heavy metal ion precipitation reaction, and performing liquid-solid separation to obtain heavy metal precipitation slag and lithium-containing purification solution;
4) and adding a lithium precipitator into the lithium-containing purified liquid, adjusting the pH value of the lithium-containing purified liquid to be weakly acidic or alkaline, carrying out lithium ion precipitation reaction, and then carrying out liquid-solid separation to obtain a lithium salt product.
2. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 1, wherein the method comprises the following steps: the leaching conditions are as follows: 1g of leaching solution with a solid-to-solid ratio of 2-8 mL, 40-90 ℃, 1.0-5.0 h of time, 0.5-1.5 times of the theoretical molar amount of acid needed for converting all Fe, Li and Al into corresponding salts, wherein the acid solution is a sulfuric acid solution, a hydrochloric acid solution or a mixed solution of sulfuric acid and hydrochloric acid.
3. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 1, wherein the method comprises the following steps: the iron-phosphorus ratio of the leachate is adjusted to 1: 1.1-1.5.
4. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 1, wherein the method comprises the following steps:
the oxidant is at least one of hydrogen peroxide, potassium peroxide, sodium peroxide and persulfate;
the dosage of the oxidant is 1-2 times of the theoretical molar quantity of the oxidant required for completely converting ferrous ions in the leachate into iron ions.
5. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 1 or 4, wherein the method comprises the following steps: the conditions of the oxidation reaction are as follows: the temperature is 30-80 ℃ and the time is 1.0-2.0 h.
6. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 1, wherein the method comprises the following steps: the conditions of the heavy metal ion precipitation reaction are as follows: the temperature is 30-80 ℃, the time is 1.5-5.0 h, and the dosage of the heavy metal precipitator is 0.8-2.5 times of the theoretical molar quantity of the heavy metal precipitator required for completely converting heavy metal ions in the lithium-containing solution into precipitates.
7. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 6, wherein the method comprises the following steps: the heavy metal ion precipitator is at least one of water-soluble hydroxide, water-soluble sulfide salt and water-soluble hydrosulfate, or insoluble active ferrous material (such as ferrous sulfide).
8. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 1, wherein the method comprises the following steps: the conditions of the lithium ion precipitation reaction are as follows: the temperature is 30-80 ℃, the time is 1.5-3.0 h, and the dosage of the lithium precipitator is 1-1.5 times of the theoretical molar quantity of the lithium precipitator required for completely converting lithium ions in the lithium-containing purification liquid into precipitates.
9. The method for comprehensively utilizing the waste lithium iron phosphate anode material as claimed in claim 8, wherein the method comprises the following steps: the lithium precipitant is at least one of water-soluble carbonate, water-soluble hydrogen carbonate, water-soluble phosphate, water-soluble hydrogen phosphate and water-soluble dihydrogen phosphate.
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