CN106684485B - Method for recycling waste lithium iron phosphate anode material by acid leaching method - Google Patents
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Abstract
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a method for recovering and treating waste lithium iron phosphate anode materials by an acid leaching method. The method of the inventionThe method comprises the following steps: a. acid leaching: taking a lithium iron phosphate anode material, adding acid and leaching to obtain a suspension, and filtering to obtain a filtrate; b. and (3) oxidation: b, taking the filtrate obtained in the step a, adjusting the pH value of the filtrate to be less than 1, adding an oxidant, and oxidizing ferrous ions in the filtrate into ferric ions to obtain a mixed solution; c. separation: and (c) taking the mixed solution obtained in the step (b), adjusting the pH value to be 1.5-4, reacting for 1-3 h at the temperature of 60-95 ℃, generating iron phosphate precipitate, filtering, and washing to obtain lithium-containing filtrate and iron phosphate. The method has the advantages of simple process, continuous circulation, low cost, easy industrialization, environmental protection, high recovery rate of Li, Fe and P up to more than 95 percent, and FePO prepared subsequently4The iron phosphate is low in impurity content, 1-6 mu m in particle size, narrow in uniform size distribution and controllable in morphology, and is battery-grade iron phosphate.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a method for recovering and treating waste lithium iron phosphate anode materials by an acid leaching method.
Background
At present, energy and environmental problems are becoming one of the most important problems to people. From wind energy, water power to nuclear energy, footfalls of people exploring new energy sources are not stopped all the time. However, due to the restriction of seasons, geographical locations, technical levels and other conditions, the appearance of these new energy sources does not completely solve the energy problem. With the rapid development of electronic technology, various electronic products such as mobile phones, digital cameras and notebook computers are being miniaturized, and a wider demand is imposed on the miniaturization of power supplies, so that various lithium ion batteries are produced. In 2012, China became the largest lithium battery producing and consuming country in the world except Japan. The large production volumes result in large quantities of spent lithium batteries. How to handle huge waste lithium battery becomes the problem that people cared about.
Although China has a large number of lithium battery recycling enterprises, most of China is in an 'eating-unsaturated' state. The problem of recycling waste batteries is the biggest obstacle to recycling waste lithium batteries. The country should increase the investment of waste battery resource utilization research and establish a perfect waste battery recovery system to deal with the more and more serious resource and energy problems and realize sustainable development. The condition of large-scale scrapping of the automotive power battery in China does not exist. The conventional recovery system also has a hysteresis phenomenon and a low recovery efficiency. There are several main reasons for this: the recovery amount of the battery is small; recovery network is not sound; the environmental protection risk is large.
With the promotion of related domestic industrial policies, the lithium iron phosphate battery inevitably becomes the mainstream of the development of domestic power batteries in the coming years. The lithium iron phosphate material is mainly applied to the anode of a power battery or the anode of an energy storage battery, and the requirement of the power and energy storage battery on the battery material is greater than that of a conventional small battery, so that the lithium iron phosphate material has high social value in recycling, but the recycling cost is very high. Therefore, the key for solving the problem of recycling the lithium iron phosphate battery is to reduce the recycling cost, and before the recycling heat of the lithium iron phosphate battery arrives, a more efficient and environment-friendly recycling process is researched. At present, the existing lithium iron phosphate recovery technology has a great problem. First, the process is complicated and has a problem of contamination, and the recovery rate of lithium is low. Secondly, the prior art does not specifically aim at the subsequent continuous recovery of iron and phosphorus.
For example: the publication number is 'CN 104953200A', the invention name is 'a method for recovering battery-grade iron phosphate from lithium iron phosphate batteries and preparing lithium iron phosphate cathode materials by utilizing waste lithium iron phosphate batteries', and discloses a method for recovering lithium iron phosphate cathode materials by adopting the following method: firstly, crushing a positive plate and carrying out heat treatment; secondly, dissolving in acid liquor; thirdly, adding a surfactant; and fourthly, adding alkali liquor to obtain the battery-grade iron phosphate. Fifthly, adding sodium carbonate to obtain lithium carbonate; sixthly, mixing iron phosphate, lithium carbonate and a carbon source reducing agent; and seventhly, calcining. This patent need earlier through high temperature thermal treatment, needs earlier to roast the raw materials promptly, carries out the acid leaching again, like this at the calcination in-process, has ferrous ion's oxidation when burning off the organic matter, and the iron phosphate that generates after the oxidation is stayed the solid phase easily, is unfavorable for leaching, leads to the rate of recovery low.
Therefore, the research and research of environment-friendly continuous recyclable recycled waste LiFePO are needed4Preparation of lithium salt and FePO from positive electrode material4The method achieves the purposes of simple process, continuous circulation, low cost, easy industrialization, environmental protection, high recovery rate of Li, Fe and P and controllable shape and particle size of the subsequently prepared FP.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for recycling waste lithium iron phosphate anode materials by using an acid leaching method.
The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method comprises the following steps:
a. acid leaching: adding acid into the waste lithium iron phosphate anode material, leaching to obtain a suspension, and filtering to obtain a filtrate;
b. and (3) oxidation: b, taking the filtrate obtained in the step a, adjusting the pH value of the filtrate to be less than 1, adding an oxidant, and oxidizing ferrous ions in the filtrate into ferric ions to obtain a mixed solution;
c. separation: and c, taking the mixed solution obtained in the step b, adjusting the pH value of the mixed solution to be 1.5-4, reacting for 1-3 h at the temperature of 60-95 ℃ to generate iron phosphate precipitate, filtering, and washing to obtain lithium-containing filtrate and iron phosphate.
The method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step a, wherein at least one of sulfuric acid, hydrochloric acid and nitric acid is used for acid leaching.
The method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the following steps of a, adding acid in the step a, and then, adding 0-300% of the acid in an excessive manner; preferably, the acid is in excess of 100 to 300 percent.
Further, the method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step a, wherein the liquid-solid ratio of the added acid is 1.5-5: 1.
The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method comprises the following steps of performing acid leaching at the temperature of 25-95 ℃ for 30-180 min.
The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method is characterized in that in the step b, the oxidant is at least one of hydrogen peroxide, sodium peroxide and potassium permanganate; preferably hydrogen peroxide.
The method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step b, wherein the excess amount of the oxidant added in the step b is 50-200%.
The method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step b, wherein the oxidation temperature is 45-60 ℃, and the oxidation time is 1-5 hours.
And c, adding a surfactant into the mixed solution before adjusting the pH value of the mixed solution.
Further, in the method for recovering and treating the waste lithium iron phosphate positive electrode material by the acid leaching method, the surfactant is preferably at least one of cetyltrimethylammonium chloride, sodium dodecyl sulfate and polyvinylpyrrolidone.
The invention provides an environment-friendly continuous recyclable recovered waste LiFePO4Preparation of lithium salt and FePO from positive electrode material4The method has the advantages of simple process, continuous circulation, low cost, easy industrialization, environmental protection, high recovery rate of Li, Fe and P up to more than 95 percent, and subsequent preparation of FePO4The iron phosphate is low in impurity content, 1-6 mu m in particle size, narrow in uniform size distribution and controllable in morphology, and is battery-grade iron phosphate.
Detailed Description
The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method comprises the following steps:
a. acid leaching: adding acid into the waste lithium iron phosphate anode material, leaching to obtain a suspension, and filtering to obtain a filtrate;
the lithium iron phosphate anode material can be a waste lithium ion battery anode material subjected to crushing, purification and the like;
b. and (3) oxidation: b, taking the filtrate obtained in the step a, adjusting the pH value of the filtrate to be less than 1, adding an oxidant, and oxidizing ferrous ions in the filtrate into ferric ions to obtain a mixed solution;
c. separation: b, adding alkali liquor into the mixed solution obtained in the step b, adjusting the pH value of the mixed solution to be 1.5-4, reacting for 1-3 hours at the temperature of 60-95 ℃ to generate iron phosphate precipitate, filtering, and washing to obtain lithium-containing filtrate and iron phosphate; the alkali liquor can be conventional alkali liquor, such as sodium hydroxide, potassium hydroxide and the like, but in order to reduce the impurity content and avoid the addition of external impurities, the alkali liquor is preferably lithium hydroxide;
the pH value is adjusted in the step c in order to control the particle size and the impurity content of the generated iron phosphate, and the temperature is adjusted because the solubility of the iron phosphate and the temperature are in an inverse proportion relation.
The method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step a, wherein at least one of sulfuric acid, hydrochloric acid and nitric acid is used for acid leaching. The excess is 0-300%, and the excess coefficient is calculated according to the leaching equation and the mass of the waste battery raw material adopted in each experiment. In the method for recovering the lithium iron phosphate cathode material by the acid leaching method, after the acid is added in the step a, the acid is preferably excessive by 0-300%; more preferably 100-300%.
Further, the method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step a, wherein the liquid-solid ratio of the added acid is 1.5-5: 1.
The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method comprises the following steps of performing acid leaching at the temperature of 25-95 ℃ for 30-180 min.
The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method is characterized in that in the step b, the oxidant is at least one of hydrogen peroxide, sodium peroxide and potassium permanganate; preferably hydrogen peroxide.
In the method for recycling the waste lithium iron phosphate anode material by the acid leaching method, in order to oxidize ferrous ions into iron ions, the amount of the oxidant added in the step b is 50-200% in excess.
The method for recycling the waste lithium iron phosphate anode material by the acid leaching method comprises the step b, wherein the oxidation temperature is 45-60 ℃, and the oxidation time is 1-5 hours.
And c, adding a surfactant into the mixed solution before adjusting the pH value of the mixed solution. The surfactant is added into 1 wt% of the iron phosphate theoretically generated, so that the reaction system tends to be homogeneous, and the particle size distribution of the generated powder is more uniform.
Further, in the method for recovering and treating the waste lithium iron phosphate positive electrode material by the acid leaching method, the surfactant is preferably at least one of cetyltrimethylammonium chloride, sodium dodecyl sulfate and polyvinylpyrrolidone.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) Weighing 50g of the anode active material of the waste lithium iron phosphate battery, and adding the anode active material into a sulfuric acid solution. The sulfuric acid is in excess of 0% calculated on the stoichiometric amount of lithium in the raw material. Controlling the liquid-solid ratio to be 1.5:1, the leaching temperature to be 25 ℃, and the leaching time to be 30min to obtain a suspension. The suspension was filtered.
The waste lithium ion battery material treated in the step can be a waste lithium ion battery anode material which is subjected to crushing and purification treatment.
(2) Oxidation of ferrous ions: adjusting the pH value of the filtrate to be less than 1, adding hydrogen peroxide to oxidize ferrous ions, wherein the hydrogen peroxide is excessive by 50 percent, the oxidation temperature is 45 ℃, and reacting for 1 h.
(3) Lithium and iron phosphorus separation to prepare iron phosphate: and (3) adding LiOH into the reaction liquid obtained in the step (2), adjusting the pH to 1.5, controlling the temperature to be 60 ℃, reacting for 2 hours to generate iron phosphate precipitate, filtering and washing to obtain the iron phosphate. The filtrate isContaining Li+And (3) solution.
The final results of recovery of Li, Fe, and P, particle size of iron phosphate, and the like are shown in table 1.
Example 2
(1) And weighing the anode active material 50 of the waste lithium iron phosphate battery, and adding the anode active material into a sulfuric acid solution. The sulfuric acid is in excess of 0% calculated on the stoichiometric amount of lithium in the raw material. Controlling the liquid-solid ratio to be 1.5:1, the leaching temperature to be 60 ℃, and the leaching time to be 100min to obtain a suspension. The suspension was filtered.
The waste lithium ion battery material treated in the step can be a waste lithium ion battery anode material which is subjected to crushing and purification treatment.
(2) Oxidation of ferrous ions: adjusting the pH value of the filtrate to be less than 1, adding hydrogen peroxide to oxidize ferrous ions, wherein the hydrogen peroxide is excessive by 100 percent, the oxidation temperature is 45 ℃, and reacting for 5 hours.
(3) Lithium and iron phosphorus separation to prepare iron phosphate: and (3) adding LiOH into the reaction liquid obtained in the step (2), adjusting the pH value to 2, controlling the temperature to be 60 ℃, reacting for 1 hour to generate iron phosphate precipitate, and filtering and washing to obtain the iron phosphate. The filtrate is Li-containing+And (3) solution.
The results of the recovery rates of Li, Fe, and P and the particle diameters of iron phosphate obtained are shown in table 1.
Example 3
(1) Weighing 50g of the anode active material of the waste lithium iron phosphate battery, and adding the anode active material into a sulfuric acid solution. The sulfuric acid is 100% excess based on the stoichiometric amount of lithium in the raw material. Controlling the liquid-solid ratio to be 2.5:1, the leaching temperature to be 60 ℃, and the leaching time to be 100min to obtain a suspension. The suspension was filtered.
The waste lithium ion battery material treated in the step can be a waste lithium ion battery anode material which is subjected to crushing and purification treatment.
(2) Oxidation of ferrous ions: adjusting the pH value of the filtrate to be less than 1, adding hydrogen peroxide to oxidize ferrous ions, wherein the hydrogen peroxide is excessive by 100 percent, the oxidation temperature is 45 ℃, and reacting for 2 hours.
(3) Lithium and iron phosphorus separation to prepare iron phosphate: adding LiOH into the reaction liquid in the step (2), adjusting the pH value to be 2, and controlling the temperature to be 60Reacting for 1.5h to generate iron phosphate precipitate, filtering and washing to obtain the iron phosphate. The filtrate is Li-containing+And (3) solution.
The results of the recovery rates of Li, Fe, and P and the particle diameters of iron phosphate obtained are shown in table 1.
Example 4
(1) Weighing 50g of the anode active material of the waste lithium iron phosphate battery, and adding the anode active material into a sulfuric acid solution. The sulfuric acid is 100% excess based on the stoichiometric amount of lithium in the raw material. Controlling the liquid-solid ratio to be 4:1, the leaching temperature to be 60 ℃, and the leaching time to be 100min to obtain a suspension. The suspension was filtered.
The waste lithium ion battery material treated in the step can be a waste lithium ion battery anode material which is subjected to crushing and purification treatment.
(2) Oxidation of ferrous ions: adjusting the pH value of the filtrate to be less than 1, adding hydrogen peroxide to oxidize ferrous ions, wherein the hydrogen peroxide is excessive by 100 percent, the oxidation temperature is 60 ℃, and reacting for 2 hours.
(3) Lithium and iron phosphorus separation to prepare iron phosphate: and (3) adding LiOH into the reaction liquid obtained in the step (2), adjusting the pH to be about 4, controlling the temperature to be 95 ℃, reacting for 3 hours to generate iron phosphate precipitate, and filtering and washing to obtain the iron phosphate. The filtrate is Li-containing+And (3) solution.
The results of the recovery rates of Li, Fe, and P and the particle diameters of iron phosphate obtained are shown in table 1.
Example 5
(1) Weighing 50g of the anode active material of the waste lithium iron phosphate battery, and adding the anode active material into a sulfuric acid solution. The sulfuric acid is in excess of 300% calculated on the stoichiometric amount of lithium in the raw material. Controlling the liquid-solid ratio to be 5:1, the leaching temperature to be 95 ℃, and the leaching time to be 180min to obtain a suspension. The suspension was filtered.
The waste lithium ion battery material treated in the step can be a waste lithium ion battery anode material which is subjected to crushing and purification treatment.
(2) Oxidation of ferrous ions: adjusting the pH value of the filtrate to be less than 1, adding hydrogen peroxide to oxidize ferrous ions, wherein the hydrogen peroxide is excessive by 200 percent, the oxidation temperature is 50 ℃, and reacting for 5 hours.
(3) Lithium and iron phosphorus separationPreparing iron phosphate: and (3) adding LiOH into the reaction liquid obtained in the step (2), adjusting the pH to be about 4, controlling the temperature to be 95 ℃, reacting for 3 hours to generate iron phosphate precipitate, and filtering and washing to obtain the iron phosphate. The filtrate is Li-containing+And (3) solution.
The results of the recovery rates of Li, Fe, and P and the particle diameters of iron phosphate obtained are shown in table 1.
Example 6
(1) Weighing 50g of the anode active material of the waste lithium iron phosphate battery, and adding the anode active material into a sulfuric acid solution. The sulfuric acid is in excess of 0% calculated on the stoichiometric amount of lithium in the raw material. Controlling the liquid-solid ratio to be 1.5:1, the leaching temperature to be 95 ℃, and the leaching time to be 180min to obtain a suspension. The suspension was filtered.
The waste lithium ion battery material treated in the step can be a waste lithium ion battery anode material which is subjected to crushing and purification treatment.
(2) Oxidation of ferrous ions: adjusting the pH value of the filtrate to be less than 1, adding hydrogen peroxide to oxidize ferrous ions, wherein the hydrogen peroxide is excessive by 200 percent, the oxidation temperature is 50 ℃, and reacting for 5 hours.
(3) Lithium and iron phosphorus separation to prepare iron phosphate: and (3) adding 1% by weight of iron phosphate into the reaction solution obtained in the step (2) according to theory, adding hexadecyl trimethyl ammonium chloride, adding LiOH, adjusting the pH to be about 4, controlling the temperature to be 95 ℃, reacting for 3 hours to generate iron phosphate precipitate, and filtering and washing to obtain the iron phosphate. The filtrate is Li-containing+And (3) solution.
The results of the recovery rates of Li, Fe and P and the particle size of the iron phosphate obtained finally are shown in Table 1, and the particle size of the finally generated iron phosphate is smaller and the distribution is narrower due to the addition of the surfactant.
Comparative example 1
(1) Weighing 50g of waste lithium iron phosphate battery positive active material, splitting, crushing, carrying out heat treatment at 400 ℃ for 2h, then carrying out oscillating screening, and taking mixed powder below the screen;
(2) adding sulfuric acid into the mixed powder, and leaching with the excess coefficient of 100%;
(3) filtering, and adding a surfactant cetyl trimethyl ammonium chloride into the filtrate according to 1 wt% of the theoretically generated iron phosphate;
(4) adding LiOH into the solution added with the surfactant in the step (3) to adjust the pH value to 2, controlling the temperature to be 60 ℃, reacting for 1.5h to generate iron phosphate precipitate, and then filtering, washing and drying the precipitate to obtain battery-grade iron phosphate and Li-containing iron phosphate+And (3) solution.
The results of the recovery rates of Li, Fe and P and the particle size of iron phosphate and the like finally obtained are shown in Table 1; as can be seen from table 1, the recovery rates of lithium, iron and phosphorus in the battery are low through the steps of high-temperature oxidation and acid leaching, and the raw materials are roasted first and then subjected to acid leaching, so that in the roasting process, the oxidation of ferrous ions exists while the organic matters are burnt, and the iron phosphate generated after oxidation is easily left in a solid phase and is not beneficial to leaching, thereby resulting in low recovery rate.
TABLE 1 examples and comparative examples obtained recovery rates of Li, P and Fe and iron phosphate particle diameters
In conclusion, in the separation step, the pH and the reaction temperature are strictly controlled, the pH and the temperature are basically unchanged in the reaction process, the growth rate of the particles is slow, the prepared iron phosphate is basically spherical or spheroidal particles, and the shape is regular.
Claims (9)
1. The method for recycling and treating the waste lithium iron phosphate anode material by an acid leaching method is characterized by comprising the following steps of:
a. acid leaching: adding acid into the waste lithium iron phosphate anode material, carrying out acid leaching to obtain a suspension, and filtering to obtain a filtrate, wherein after adding the acid, the acid is excessive by 0-300%, the liquid-solid ratio after adding the acid is 1.5-5: 1, the acid leaching temperature is 25-95 ℃, and the acid leaching time is 30-180 min;
b. and (3) oxidation: b, taking the filtrate obtained in the step a, adjusting the pH value of the filtrate to be less than 1, adding an oxidant, and oxidizing ferrous ions in the filtrate into ferric ions to obtain a mixed solution; the oxidant is at least one of hydrogen peroxide, sodium peroxide and potassium permanganate; the oxidation temperature is 45-60 ℃, and the oxidation time is 1-5 h;
c. separation: and c, taking the mixed solution obtained in the step b, adjusting the pH value of the mixed solution to be 1.5-4, reacting for 1-3 h at the temperature of 60-95 ℃ to generate iron phosphate precipitate, filtering, and washing to obtain lithium-containing filtrate and iron phosphate.
2. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to claim 1, which is characterized by comprising the following steps: and a, adopting at least one of sulfuric acid, hydrochloric acid and nitric acid to carry out acid leaching in the step a.
3. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to claim 1, which is characterized by comprising the following steps: and (b) after adding acid in the step (a), the acid is excessive by 100-300%.
4. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to claim 1, which is characterized by comprising the following steps: in the step b, the oxidizing agent is hydrogen peroxide.
5. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to any one of claims 1 to 4, which is characterized by comprising the following steps: and c, adding an oxidant in the step b in an excess amount of 50-200%.
6. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to any one of claims 1 to 4, which is characterized by comprising the following steps: and c, adding a surfactant into the mixed solution before adjusting the pH value of the mixed solution.
7. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to claim 5, is characterized in that: and c, adding a surfactant into the mixed solution before adjusting the pH value of the mixed solution.
8. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to claim 6, is characterized in that: the surfactant is at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl sulfate and polyvinylpyrrolidone.
9. The method for recycling and treating the waste lithium iron phosphate anode material by the acid leaching method according to claim 7, is characterized in that: the surfactant is at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl sulfate and polyvinylpyrrolidone.
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