CN114644326A - Method and device for catalytically recovering black powder of waste lithium ion battery - Google Patents

Method and device for catalytically recovering black powder of waste lithium ion battery Download PDF

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CN114644326A
CN114644326A CN202210209978.3A CN202210209978A CN114644326A CN 114644326 A CN114644326 A CN 114644326A CN 202210209978 A CN202210209978 A CN 202210209978A CN 114644326 A CN114644326 A CN 114644326A
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black powder
lithium ion
waste lithium
ion battery
oxidant
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刘雅婷
陈传林
檀智祥
吴宇鹏
程光生
李安国
韩恒
苏俊
黄兵
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Jiujiang Tinci Advanced Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
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    • C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • 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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

The invention relates to the field of lithium ion batteries, in particular to a method and a device for catalytically recovering black powder of a waste lithium ion battery, electronic equipment and a computer readable storage medium. The catalytic recovery method of the black powder of the waste lithium ion battery comprises the following steps: pretreating a waste lithium ion battery to obtain black powder, wherein the black powder comprises lithium iron phosphate, copper and aluminum;adding water into the black powder, stirring to prepare slurry, adding soluble ferric iron salt into the slurry for reaction, adding an oxidant and an inorganic acid solution for reaction, filtering the slurry after the reaction is finished to obtain a solid containing iron phosphate, and obtaining the rest of the solid containing Li+、Cu2+、Al3+、Fe3+The solution of (1). Therefore, in the catalytic recovery process of the black powder, the required additive materials are reasonably used and recovered, and the recovery steps are simplified. The invention also provides a waste lithium ion battery black powder catalytic recovery device, electronic equipment and a computer readable storage medium.

Description

Method and device for catalytically recovering black powder of waste lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a method for catalytically recovering black powder of a waste lithium ion battery, a device for catalytically recovering black powder of a waste lithium ion battery, electronic equipment and a computer readable storage medium.
Background
The waste lithium ion battery mainly comprises an outer packaging material, electrolyte, a positive pole piece, a negative pole piece and a plastic film. The existing waste lithium ion battery recovery process generally adopts the steps of crushing, sorting, thermal decomposition, re-sorting, impurity removal, precipitation and replacement to realize the recovery. The black mixture obtained after the recleaning step is generally referred to as "black powder". The black powder is obtained by crushing the whole waste lithium ion battery and performing pretreatment, so that the black powder inevitably comprises aluminum in the positive electrode piece and copper in the negative electrode piece besides main components of a negative electrode active material, lithium iron phosphate and lithium fluoride. In the black powder recovery step including lithium iron phosphate, copper, and aluminum, two methods are generally used for recovery. The first is to add a large amount of inorganic acid solution to black powder to dissolve blackThe powder is then oxidized by adding an oxidizing agent and the pH is adjusted to obtain a precipitate of iron phosphate, but also Al3+The precipitate of (4). Wherein the pH adjustment step requires a base to neutralize the large amount of acid added in the initial step. This results in low purity of the recovered iron phosphate and waste of the added materials. Secondly, adding a large amount of soluble ferric iron salt into the black powder to obtain ferric phosphate precipitate, filtering to obtain ferric phosphate, and adding a large amount of oxidant into the residual solution to react with Fe2+Oxidation of Fe3+Adding PO thereto4 3-And reacting to obtain the iron phosphate. Thus, the consumption of the soluble ferric salt is large, and a step of recovering a large amount of iron again is added.
Disclosure of Invention
The method aims to solve the problems of how to reasonably use and recycle required added materials and simplify the recycling step in the recycling process of the black powder of the waste lithium ion battery. The invention provides a method and a device for catalytically recovering black powder of a waste lithium ion battery, electronic equipment and a computer readable storage medium.
In a first aspect, the invention provides a method for catalytically recovering black powder of a waste lithium ion battery, which comprises the following steps:
step S11, performing pretreatment on the waste lithium ion battery to obtain black powder, wherein the black powder comprises lithium iron phosphate, copper and aluminum;
step S12, adding water into the black powder, stirring to prepare slurry, adding soluble ferric iron salt into the slurry for reaction, adding an oxidant and an inorganic acid solution for reaction, filtering the slurry after reaction to obtain a solid containing iron phosphate, and the balance being Li+、Cu2+、Al3+、Fe3+The solution of (1).
In some embodiments, the molar amount of the soluble ferric salt is 0.01-1 times of the molar amount of iron in the black powder, wherein the soluble ferric salt comprises one or more of ferric sulfate, ferric chloride and ferric nitrate.
In some embodiments, the re-oxidizer is reacted with the mineral acid solution, wherein the oxidizer is added in one or more portions.
In some embodiments, the oxidant is added in one or more times, and the molar amount of the oxidant added in one time or the total molar amount of the oxidant added in multiple times is 0.1-2 times of the molar amount of iron in the black powder, wherein the oxidant comprises one or more of oxygen, air, ozone, peroxymonosulfuric acid, hydrogen peroxide, peroxydisulfuric acid, ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite and sodium perchlorate.
In some embodiments, the oxidizing agent is added in one or more portions, wherein the total time between the initial addition of the oxidizing agent to the complete addition and completion of the reaction is between 2 hours and 6 hours.
In some embodiments, the re-oxidizer is reacted with a solution of inorganic acid, wherein the inorganic acid is used to adjust the pH of the slurry to 0.5 to 3, and wherein the inorganic acid comprises one or more of sulfuric acid, phosphoric acid, nitric acid, perchloric acid, hydrochloric acid, hydrofluoric acid, and hydrobromic acid.
In some embodiments, the temperature at which the additional oxidizer and the mineral acid solution are reacted is from 10 ℃ to 90 ℃.
In a second aspect, the present invention provides a catalytic recovery device for black powder of a waste lithium ion battery, which is characterized in that the catalytic recovery device for black powder of a waste lithium ion battery comprises:
the pretreatment device 21 is used for pretreating the waste lithium ion battery to obtain black powder, wherein the black powder comprises lithium iron phosphate, copper and aluminum;
a separating device 22, configured to add water to the black powder and stir the black powder to prepare a slurry, add a soluble ferric salt to the slurry for reaction, add an oxidant and an inorganic acid solution for reaction, filter the reacted slurry to obtain a solid containing iron phosphate, and the remainder is Li+、Cu2+、Al3+、Fe3+The solution of (1).
In a third aspect, the present invention provides an electronic device comprising: a memory to store instructions; and the processor is used for calling the instructions stored in the memory to execute the catalytic recovery method of the waste lithium ion battery in any one of the first aspect.
In a fourth aspect, the present invention provides a computer-readable storage medium storing instructions, which when executed by a processor, perform the method for catalytically recovering a used lithium ion battery according to any one of the first aspects.
In order to solve the problems of how to reasonably use and recycle the required added materials and the simplified recycling steps in the recycling process of the black powder. The invention has the following advantages:
adding water into the black powder, stirring to prepare slurry, adding soluble ferric salt into the slurry for reaction, and then adding inorganic acid and an oxidant. Fe in soluble ferric salts3+Can be rapidly reacted with PO in lithium iron phosphate4 3-The iron phosphate precipitate is generated by conversion and combination, and simultaneously the Fe in the lithium iron phosphate is released2+，Fe2+Reacting with oxidant to produce Fe3+. Therefore, the conversion of the lithium iron phosphate is accelerated, and the catalytic effect is achieved. Simultaneously avoids the multiplied increase of the iron-containing by-product caused by only using soluble ferric salt, and can also overcome the defect of Fe in the lithium iron phosphate when only using an oxidant2+The oxidation efficiency is low. The pH value is adjusted by adding a small amount of inorganic acid after adding soluble ferric salt in the step S12, so that copper and aluminum in the black powder can be changed into Cu2+And Al3+Dissolution in the slurry also prevents precipitation of aluminum phosphate, preventing its mixing with the filtered solids and facilitating separation separately in the next process.
Drawings
Fig. 1 shows a flow diagram of a black powder recovery method for a waste lithium ion battery according to some embodiments;
FIG. 2 shows a black powder recycling device diagram of a waste lithium ion battery according to some embodiments;
fig. 3 shows a schematic diagram of an electronic device.
Detailed Description
The content of the invention will now be discussed with reference to a number of exemplary embodiments. It is to be understood that these examples are discussed only to enable those of ordinary skill in the art to better understand and thus implement the teachings of the present invention, and are not meant to imply any limitations on the scope of the invention.
As used herein, the term "include" and its variants are to be read as open-ended terms meaning "including, but not limited to. The term "based on" is to be read as "based, at least in part, on". The terms "one embodiment" and "an embodiment" are to be read as "at least one embodiment". The term "another embodiment" is to be read as "at least one other embodiment".
The lithium ion battery has the advantages of high voltage, small volume, high specific energy, small self-discharge, high safety and the like, and is widely applied to the fields of consumer electronics, electric vehicles, industrial energy storage and the like. With the rapid development of the new energy automobile industry, the reserve of new energy automobiles in China is rapidly increased, and the retirement amount of lithium ion batteries is continuously increased. According to statistics of solid waste and chemical management technical departments of China ministry of ecological environment, the accumulative amount of China retired lithium ion batteries is about 20 ten thousand tons in 2020, and the amount of the China retired lithium ion batteries is estimated to exceed 70 ten thousand tons in 2025. Therefore, recycling of spent lithium ion batteries becomes critical. The recycling of black powder, which is one of the important links in the recycling of lithium ion batteries, is also becoming more and more important.
The embodiment discloses a method 10 for catalytically recovering black powder of a waste lithium ion battery, which is used for catalytically recovering black powder of a waste lithium ion battery, and as shown in fig. 1, the method may include steps S11 to S12, and the following respectively describes the above in detail:
step S11, performing pretreatment on the waste lithium ion battery to obtain black powder, wherein the black powder comprises lithium iron phosphate, copper and aluminum.
In the embodiment of the disclosure, the waste lithium ion battery to be recovered is firstly pretreated, and mainly subjected to crushing treatment, volatilization treatment, first sorting treatment, cracking treatment and second sorting treatment to obtain black powder containing copper and aluminum. The crushing can be performed after the waste lithium ion battery is discharged, so that potential safety hazards are avoided; or the crushing can be directly carried out in an inert gas environment without carrying out discharge treatment, thereby improving the recovery efficiency. Lithium ion batteries including cylindrical steel shell batteries, square aluminum shell batteries and square soft package batteries can be subjected to crushing treatment in the pretreatment process of the waste lithium ion batteries. And volatilizing the solvent in the electrolyte of the waste lithium ion battery by volatilization treatment, and condensing to recover the electrolyte solvent. The separation treatment is used for separating the crushed materials, and the separated materials comprise a shell, a pile head and a plastic film, so that the amount of substances to be treated in the cracking step is reduced, and the efficiency is improved. The cracking treatment decomposes the binder in the crushed material and separates the materials bonded together so as to separate different materials by a second separation; the cracking treatment can also be carried out in two steps, firstly, the electrolyte in the crushed material is decomposed into gaseous phosphorus pentafluoride and solid lithium fluoride, and then the cracking temperature is increased to decompose the adhesive after the gaseous phosphorus pentafluoride is recovered. And the copper and the aluminum can be recovered through second separation, and black powder containing a small amount of copper and aluminum is obtained after the copper and the aluminum are remained. In some embodiments, also in the production process of the lithium ion battery, the positive pole piece which is poor due to production can obtain a black mixture after being subjected to crushing treatment, cracking treatment and secondary separation treatment. And unqualified products or overdue products generated in the production and use processes of the lithium iron phosphate material. Such black mixtures, lithium iron phosphate defective products and expired products may also be referred to as "black powders", and may also be recovered as recovered raw materials by the present method.
Step S12, adding water into the black powder, stirring to prepare slurry, adding soluble ferric salt into the slurry for reaction, adding an oxidant and an inorganic acid solution for reaction, filtering the slurry after reaction to obtain a solid containing ferric phosphate, and the balance being Li+、Cu2+、Al3+、Fe3+The solution of (1).
In the embodiment of the disclosure, the black powder is put into the separation device 22, and water with the weight 2-10 times of that of the black powder can be added and stirred to prepare slurry, so that other reactants can be added and then fully mixed, and the reaction speed is improved; firstly adding soluble ferric salt which is 0.01-1 time of the molar weight of iron in the black powder into the slurry for reaction, and adding Fe3+And PO in lithium iron phosphate in black powder4 3-The reaction generates precipitated iron phosphate and releases Fe2+(ii) a Then adding inorganic acid and black powderOxidizing agent with 0.1-2 times of molar weight of the content of the medium iron, stirring and reacting for 2-6 hours at the temperature of 10-90 ℃ to generate iron phosphate precipitate, then filtering to obtain solid containing iron phosphate, and the rest containing Li+、Cu2+、Al3+、Fe3+The filtrate of (1). In step S12, a small amount of soluble ferric salt, Fe in the small amount of soluble ferric salt, in combination with an oxidizing agent is used3+Can be rapidly reacted with PO in lithium iron phosphate4 3-The iron phosphate precipitate is generated by conversion and combination, and simultaneously the Fe in the lithium iron phosphate is released2+，Fe2+Reacting with oxidant to produce Fe3+. Therefore, the conversion of the lithium iron phosphate is accelerated, and the catalytic effect is achieved. Simultaneously avoids the multiplied increase of the iron-containing by-product caused by only using soluble ferric salt, and can also overcome the defect of Fe in the lithium iron phosphate when only using an oxidant2+The oxidation efficiency is low. The pH value is adjusted by adding a small amount of inorganic acid after adding soluble ferric salt in the step S12, so that copper and aluminum in the black powder can be changed into Cu2+And Al3+Dissolution in the slurry also prevents precipitation of aluminum phosphate, preventing its mixing in the filtered solids and facilitating separation separately in the next process.
In some embodiments, the molar amount of the soluble ferric salt is 0.01 to 1 times of the molar amount of iron in the black powder, wherein the soluble ferric salt comprises one or more of ferric sulfate, ferric chloride and ferric nitrate.
In the embodiment, only 0.01-1 time of the molar weight of the iron in the black powder is needed to be added into the soluble ferric salt3+Act as a catalyst to promote the generation of iron phosphate; the soluble ferric salt comprises one or more of ferric sulfate, ferric chloride and ferric nitrate, can be rapidly dissolved in the aqueous solution and provides Fe3+. In other embodiments, the molar weight of the soluble ferric salt can be 0.2-0.4 times of the molar weight of iron in the black powder, so that the normal reaction can be ensured, and the reasonable amount is controlled. In other embodiments, the soluble ferric salt can be ferric sulfate, which is not highly corrosive and does not contribute to the reaction assemblyPut higher demands on SO4 2-The method can not react with other ions in the whole process to generate precipitate substances to influence the recovery.
In some embodiments, the re-oxidizer is reacted with the mineral acid solution, wherein the oxidizer is added in one or more portions.
In this example, the oxidizing agent is added in one or more portions, which allows the reaction to proceed completely. In other embodiments, the oxidant may be added 4 times, and the amount of each time of addition may be 1/4 of the total amount, so that the addition of the oxidant by several times can be uniform, the oxidant is prevented from being distributed locally and concentrated to oxidize copper and aluminum substances, and the amount of the oxidant can be controlled reasonably.
In some embodiments, the oxidant is added in one or more times, and the molar amount of the oxidant added in one time or the total molar amount of the oxidant added in multiple times is 0.1-2 times of the molar amount of iron in the black powder, wherein the oxidant comprises one or more of oxygen, air, ozone, peroxymonosulfuric acid, hydrogen peroxide, peroxydisulfuric acid, ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite and sodium perchlorate.
In the embodiment, the oxidant with 0.1-2 times of the molar weight of the iron in the black powder is used for adding Fe in the slurry2+Oxidation to Fe3+Then Fe3+Then with PO in lithium iron phosphate4 3-Reacting to generate iron phosphate; the oxidant comprises one or more of oxygen, air, ozone, peroxymonosulfuric acid, hydrogen peroxide, peroxydisulfuric acid, ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite and sodium perchlorate, and can be provided for oxidizing Fe2+. In some embodiments, the molar weight of the oxidant can be 0.5-1.0 times of the molar weight of iron in the black powder, so that normal reaction can be ensured, and the reasonable amount of the oxidant can be controlled. In other embodiments, the oxidant may be hydrogen peroxide, which is readily available and low in cost.
In some embodiments, the oxidizing agent is added in one or more portions, wherein the total time between the initial addition of the oxidizing agent to the complete addition and completion of the reaction is between 2 hours and 6 hours.
In this embodiment, the oxidizing agent is added in one or more portions, wherein the total time from the beginning of the addition of the oxidizing agent to the completion of the addition and the completion of the reaction is 2 to 6 hours, which ensures the completion of the reaction. In other embodiments, the oxidizing agent may be added in 1 portion, and the total time may be 2 hours to 4 hours, which may ensure completion of the reaction. In some other embodiments, the oxidant can be added 4 times, the total time can be 2 hours to 4 hours, and the reaction time of each time is 0.5 hour to 1 hour, so that complete completion of each reaction can be ensured, and the dosage of the oxidant can be accurately controlled by adding the oxidant for multiple times.
In some embodiments, the re-oxidizer is reacted with a solution of inorganic acid, wherein the inorganic acid is used to adjust the pH of the slurry to 0.5 to 3, and wherein the inorganic acid comprises one or more of sulfuric acid, phosphoric acid, nitric acid, perchloric acid, hydrochloric acid, hydrofluoric acid, and hydrobromic acid.
In the embodiment, the inorganic acid is used for adjusting the pH value to be 0.5-3, so that the copper and aluminum in the black powder can be changed into Cu2+And Al3+Dissolution in the slurry also prevents precipitation of aluminum phosphate, preventing its mixing with the filtered solids and facilitating separation separately in the next process. The inorganic acid comprises one or more of sulfuric acid, phosphoric acid, nitric acid, perchloric acid, hydrochloric acid, hydrofluoric acid and hydrobromic acid, so that the pH value can be conveniently adjusted. In other embodiments, the inorganic acid is used for adjusting the pH value to 1-2, so that the normal reaction can be ensured, and the reasonable dosage can be controlled. Meanwhile, in order to reach the pH value required by the reaction, the addition of the inorganic acid can be divided into a plurality of times, and the addition amount of each time is based on whether the pH value of the actual solution is in a range or not. In other embodiments, the mineral acid may be hydrochloric acid, since hydrochloric acid more readily removes oxides from the aluminum surface.
In some embodiments, the oxidizing agent and the mineral acid solution are added at a reaction temperature of 10 ℃ to 90 ℃.
In this embodiment, the reaction temperature of the added oxidant and the inorganic acid solution is 10 ℃ to 90 ℃, so that the normal reaction can be ensured. In other embodiments, the reaction temperature may be 50 ℃ to 60 ℃, which not only ensures the reaction to be completed quickly, but also saves energy consumption.
The embodiment discloses a method for catalytically recovering black powder of a waste lithium ion battery, which comprises the following implementation steps:
and (3) putting 1t of waste lithium ion battery into a crushing device, and crushing under the protection of nitrogen to obtain a third battery crushed object, wherein the diameter of the crushed object is 10 mm.
And volatilizing the third battery crushed object in a low-temperature volatilization rotary kiln at the temperature of 140 ℃ under the nitrogen protection environment for 90 minutes, condensing the volatilized gas in a condensation recovery device at the condensation temperature of 5 ℃ to obtain 77.9kg of solvent of the electrolyte of the waste lithium ion battery, and obtaining the rest of the fourth battery crushed object.
And conveying the fourth battery crushed object to a closed and bent conveying pipeline, introducing nitrogen airflow into an inlet of the conveying pipeline, arranging a plurality of air suction holes on the upper side of the conveying pipeline, connecting the air suction holes on the upper side with a negative pressure ventilating pipeline, and taking away the plastic film with lower density, the electrolyte and the positive and negative electrode plates in a separated manner by the airflow in the negative pressure ventilating pipeline. The bent conveying pipeline increases the tumbling of the crushed materials in the pipeline, and the separation of the step is more complete. This gave 125.5kg of a mixture of jacket and spud head. The plastic film, the electrolyte and the positive and negative electrode plates which are taken away by the airflow enter a sorting device with small negative pressure, the plastic film with smaller density is separated out by the negative pressure airflow, 56.3kg of plastic film is obtained, and the rest is the first battery crushed object containing the electrolyte and the positive and negative electrode plates.
And cracking the crushed first battery in a first cracking device for 90 minutes at the temperature of 250 ℃ in the environment of nitrogen protection, so that the electrolyte lithium hexafluorophosphate is cracked to obtain solid lithium fluoride and gaseous phosphorus pentafluoride. And (3) carrying the gas phosphorus pentafluoride into an absorption device containing potassium fluoride solution through nitrogen gas flow, wherein the concentration of the potassium fluoride solution is 1.8mol/L, reacting with potassium fluoride to obtain potassium hexafluorophosphate, recycling to obtain the hexafluorophosphate, and leaving the second tail gas. And (3) introducing the second tail gas into an absorption device containing a potassium fluoride solution again, wherein the concentration of the potassium fluoride solution is 1.8mol/L, reacting with potassium fluoride to obtain potassium hexafluorophosphate, recycling to obtain hexafluorophosphate, and leaving the third tail gas. The two absorption solutions were absorbed and recovered to obtain 4.2kg of potassium hexafluorophosphate. And after the first cracking is finished, the second battery crushed object containing lithium fluoride and positive and negative pole pieces is remained.
And under the environment of 560 ℃ and nitrogen protection, cracking the second crushed battery in a second cracking device for 90 minutes to remove the adhesive in the positive and negative electrode plates, separating the copper foil from the negative electrode material in the negative electrode plate, simultaneously separating the aluminum foil from the lithium iron phosphate in the positive electrode plate, and leaving the fifth crushed battery containing lithium fluoride, the copper foil, the aluminum foil, graphite and the lithium iron phosphate.
Screening the crushed fifth battery by using a screen, and separating black powder containing lithium fluoride, graphite, lithium iron phosphate, a small amount of copper and a small amount of aluminum impurities to obtain 540.5kg of black powder. The rest copper foil and aluminum foil enter a gravity sorting device for primary sorting to respectively obtain an aluminum foil containing a small amount of copper foil and a copper foil containing a small amount of aluminum foil; the aluminum foil containing a small amount of copper foil enters a gravity sorting device for sorting again to separate the small amount of copper foil from the aluminum foil, so as to obtain the copper foil and the aluminum foil respectively; the copper foil containing a small amount of aluminum foil enters a gravity sorting device for sorting again to separate the small amount of aluminum foil from the copper foil; carrying out gravity separation twice to respectively obtain 96.3kg of copper foil and 36.8kg of aluminum foil; the copper foil and the aluminum foil form granular copper particles and aluminum particles during the separation process.
540.5kg of black powder is put into a separation device 22, 3t of water is added and stirred to prepare slurry, 243.2kg of ferric sulfate hexahydrate is added, 43.2kg of sulfuric acid and 54.1kg of hydrogen peroxide are added for 4 times, and the stirring reaction is carried out at 55 ℃ after the interval of 45 minutes between the addition of the sulfuric acid and the hydrogen peroxide each time; after the 4 th addition of the sulfuric acid and the hydrogen peroxide, the mixture is stirred and reacted for 60 minutes at 55 ℃, and then the mixture is filtered by a filtering device to obtain a mixture of 249.7kg of iron phosphate and 203.2kg of graphite and Li+、Cu2+、Al3+、Fe2+、Fe3+The solution of (1). In the step, a small amount of ferric sulfate and hydrogen peroxide are combined, and Fe in the small amount of ferric sulfate3+Can be rapidly reacted with PO in lithium iron phosphate4 3-The iron phosphate precipitate is generated by conversion and combination, and simultaneously the Fe in the lithium iron phosphate is released2+，Fe2+Reacting with hydrogen peroxide to generate Fe3 +. Therefore, the conversion of the lithium iron phosphate is accelerated, and the catalytic effect is achieved. Meanwhile, the method avoids the multiplied increase of iron-containing byproducts caused by only using ferric sulfate and can overcome the defect of low conversion efficiency of the lithium iron phosphate when only using hydrogen peroxide. In the step, a small amount of hydrochloric acid is added, so that the simple substances of copper and aluminum in the black powder can be changed into Cu2+And Al3+Dissolved in water to prevent it from mixing in the filtered solids and facilitate separation separately in the next step.
To contain Li+、Cu2+、Al3+、Fe2+、Fe3+Adding 35.1kg of iron powder into the solution, heating to 55 ℃, reacting for 2h, and filtering to respectively obtain 11.4kg of sponge copper solid and Li+、Al3+、Fe2+The first filtrate of (1).
Adding 5% NaOH solution into the first filtrate, reacting at 30 deg.C and pH 5.0 for 0.5 hr, and filtering to obtain 18.9kg aluminum hydroxide solid and Li+、Fe2+The second filtrate of (1).
Adding 73.0 kg of concentrated sulfuric acid, 89.7kg of hydrogen peroxide and 238.4kg of sodium phosphate into the second filtrate, and stirring and reacting at 55 ℃ for 2 hours to respectively obtain 218.9kg of iron phosphate and Li-containing lithium+The third filtrate of (4);
to the third filtrate, 5.0% NaOH solution was added to adjust pH to 10.6, and 99.5kg sodium carbonate was added to obtain 69.2kg lithium carbonate and a recyclable filtrate. The recovery of lithium was 98.8%.
It will be understood by those skilled in the art that the foregoing embodiments are specific to a particular implementation of the invention and that various changes in form and detail may be made therein without departing from the spirit and scope of the invention in its practical application.
Based on the same inventive concept, the present disclosure further provides a catalytic recycling apparatus 20 for black powder of waste lithium ion batteries, which is used for recycling black powder of waste lithium ion batteries, as shown in fig. 2:
the pretreatment device 21 is used for pretreating the waste lithium ion battery to obtain black powder, wherein the black powder comprises copper and aluminum.
In the embodiment of the present disclosure, the pretreatment device 21 crushes the waste lithium ion batteries to obtain a third crushed battery; volatilizing the third battery crushed object to obtain a fourth battery crushed object and fourth tail gas; condensing the introduced fourth tail gas to obtain a liquid electrolyte solvent; and separating the fourth broken battery, recovering the plastic film, the shell and the pile head, and leaving the first broken battery comprising the electrolyte and the positive and negative pole pieces. Cracking the first battery crushed object comprising electrolyte and positive and negative pole pieces, and cracking the electrolyte into solid lithium fluoride and gaseous phosphorus pentafluoride to obtain a second battery crushed object comprising the lithium fluoride and the positive and negative pole pieces and first tail gas comprising the phosphorus pentafluoride; absorbing the first tail gas by using a first absorption liquid, and reacting to obtain hexafluorophosphate and a second tail gas; and absorbing the second tail gas by using a second absorption liquid, and reacting to obtain hexafluorophosphate and a third tail gas. Cracking the second battery crushed object, and removing the adhesive in the positive and negative electrode plates to obtain a fifth battery crushed object and a sixth tail gas, wherein the fifth battery crushed object comprises lithium fluoride, copper, aluminum, a negative electrode active material and lithium iron phosphate; and sorting the crushed materials of the fifth battery, recovering copper and aluminum, and obtaining black powder comprising lithium fluoride, graphite, lithium iron phosphate, a small amount of copper and a small amount of aluminum in the rest.
A separating device 22, configured to add water to the black powder and stir the black powder to prepare a slurry, add a soluble ferric salt to the slurry for reaction, add an oxidant and an inorganic acid solution for reaction, filter the reacted slurry to obtain a solid containing iron phosphate, and leave a remainder including Li+、Cu2+、Al3+、Fe3+The solution of (1).
In the embodiment of the present disclosure, the black powder is put into the separation device 22, water is added and stirred to prepare a slurry, the slurry is firstly added with the soluble ferric salt for reaction, then the oxidant and the inorganic acid solution are added for reaction, a solid containing the iron phosphate is obtained by filtration, and the remainder is Li+、Cu2+、Al3+、Fe3+The solution of (1). Thus recyclingAnd the iron phosphate also changes the copper and aluminum into an ionic state to be dissolved in the solution, so that the copper and aluminum are prevented from being mixed in the iron phosphate.
As shown in fig. 3, one embodiment of the present disclosure provides an electronic device 400. The electronic device 400 includes a memory 401, a processor 402, and an Input/Output (I/O) interface 403. The memory 401 is used for storing instructions. And the processor 402 is configured to call the instruction stored in the memory 401 to execute the method for catalytically recovering the black powder of the waste lithium ion battery according to the embodiment of the disclosure. The processor 402 is connected to the memory 401 and the I/O interface 403 respectively, for example, via a bus system and/or other connection mechanism (not shown). The memory 401 may be used to store programs and data, including the programs of the catalytic recycling method for black powder of waste lithium ion batteries according to the embodiments of the present disclosure, and the processor 402 executes various functional applications and data processing of the electronic device 400 by running the programs stored in the memory 401.
The processor 402 in the embodiment of the present disclosure may be implemented in at least one hardware form of a Digital Signal Processor (DSP), a Field-Programmable Gate Array (FPGA), a Programmable Logic Array (PLA), and the processor 402 may be one or a combination of several Central Processing Units (CPUs) or other Processing units with data Processing capability and/or instruction execution capability.
Memory 401 in the disclosed embodiments may comprise one or more computer program products that may include various forms of computer-readable storage media, such as volatile memory and/or non-volatile memory. The volatile Memory may include, for example, a Random Access Memory (RAM), a cache Memory (cache), and/or the like. The nonvolatile Memory may include, for example, a Read-Only Memory (ROM), a Flash Memory (Flash Memory), a Hard Disk Drive (HDD), a Solid-State Drive (SSD), or the like.
In the embodiment of the present disclosure, the I/O interface 403 may be used to receive input instructions (e.g., numeric or character information, and generate key signal inputs related to user settings and function control of the electronic device 400, etc.), and may also output various information (e.g., images or sounds, etc.) to the outside. The I/O interface 403 may include one or more of a physical keyboard, function keys (e.g., volume control keys, switch keys, etc.), a mouse, a joystick, a trackball, a microphone, a speaker, a touch panel, and the like in embodiments of the present disclosure.
It is to be understood that although operations are depicted in the drawings in a particular order, this is not to be understood as requiring that such operations be performed in the particular order shown or in serial order, or that all illustrated operations be performed, to achieve desirable results. In certain environments, multitasking and parallel processing may be advantageous.
The methods and apparatus of embodiments of the present disclosure can be accomplished with standard programming techniques with rule-based logic or other logic to accomplish the various method steps. It should also be noted that the words "means" and "module," as used herein and in the claims, is intended to encompass implementations using one or more lines of software code, and/or hardware implementations, and/or equipment for receiving inputs.
Any of the steps, operations, or procedures described herein may be performed or implemented using one or more hardware or software modules, alone or in combination with other devices. In one embodiment, the software modules are implemented using a computer program product comprising a computer readable medium embodying computer program code, which is executable by a computer processor to perform any or all of the described steps, operations, or procedures.
The foregoing description of implementations of the present disclosure has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the disclosure. The embodiments were chosen and described in order to explain the principles of the disclosure and its practical application to enable one skilled in the art to utilize the disclosure in various embodiments and with various modifications as are suited to the particular use contemplated.

Claims (10)

1. A catalytic recovery method of black powder of waste lithium ion batteries is characterized by comprising the following steps:
step S11, performing pretreatment on the waste lithium ion battery to obtain black powder, wherein the black powder comprises lithium iron phosphate, copper and aluminum;
step S12, adding water into the black powder, stirring to prepare slurry, adding soluble ferric iron salt into the slurry for reaction, adding an oxidant and an inorganic acid solution for reaction, filtering the slurry after reaction to obtain a solid containing iron phosphate, and the balance being Li+、Cu2+、Al3+、Fe3+The solution of (1).
2. The catalytic recovery method for the black powder of the waste lithium ion battery according to claim 1, wherein the molar amount of the soluble ferric salt is 0.01 to 1 time of the molar amount of iron in the black powder, and the soluble ferric salt comprises one or more of ferric sulfate, ferric chloride and ferric nitrate.
3. The method for catalytically recovering the black powder of the waste lithium ion battery as claimed in claim 1, wherein the re-adding of the oxidant and the inorganic acid solution are carried out, wherein the oxidant is added in one or more times.
4. The catalytic recovery method of the black powder of the waste lithium ion battery according to claim 3, wherein the oxidant is added in one or more times, the molar weight of the oxidant added in one time or in multiple times is 0.1-2 times of the molar weight of iron in the black powder, and the oxidant comprises one or more of oxygen, air, ozone, peroxymonosulfuric acid, hydrogen peroxide, peroxydisulfuric acid, ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite and sodium perchlorate.
5. The method for catalytically recovering the black powder of the waste lithium ion battery according to claim 3, wherein the oxidant is added in one or more times, and the total time of the oxidant which is added from the beginning to the whole and is reacted is 2 to 6 hours.
6. The catalytic recovery method of black powder of waste lithium ion batteries according to claim 1, wherein the re-oxidant is reacted with an inorganic acid solution, wherein the inorganic acid is used for adjusting the pH of the slurry to 0.5-3, and wherein the inorganic acid comprises one or more of sulfuric acid, phosphoric acid, nitric acid, perchloric acid, hydrochloric acid, hydrofluoric acid, and hydrobromic acid.
7. The catalytic recovery method of black powder of waste lithium ion batteries according to claim 1, characterized in that the temperature of the reaction of adding the oxidant and the inorganic acid solution is 10 ℃ to 90 ℃.
8. The utility model provides a waste lithium ion battery black powder catalysis recovery unit which characterized in that, waste lithium ion battery black powder catalysis recovery unit includes:
the pretreatment device is used for pretreating the waste lithium ion battery to obtain black powder, wherein the black powder comprises lithium iron phosphate, copper and aluminum;
the separation device is used for adding water into the black powder and stirring the black powder to prepare slurry, firstly adding soluble ferric salt into the slurry for reaction, then adding an oxidant and an inorganic acid solution for reaction, filtering the slurry after the reaction to obtain a solid containing iron phosphate, and the rest is Li+、Cu2+、Al3+、Fe3+The solution of (1).
9. An electronic device, comprising: a memory to store instructions; and the processor is used for calling the instruction stored by the memory to execute the catalytic recovery method of the black powder of the waste lithium ion battery as claimed in any one of claims 1 to 7.
10. A computer readable storage medium, storing instructions, which when executed by a processor, perform the method for catalytic recovery of black powder from waste lithium ion batteries according to any one of claims 1 to 7.
CN202210209978.3A 2022-03-03 2022-03-03 Method and device for catalytically recovering black powder of waste lithium ion battery Pending CN114644326A (en)

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