CN114394610A - Recovery method of waste lithium iron phosphate battery - Google Patents
Recovery method of waste lithium iron phosphate battery Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
A method for recovering waste lithium iron phosphate batteries comprises the following steps: pretreating a waste lithium iron phosphate battery to obtain electrode active material powder; ball milling and mixing the obtained material and sodium salt; roasting the mixture in a muffle furnace to obtain a roasted material; leaching the roasted material with low-temperature water, and filtering to obtain a phosphorus enrichment solution and leaching residues; evaporating and concentrating the phosphorus-enriched liquid to obtain industrial-grade sodium phosphate, and leaching residues by adopting diluted acid oxygen pressure to obtain a lithium-enriched liquid and iron-enriched residues; and after purifying and removing impurities from the lithium enrichment solution, adding a saturated sodium carbonate solution to prepare the battery-grade lithium carbonate. According to the invention, sodium salt auxiliary agent is adopted to assist roasting to promote crystal form transformation of the waste lithium iron phosphate battery powder to separate phosphorus, and then iron and lithium are separated by adopting a dilute acid oxygen pressure leaching mode, so that extraction and separation of iron, phosphorus and lithium in the waste lithium iron phosphate battery powder are synchronously realized.
Description
Technical Field
The invention relates to the technical field of waste battery recovery, in particular to a recovery method of waste lithium iron phosphate batteries.
Background
With the rapid development of modern technology, the pollution problem of social energy and environment ecology becomes more and more prominent, and the pollution problem of various waste batteries to the environment and the ecology becomes the focus of social attention. Lithium ion batteries are widely used in power batteries and energy storage batteries due to their high capacity, stable cycle performance, high platform voltage, and the like, and the demand of power and energy storage batteries on battery materials is generally greater than that of conventional small batteries. Therefore, in the future 3-5 years, a large number of lithium ion batteries are scrapped, and the recycling of the lithium ion batteries has high social value.
However, the current domestic technical route for recycling waste lithium iron phosphate still has defects, and the main way for treating the electrode active material of the waste lithium iron phosphate battery is to obtain Li-containing lithium by acid reduction leaching+、Fe2+、PO4 3-、F-、Al3+And Fe3+Precipitating the plasma leachate to remove aluminum and adsorbing to remove aluminumThen adjusting the pH value of fluorine, adding an oxidant and precipitating to obtain FePO4Finally, the pH is adjusted and Na is added2CO3To obtain Li2CO3. For example, in a method for preparing a lithium iron phosphate positive electrode material from waste lithium iron phosphate batteries, which is disclosed in chinese patent CN111009660B, valuable metals in the waste lithium iron phosphate batteries are recovered by an acid leaching-precipitation method, an electrode active material is leached by inorganic acid to obtain a leachate, copper is removed by iron powder displacement, aluminum is removed by precipitation, then iron phosphate is obtained by adding alkali and an oxidant to control the pH value, and finally lithium is recovered. Also, as disclosed in chinese patent CN110459828A, "a comprehensive recovery method of positive electrode materials of waste lithium iron phosphate batteries," leaching the positive electrode powder of waste lithium iron phosphate batteries with dilute acid and an oxidant to obtain a lithium-enriched solution, and then purifying and removing impurities by a precipitation method to obtain lithium carbonate; performing acid leaching on the leached residue to purify and remove impurities to obtain FePO4The method realizes the recovery of the waste lithium iron phosphate batteries, but the leaching residue of the pre-extracted lithium iron phosphate batteries adopts acid leaching to strictly control the reduction conditions to prevent Fe3+And in Fe2+The solution is difficult to remove impurities under existing conditions.
There are also methods of peeling the positive plate to obtain a positive material, then performing acid leaching full leaching or lithium pre-extraction to obtain a leaching solution containing Li, Fe and P or to obtain a Li-rich leaching solution and leaching residues, and extracting Li from the leaching solution after extracting Fe and P in advance or directly extracting Li.
The conventional method for recovering the cathode material easily causes lithium loss, the lithium recovery rate is low, and in addition, the impurity removal of the iron-containing leachate in the recovery process is difficult, so that battery-grade iron phosphate meeting the industrial standard is difficult to obtain.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for recovering waste lithium iron phosphate batteries.
The invention is realized by the following technical scheme.
A method for recovering waste lithium iron phosphate batteries is characterized by comprising the following steps:
(1) pretreating a waste lithium iron phosphate battery to obtain electrode active material powder, and performing alkali washing and drying to obtain a material to be treated;
(2) ball-milling and mixing the material to be treated obtained in the step (1) and sodium salt;
(3) roasting the mixture obtained in the step (2) in a muffle furnace to obtain a roasted material;
(4) leaching the roasted material obtained in the step (3) by low-temperature water, and filtering to obtain a phosphorus enrichment solution (leachate) and leaching residues;
(5) evaporating and concentrating the phosphorus-enriched solution obtained in the step (4) to obtain industrial-grade sodium phosphate, and leaching residues by adopting diluted acid oxygen pressure to obtain a lithium-enriched solution and iron-enriched residues;
(6) and (5) purifying the lithium enrichment solution obtained in the step (5) to remove impurities, and adding a saturated sodium carbonate solution to prepare the battery-grade lithium carbonate.
Further, the pretreatment in the step (1) comprises the steps of carrying out short-circuit discharge, disassembly, crushing, roasting and screening on the waste lithium iron phosphate battery.
Further, the sodium salt in the step (2) is NaOH or Na2CO3、NaHCO3、Na2SO4、NaHSO4、Na2SO3And/or NaCl; the mass ratio of the material to be treated to the sodium salt is controlled to be 1: (2-10).
Further, in the roasting process in the step (3), the roasting temperature is controlled to be 150-; the roasting temperature is preferably 200-300 ℃, and the roasting time is 30-90 min.
Further, in the low-temperature water leaching process in the step (4), the leaching temperature is controlled to be 0-30 ℃, the time is 10-30min, and the leaching solid-liquid ratio (namely the ratio of the roasting material to water) is controlled to be 50-200 g/L.
Further, the phosphorus enrichment liquid in the step (5) is evaporated and concentrated by adopting an MVR (mechanical vapor recompression) systemCondensing, controlling the evaporation temperature at 40-100 deg.C, controlling the volume of the residual liquid at 10-50%, and obtaining industrial grade Na3PO4·12H2O。
Further, in the dilute acid oxygen pressure leaching process in the step (5), the leaching temperature is controlled to be 100-300 ℃, the concentration of the dilute acid is controlled to be 0.01-0.1mol/L, the leaching time is 30-120min, the leaching solid-liquid ratio (namely the ratio of the leaching slag to the dilute acid) is controlled to be 50-200g/L, the oxygen partial pressure is controlled to be 0.3-0.8MPa, and the kettle pressure is 0.5-1.5 MPa; filtering and drying the iron-enriched slag to obtain the industrial-grade iron oxide red.
Further, the dilute acid is one or two of sulfuric acid, hydrochloric acid and phosphoric acid.
Further, in the process of purifying and impurity removing of the lithium-rich liquid in the step (6), adding a NaOH solution with the mass fraction of 30% to adjust the pH of the lithium-rich liquid to be between 4 and 5 to remove iron and aluminum, and continuing to increase the pH of the solution to 8 to 10 to remove copper.
Further, in the step (6), NaOH solution is added into the leachate obtained by purifying and removing impurities from the lithium-rich solution to adjust the pH of the solution to 11-12, then saturated sodium carbonate solution with 2 times of theoretical excess is added, the temperature is controlled to be 80-90 ℃, the time is 30-60min, and precipitation and filtration are carried out to obtain battery grade Li2CO3。
The invention has the beneficial technical effects that:
1) the method can be used for treating the waste lithium iron phosphate batteries with different models, does not need to be recovered respectively, has simple process and good process repeatability, and is particularly suitable for industrial scale-up production.
2) According to the method, sodium salt auxiliary agent is innovatively adopted to assist roasting to promote crystal form transformation of waste lithium iron phosphate battery powder to separate phosphorus, and then iron and lithium are separated in a dilute acid oxygen pressure leaching mode, so that extraction and separation of iron, phosphorus and lithium in the waste lithium iron phosphate battery powder are synchronously realized.
3) Compared with the existing waste lithium iron phosphate battery recovery technology, the method has the advantages that no harmful gas is generated in the treatment process, no protective atmosphere is needed, the reaction endpoint is easy to control, and the like. And the acid or alkali consumed in the recovery process is greatly reduced, so that the requirements on production equipment and the production cost of the whole recovery process can be greatly lowered.
4) The method is suitable for forming a closed-loop process, does not generate secondary pollution, has environmental protection and economic benefits, has simple process and low production cost, and is suitable for large-scale industrial production.
5) The method can be compatible with the existing lithium iron phosphate battery positive electrode material production line, and realizes low-cost high-value recovery and regeneration of valuable elements.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
FIG. 2 is an XRD pattern of the calcine obtained in example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) soaking the waste lithium iron phosphate battery in 5% NaCl solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, then carrying out mechanical force integral crushing, roasting and screening to obtain electrode active material powder with the particle size of less than 0.1mm, and filtering and drying after alkaline washing to obtain a material to be treated;
(2) performing ball milling mixing on the material obtained in the step (1) and NaOH according to the mass ratio of 1:2 to obtain a mixture to be roasted;
(3) and (3) roasting the mixture obtained in the step (2) in a muffle furnace at a low temperature, wherein the specific process parameters are as follows: the roasting temperature is 250 ℃, and the roasting time is 30 min;
(4) soaking the roasted material in water, and the specific process comprises the following steps: soaking in water at 20 deg.C for 30min to obtain a solid-to-liquid ratio of 100g/L, and filtering to obtain phosphorus-enriched solution and leached residue;
(5) carrying out evaporation concentration on the phosphorus enrichment solution by adopting an MVR system, wherein the evaporation temperature is 60 ℃, the volume of the evaporation residual liquid is 50%, and filtering crystals and drying to obtain industrial-grade sodium phosphate; the leaching residue is leached by dilute sulphuric acid oxygen pressure, and the specific process is as follows: the concentration of sulfuric acid is 0.01mol/L, the temperature is 200 ℃, the time is 60min, the solid-to-liquid ratio is 100g/L, the oxygen partial pressure is controlled to be 0.3MPa, the kettle pressure is 1.5MPa, lithium enrichment liquid and iron enrichment slag are obtained by filtering, wherein the iron enrichment slag is filtered and dried to obtain industrial iron oxide red;
(6) adding 30% sodium hydroxide solution into the lithium enrichment solution to adjust the pH of the lithium enrichment solution for impurity removal, and adding saturated sodium carbonate solution for precipitation to prepare battery-grade lithium carbonate;
the specific purification and impurity removal process is that the pH of the solution is firstly adjusted to 4.5 by adding NaOH under the condition of room temperature, and Fe (OH)3And Al (OH)3Removing Fe and Al, and continuously raising the pH value of the solution to 9 to obtain Cu (OH)2Removing Cu in the form of;
the lithium deposition process to obtain lithium carbonate includes adding NaOH to the leached liquid to regulate pH value to 12, controlling reaction temperature at 80 deg.c and adding saturated Na in 2 times over theoretical amount2CO3Precipitating and filtering the solution after reacting for 60min to obtain battery grade Li2CO3The solution after lithium precipitation is used as mother solution for leaching subsequent filter residue;
the recovery rate of lithium is over 85 percent, and the obtained Li2CO3The purity of the iron oxide red is more than 99.95 percent, the recovery rate of iron phosphorus is more than 95 percent, the purity of the obtained iron oxide red is more than 99 percent, and the purity of the sodium phosphate is more than 98 percent.
Example 2
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) soaking the waste lithium iron phosphate battery in 5% NaCl solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, then carrying out mechanical force integral crushing, roasting and screening to obtain electrode active material powder with the particle size of less than 0.1mm, and filtering and drying after alkaline washing to obtain a material to be treated;
(2) mixing the material obtained in the step (1) with NaHCO3Performing ball milling and mixing according to the mass ratio of 1:7 to obtain a mixture to be roasted;
(3) and (3) roasting the mixture obtained in the step (2) in a muffle furnace at a low temperature, wherein the specific process parameters are as follows: the roasting temperature is 150 ℃, and the roasting time is 80 min;
(4) soaking the roasted material in water, and the specific process comprises the following steps: soaking in water at 10 deg.C for 20min to obtain water extract solid-liquid ratio of 55g/L, and filtering to obtain phosphorus-enriched solution and leached residue;
(5) carrying out evaporation concentration on the phosphorus enrichment solution by adopting an MVR system, wherein the evaporation temperature is 70 ℃, the volume of the evaporation residual solution is 30%, and filtering crystals and drying to obtain industrial-grade sodium phosphate; the leaching residue is leached by using dilute hydrochloric acid oxygen pressure, and the specific process is as follows: the concentration of sulfuric acid is 0.05mol/L, the temperature is 150 ℃, the time is 35min, the solid-to-liquid ratio is 70g/L, the oxygen partial pressure is controlled to be 0.8MPa, the kettle pressure is 0.6MPa, lithium enrichment liquid and iron enrichment slag are obtained by filtering, wherein the iron enrichment slag is filtered and dried to obtain industrial iron oxide red;
(6) adding 30% sodium hydroxide solution into the lithium enrichment solution to adjust the pH of the lithium enrichment solution for impurity removal, and adding saturated sodium carbonate solution for precipitation to prepare battery-grade lithium carbonate;
the specific purification and impurity removal process is that the pH of the solution is firstly adjusted to 5 by adding NaOH under the condition of room temperature, and Fe (OH) is used3And Al (OH)3Removing Fe and Al, and continuously raising the pH value of the solution to 8 to obtain Cu (OH)2Removing Cu in the form of;
the lithium deposition process to obtain lithium carbonate includes adding NaOH to the leached liquid to regulate pH to 11, controlling reaction temperature at 85 deg.c and adding saturated Na in 2 times over theoretical amount2CO3Precipitating and filtering the solution after reacting for 30min to obtain battery grade Li2CO3The solution after lithium precipitation is used as mother solution for leaching subsequent filter residue;
the recovery rate of lithium exceeds 80 percent, and the obtained Li2CO3The purity of the iron oxide red is more than 99.95 percent, the recovery rate of iron phosphorus is more than 95 percent, the purity of the obtained iron oxide red is more than 99 percent, and the purity of the sodium phosphate is more than 98 percent.
Example 3
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) soaking the waste lithium iron phosphate battery in 5% NaCl solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, then carrying out mechanical force integral crushing, roasting and screening to obtain electrode active material powder with the particle size of less than 0.1mm, and filtering and drying after alkaline washing to obtain a material to be treated;
(2) mixing the material obtained in the step (1) with Na2SO4Performing ball milling and mixing according to the mass ratio of 1:10 to obtain a mixture to be roasted;
(3) roasting the mixture obtained in the step (2) in a muffle furnace, wherein the specific process parameters are as follows: the roasting temperature is 500 ℃, and the roasting time is 200 min;
(4) soaking the roasted material in water, and the specific process comprises the following steps: soaking in water at 30 deg.C for 10min to obtain 200g/L solid-liquid ratio, and filtering to obtain phosphorus-enriched solution and leached residue;
(5) carrying out evaporation concentration on the phosphorus enrichment solution by adopting an MVR system, wherein the evaporation temperature is 60 ℃, the volume of the evaporation residual liquid is 20%, and filtering crystals and drying to obtain industrial-grade sodium phosphate; the leaching residue is leached by dilute phosphoric acid under oxygen pressure, and the specific process is as follows: the concentration of sulfuric acid is 0.09mol/L, the temperature is 300 ℃, the time is 100min, the solid-to-liquid ratio is 180g/L, the oxygen partial pressure is controlled to be 0.5MPa, the kettle pressure is 0.7MPa, lithium enrichment liquid and iron enrichment slag are obtained by filtering, wherein the iron enrichment slag is filtered and dried to obtain industrial iron oxide red;
(6) adding 30% sodium hydroxide solution into the lithium enrichment solution to adjust the pH of the lithium enrichment solution for impurity removal, and adding saturated sodium carbonate solution for precipitation to prepare battery-grade lithium carbonate;
the specific purification and impurity removal process is that the pH of the solution is firstly adjusted to 4 by adding NaOH under the condition of room temperature, and Fe (OH) is used3And Al (OH)3Removing Fe and Al, and continuously raising the pH value of the solution to 10 to obtain Cu (OH)2Removing Cu in the form of;
the lithium deposition process to obtain lithium carbonate includes adding NaOH to the leached liquid to regulate pH value to 12, controlling reaction temperature at 90 deg.c and adding saturated Na in 2 times over theoretical amount2CO3Precipitating and filtering the solution after reacting for 40min to obtain battery grade Li2CO3The solution after lithium precipitation is used as mother solution for leaching subsequent filter residue;
the recovery rate of lithium is over 85 percent, and the obtained Li2CO3The purity of the iron oxide red is more than 99.95 percent, the recovery rate of iron phosphorus is more than 97 percent, the purity of the obtained iron oxide red is more than 98 percent, and the purity of the sodium phosphate is more than 98 percent.
Example 4
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) soaking the waste lithium iron phosphate battery in 5% NaCl solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, then carrying out mechanical force integral crushing, roasting and screening to obtain electrode active material powder with the particle size of less than 0.1mm, and filtering and drying after alkaline washing to obtain a material to be treated;
(2) mixing the material obtained in the step (1) with NaHSO4、Na2SO3Performing ball milling and mixing on the mixed sodium salt according to the mass ratio of 1:5 to obtain a mixture to be roasted;
(3) roasting the mixture obtained in the step (2) in a muffle furnace, wherein the specific process parameters are as follows: the roasting temperature is 300 ℃, and the roasting time is 280 min;
(4) soaking the roasted material in water, and the specific process comprises the following steps: soaking in water at 15 deg.C for 25min to obtain 150g/L solid-liquid ratio, and filtering to obtain phosphorus-enriched solution and leached residue;
(5) carrying out evaporation concentration on the phosphorus enrichment solution by adopting an MVR system, wherein the evaporation temperature is 70 ℃, the volume of the evaporation residual solution is 10%, and filtering crystals and drying to obtain industrial-grade sodium phosphate; the leaching residue is leached by dilute phosphoric acid and dilute hydrochloric acid under oxygen pressure, and the specific process is as follows: the concentration of dilute phosphoric acid and dilute hydrochloric acid is 0.03mol/L, the temperature is 100 ℃, the time is 80min, the solid-to-liquid ratio is 150g/L, the oxygen partial pressure is controlled to be 0.7MPa, the kettle pressure is 1.0MPa, lithium enrichment liquid and iron enrichment slag are obtained by filtration, wherein the industrial iron oxide red is obtained by filtering and drying the iron enrichment slag;
(6) adding 30% sodium hydroxide solution into the lithium enrichment solution to adjust the pH of the lithium enrichment solution for impurity removal, and adding saturated sodium carbonate solution for precipitation to prepare battery-grade lithium carbonate;
the specific purification and impurity removal process is that the pH of the solution is firstly adjusted to 4.5 by adding NaOH under the condition of room temperature, and Fe (OH)3And Al (OH)3Removing Fe and Al, and continuously raising the pH value of the solution to 9.5 to obtain Cu (OH)2Removing Cu in the form of;
the lithium deposition process to obtain lithium carbonate includes adding NaOH to the leached liquid to regulate pH to 11.5 and controllingThe reaction temperature is 90 ℃ and saturated Na is added in a theoretical excess of 2 times2CO3Precipitating and filtering the solution after reacting for 50min to obtain battery grade Li2CO3The solution after lithium precipitation is used as mother solution for leaching subsequent filter residue;
the recovery rate of lithium exceeds 80 percent, and the obtained Li2CO3The purity of the iron oxide red is more than 99.95 percent, the recovery rate of iron phosphorus is more than 95 percent, the purity of the obtained iron oxide red is more than 99 percent, and the purity of the sodium phosphate is more than 98 percent.
Comparative example 1
Compared with the embodiment 1, the method for recovering the waste lithium iron phosphate battery by changing the adding amount of the NaOH ball-milling mixture comprises the following steps:
(1) soaking the waste lithium iron phosphate battery in 5% NaCl solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, then carrying out mechanical force integral crushing, roasting and screening to obtain electrode active material powder with the particle size of less than 0.1mm, and filtering and drying after alkaline washing to obtain a material to be treated;
(2) performing ball milling mixing on the material obtained in the step (1) and NaOH according to the mass ratio of 1:1 to obtain a mixture to be roasted;
(3) and (3) roasting the mixture obtained in the step (2) in a muffle furnace at a low temperature, wherein the specific process parameters are as follows: the roasting temperature is 250 ℃, and the roasting time is 30 min;
(4) soaking the roasted material in water, and the specific process comprises the following steps: soaking in water at 20 deg.C for 30min to obtain a solid-to-liquid ratio of 100g/L, and filtering to obtain phosphorus-enriched solution and leached residue;
(5) carrying out evaporation concentration on the phosphorus enrichment solution by adopting an MVR system, wherein the evaporation temperature is 60 ℃, the volume of the evaporation residual liquid is 50%, and filtering crystals and drying to obtain industrial-grade sodium phosphate; the leaching residue is leached by dilute sulphuric acid oxygen pressure, and the specific process is as follows: the concentration of sulfuric acid is 0.01mol/L, the temperature is 200 ℃, the time is 60min, the solid-to-liquid ratio is 100g/L, lithium enrichment liquid and iron enrichment slag are obtained through filtration, wherein the iron enrichment slag is filtered and dried to obtain industrial iron oxide red;
(6) adding 30% sodium hydroxide solution into the lithium enrichment solution to adjust the pH of the lithium enrichment solution for impurity removal, and adding saturated sodium carbonate solution for precipitation to prepare battery-grade lithium carbonate;
the specific purification and impurity removal process is that the pH of the solution is firstly adjusted to 4.5 by adding NaOH under the condition of room temperature, and Fe (OH)3And Al (OH)3Removing Fe and Al, and continuously raising the pH value of the solution to 9 to obtain Cu (OH)2Removing Cu in the form of;
the lithium deposition process to obtain lithium carbonate includes adding NaOH to the leached liquid to regulate pH value to 12, controlling reaction temperature at 80 deg.c and adding saturated Na in 2 times over theoretical amount2CO3Precipitating and filtering the solution after reacting for 60min to obtain battery grade Li2CO3The solution after lithium precipitation is used as mother solution for leaching subsequent filter residue;
the recovery rate of lithium is less than 55%, and the obtained Li2CO3The purity of the iron oxide red is more than 99.95 percent, the recovery rate of iron phosphorus is less than 70 percent, the purity of the obtained iron oxide red is less than 80 percent, and the purity of the sodium phosphate is more than 98 percent.
Comparative example 2
Compared with the embodiment 1, pure water is used as a leaching agent during oxygen pressure leaching, and the method for recovering the waste lithium iron phosphate battery comprises the following steps:
(1) soaking the waste lithium iron phosphate battery in 5% NaCl solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, then carrying out mechanical force integral crushing, roasting and screening to obtain electrode active material powder with the particle size of less than 0.1mm, and filtering and drying after alkaline washing to obtain a material to be treated;
(2) performing ball milling mixing on the material obtained in the step (1) and NaOH according to the mass ratio of 1:2 to obtain a mixture to be roasted;
(3) and (3) roasting the mixture obtained in the step (2) in a muffle furnace at a low temperature, wherein the specific process parameters are as follows: the roasting temperature is 250 ℃, and the roasting time is 30 min;
(4) soaking the roasted material in water, and the specific process comprises the following steps: soaking in water at 20 deg.C for 30min to obtain a solid-to-liquid ratio of 100g/L, and filtering to obtain phosphorus-enriched solution and leached residue;
(5) carrying out evaporation concentration on the phosphorus enrichment solution by adopting an MVR system, wherein the evaporation temperature is 60 ℃, the volume of the evaporation residual liquid is 50%, and filtering crystals and drying to obtain industrial-grade sodium phosphate; the leaching slag is leached by pure oxygen pressure, and the specific process is as follows: filtering at 200 ℃ for 60min at a solid-to-liquid ratio of 100g/L to obtain lithium enrichment liquid and iron enrichment slag, wherein the iron enrichment slag is filtered and dried to obtain industrial iron oxide red;
(6) adding 30% sodium hydroxide solution into the lithium enrichment solution to adjust the pH of the lithium enrichment solution for impurity removal, and adding saturated sodium carbonate solution for precipitation to prepare battery-grade lithium carbonate;
the specific purification and impurity removal process is that the pH of the solution is firstly adjusted to 4.5 by adding NaOH under the condition of room temperature, and Fe (OH)3And Al (OH)3Removing Fe and Al, and continuously raising the pH value of the solution to 9 to obtain Cu (OH)2Removing Cu in the form of;
the lithium deposition process to obtain lithium carbonate includes adding NaOH to the leached liquid to regulate pH value to 12, controlling reaction temperature at 80 deg.c and adding saturated Na in 2 times over theoretical amount2CO3Precipitating and filtering the solution after reacting for 60min to obtain battery grade Li2CO3The solution after lithium precipitation is used as mother solution for leaching subsequent filter residue;
the recovery rate of lithium is lower than 70 percent, and the obtained Li2CO3The purity of the iron oxide red is more than 99.95 percent, the recovery rate of iron phosphorus is more than 95 percent, the purity of the obtained iron oxide red is less than 90 percent, and the purity of sodium phosphate is more than 98 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (10)
1. A method for recovering waste lithium iron phosphate batteries is characterized by comprising the following steps:
(1) pretreating a waste lithium iron phosphate battery to obtain electrode active material powder, and performing alkali washing and drying to obtain a material to be treated;
(2) ball-milling and mixing the material to be treated obtained in the step (1) and sodium salt;
(3) roasting the mixture obtained in the step (2) in a muffle furnace to obtain a roasted material;
(4) leaching the roasted material obtained in the step (3) with low-temperature water, and filtering to obtain a phosphorus enrichment solution and leaching residues;
(5) evaporating and concentrating the phosphorus-enriched solution obtained in the step (4) to obtain industrial-grade sodium phosphate, and leaching residues by adopting diluted acid oxygen pressure to obtain a lithium-enriched solution and iron-enriched residues;
(6) and (5) purifying the lithium enrichment solution obtained in the step (5) to remove impurities, and adding a saturated sodium carbonate solution to prepare the battery-grade lithium carbonate.
2. The recycling method of the waste lithium iron phosphate batteries according to claim 1, characterized in that the pretreatment of the step (1) comprises short-circuit discharging, disassembling, crushing, roasting and screening the waste lithium iron phosphate batteries.
3. The method for recycling waste lithium iron phosphate batteries according to claim 1, wherein the sodium salt in the step (2) is NaOH or Na2CO3、NaHCO3、Na2SO4、NaHSO4、Na2SO3And/or NaCl; the mass ratio of the material to be treated to the sodium salt is controlled to be 1: (2-10).
4. The method for recycling the waste lithium iron phosphate batteries as claimed in claim 1, wherein in the roasting process in the step (3), the roasting temperature is controlled to be 150 ℃ and 500 ℃, and the roasting time is 30-300 min; the roasting temperature is preferably 200-300 ℃, and the roasting time is 30-90 min.
5. The method for recycling the waste lithium iron phosphate batteries according to claim 1, wherein in the low-temperature water leaching process in the step (4), the leaching temperature is controlled to be 0-30 ℃, the time is 10-30min, and the leaching solid-liquid ratio is controlled to be 50-200 g/L.
6. The method for recycling waste lithium iron phosphate batteries according to claim 1, wherein the phosphorus-enriched liquid obtained in the step (5) is subjected to evaporation concentration by an MVR system, the evaporation temperature is controlled to be 40-100 ℃, and the volume of the evaporation residual liquid is controlled to be 10-50%, so that industrial-grade Na is obtained3PO4·12H2O。
7. The recycling method of waste lithium iron phosphate batteries as claimed in claim 1, wherein in the dilute acid oxygen pressure leaching process in the step (5), the leaching temperature is controlled to be 100-; filtering and drying the iron-enriched slag to obtain the industrial-grade iron oxide red.
8. The method for recycling the waste lithium iron phosphate batteries according to claim 7, wherein the dilute acid is one or two of sulfuric acid, hydrochloric acid and phosphoric acid.
9. The method for recycling the waste lithium iron phosphate batteries according to claim 1, wherein in the process of purifying and decontaminating the lithium-rich liquid in the step (6), a NaOH solution with a mass fraction of 30% is added to adjust the pH of the lithium-rich liquid to 4-5 to remove iron and aluminum, and the pH of the solution is continuously raised to 8-10 to remove copper.
10. The recycling method of waste lithium iron phosphate batteries according to claim 1, characterized in that in the step (6), NaOH solution is added into leachate obtained by purifying and removing impurities from lithium-rich liquid to adjust the pH of the solution to 11-12, then saturated sodium carbonate solution with 2 times theoretical excess is added, the temperature is controlled to 80-90 ℃, the time is 30-60min, and battery grade Li is obtained by precipitation and filtration2CO3。
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