CN111994926A - Environment-friendly recovery method of lithium ion battery anode material - Google Patents
Environment-friendly recovery method of lithium ion battery anode material Download PDFInfo
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Abstract
The invention provides an environment-friendly recovery method of a lithium ion battery anode material, which comprises the steps of soaking an anode pole piece obtained by disassembling and decomposing a battery core of a lithium battery in an ammonium persulfate aqueous solution to obtain a lithium removal pole piece and a lithium-containing solution, then carrying out carbon dioxide precipitation and filtration on the lithium-containing solution to obtain lithium carbonate, soaking the lithium pole piece in an absolute ethyl alcohol solution of NMP to obtain lithium removal particles and a metal pole piece, and then carrying out soaking treatment on the lithium removal particles, CaO and SiO2Mixing and pulverizingThen plasma treatment is utilized to obtain the mixed particles of the iron silicate/the calcium silicate, and P is replaced by reaction at the same time2O5And introducing deionized water to obtain a phosphoric acid solution. According to the method provided by the invention, the lithium carbonate, the metal pole piece and the phosphoric acid can be separated out one by one through simple treatment, the whole process is free from acid-base assistance, the method is environment-friendly and simple in process, and meanwhile, the efficiency and the purity of the recovered lithium, phosphorus and metal are high, and the recovery and utilization effect is good.
Description
Technical Field
The invention relates to the technical field of recycling of lithium ion batteries, in particular to an environment-friendly recycling method of a lithium ion battery anode material.
Background
With the increasing demand of electric vehicles, smart grids and portable devices for energy storage systems, the consumption of lithium ion batteries is greatly accelerated. Since the life of the lithium ion battery is only 3-10 years, a large number of scrapped lithium batteries become a serious environmental problem which we have to face, and a large number of scrapped lithium batteries are expected to be generated in the next decade. According to the estimation of an authority, in 2021, only China has 65 million tons of waste lithium ion batteries to be recycled. Because plastic or metal shells, electrolyte salt and electrode waste materials in the waste lithium ion batteries have recovery values, the research and application of the recycling technology of the lithium batteries are generally regarded by people.
The outer layer of the lithium ion battery is wrapped by a plastic, aluminum and iron shell, and the inner layer is composed of a positive active material, a negative active material, an aluminum or copper foil current collector, a binder, a polyethylene or polypropylene porous diaphragm material, electrolyte salt dissolved in the electrolyte and the like. The positive electrode active material is mostly lithium cobaltate, lithium nickelate, lithium manganate, etc. Most of the negative electrode active materials are graphite, hard carbon, and soft carbon in which metal Li is embedded. The positive and negative active powder is coated on the aluminum foil or copper foil current collector through polyvinylidene fluoride adhesive to form the electrode. Among them, recycling of the positive electrode material is particularly important.
In recent years, the technology of recycling the positive electrode material of the lithium ion battery has been greatly improved, but the development of the recycling industry is still restricted by the high recycling cost and the practical operation problem, wherein most of the lithium iron phosphate batteries, which are commonly used lithium ion batteries, are currently recycled by aiming at lithium salts individually, and although the lithium iron phosphate batteries are not affected by transition metals, the recycling process is also complicated. Therefore, improvement of the recovery process of lithium iron phosphate is imperative.
The Chinese patent application No. 202010147050.8 discloses a comprehensive utilization method of waste lithium iron phosphate battery positive electrode powder, which comprises the steps of roasting and pretreating the lithium iron phosphate positive electrode powder in an aerobic environment; then sulfuric acid leaching is carried out, and then crude lithium liquid and slag are obtained through filtering; removing impurities from the leached material liquid, and adding ferric sulfate to remove aluminum and phosphate radicals; performing alkali conversion treatment on the leaching residue, performing alkali conversion on sodium hydroxide for more than half an hour, filtering, adjusting the pH value of filtrate by using sulfuric acid, heating, evaporating, concentrating and crystallizing to obtain sodium phosphate crystals; and (3) removing impurities from the crude lithium solution, heating the solution, and adding sodium carbonate to precipitate and dissolve lithium carbonate. Chinese patent application No. 202010224562.X discloses a resource recovery method and system of a waste lithium iron phosphate anode based on hydrochloric acid circulation, the recovery method comprises the steps of activating and screening the waste lithium iron phosphate anode to realize the separation of a current collector and a lithium iron phosphate active substance, then crushing and acid leaching with hydrochloric acid to obtain a solution containing ferrous chloride, lithium chloride and phosphoric acid, separating to obtain phosphoric acid by adopting an extraction method, realizing the separation of the phosphoric acid and the solution containing the ferrous chloride and the lithium chloride, then realizing the separation of Fe and Li by concentration pyrolysis and water leaching, and obtaining iron oxide red and a lithium chloride solution, and absorbing HCl generated in the pyrolysis process to obtain hydrochloric acid for recycling.
In order to promote the effective recycling of the positive electrode material of the lithium iron phosphate battery and solve the problems of large acid and alkali consumption and serious environmental pollution of the traditional recycling process, a novel recycling process of the positive electrode material of the lithium iron phosphate battery is necessary, and the efficient and environment-friendly recycling of the positive electrode material of the lithium iron phosphate battery is realized.
Disclosure of Invention
Aiming at the problems of large acid and alkali consumption and serious environmental pollution in the conventional lithium iron phosphate anode recovery process, the invention provides an environment-friendly recovery method of a lithium ion battery anode material, so that the lithium iron phosphate battery anode material is efficiently recycled, and meanwhile, the whole process is environment-friendly without acid-base assistance.
In order to solve the problems, the invention adopts the following technical scheme:
an environment-friendly recovery method of a lithium ion battery anode material is to disassemble and decompose a battery core of a lithium batteryThe cathode pole piece is placed in ammonium persulfate aqueous solution to be soaked to obtain a lithium removal pole piece and lithium-containing solution, then the lithium-containing solution is subjected to carbon dioxide precipitation and filtration to obtain lithium carbonate, meanwhile, the lithium pole piece is soaked in absolute ethyl alcohol solution of NMP to obtain lithium removal particles and a metal pole piece, and then the lithium removal particles, CaO and SiO are mixed with the lithium removal particles2Mixing, pulverizing, treating with plasma to obtain iron silicate/calcium silicate mixed granule, and reacting to displace P2O5And introducing deionized water to obtain a phosphoric acid solution. The specific method comprises the following steps:
(1) physically disassembling and decomposing a battery core wrapped by a lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in an ammonium persulfate aqueous solution for soaking for 50-60min, then taking out and drying the cathode pole piece to obtain a lithium pole piece removed and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP, then ultrasonically shaking for 30-40min, then soaking for 2-3h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) mixing the obtained lithium-removed particles with CaO and SiO2Mixing uniformly and pulverizing, then feeding pulverized mixed powder into plasma treatment reaction chamber by using hot air to make plasma heat treatment, removing lithium particles and Cao and SiO2The powder material is conveyed to the position near a plasma gun port through the feeding ports (1 and 3) in hot air, the bottom air inlets (6 and 7) are in a parallel dislocation state, the introduced mixed powder material and hot air flow form rotating airflow in the reaction zone (5), the powder material is melted at high temperature near the plasma gun port, the melted particles float and fully react in the reaction zone (5) and then drop, the mixture is cooled in the cooling zone (8) to form iron silicate/calcium silicate mixed particles, and the P displaced by reaction is simultaneously reacted2O5Deionized water is introduced along the air outlet (10) to obtain a phosphoric acid solution, so that the recovery of the lithium ion battery anode material is realized; the plasma heat treatment process is schematically shown in figures 1 and 2.
Preferably, the aqueous solution of ammonium persulfate in the step (1) is a saturated aqueous solution of ammonium persulfate.
Preferably, the mass concentration of the NMP anhydrous ethanol solution in the step (2) is 10-30 wt%.
Preferably, in the step (3), the lithium particles, CaO and SiO are removed in the preparation of the mixed powder2The mass ratio of (A) to (B) is 20-30: 2-3: 50-100.
Preferably, the particle size of the pulverized mixed powder in the step (3) is less than 200 μm.
Preferably, the temperature of the hot air in the step (3) is 200-300 ℃.
Preferably, the plasma gun in the step (3) is a nitrogen plasma gun, the power of the gun is 15-20kw, and the muzzle temperature is 2200-.
Preferably, in the plasma heat treatment in the step (3), an included angle between the feed port and the furnace tube wall is 30-70 degrees, and an included angle between the gas inlet and the furnace tube wall is 30-70 degrees.
Preferably, in the environment-friendly recovery process of the lithium ion battery cathode material in the step (1), the step (2) and the step (3), the liquid-solid ratio is 50-200 g/L.
The known waste lithium iron phosphate battery has high recovery cost, complex process and large acid and alkali dosage, and seriously pollutes the environment, thereby seriously restricting the development of the lithium ion battery recovery industry. The invention creatively extracts the lithium salt and the metal pole piece through the spontaneous conduction of the lithium ions, and the high-purity phosphoric acid is extracted through fusion replacement, thereby realizing the effective separation and the environmental-friendly recovery of all the raw materials of the lithium battery.
The method comprises the steps of firstly, placing a cathode pole piece soaked with electrolyte after a lithium iron phosphate battery pack is physically disassembled and decomposed into a saturated ammonium persulfate aqueous solution for soaking, reacting the lithium iron phosphate cathode pole piece with ammonium persulfate, taking out the pole piece for drying, leaching almost all lithium elements into the solution to obtain a lithium-removed pole piece and a lithium-containing solution, then introducing carbon dioxide for reaction to generate lithium carbonate precipitate, and filtering to recover the lithium carbonate.
Further, adding the dried lithium-removing pole piece into an absolute ethyl alcohol solution of NMP, soaking after ultrasonic oscillation to fully dissolve substances except the metal pole piece on the lithium-removing pole piece, taking out the pole piece, filtering and drying to obtain lithium-removing particles and the metal pole piece, wherein the lithium-removing particles mainly contain a phosphoric acid component.
Further, the lithium-removed particles are mixed with CaO and SiO2And after being uniformly mixed, crushing to obtain mixed powder, and sending the mixed powder into a plasma heat treatment reaction chamber for treatment. In the plasma heat treatment process, hot air conveys mixed powder to the vicinity of a plasma gun port through feed inlets (1 and 3) with certain included angles, bottom air inlets (6 and 7) also have certain included angles with the wall of a furnace tube and are in a parallel dislocation state, so that the introduced mixed powder and air flow form rotary air flow in a reaction zone (5), the powder is rapidly melted into a liquid drop shape and stays in the reaction zone under the action of the rotary air flow, the liquid drops melted by particles are fully reacted through the rotary air flow, and the accumulation of excessive melted powder is avoided, thereby effectively improving the treatment efficiency of the powder and the yield of phosphoric acid; the molten particles float in the reaction zone (5) and react sufficiently, then drip down, are cooled in the cooling zone (8) to form iron silicate/calcium silicate mixed particles, and P displaced by the reaction2O5Introducing deionized water along the gas outlet (10) to obtain a phosphoric acid solution; the whole process does not need acid-base assistance, and is environment-friendly.
The existing lithium iron phosphate anode has the problems of serious environmental pollution due to large recycling amount of acid and alkali, and the application of the existing lithium iron phosphate anode is limited. In view of the above, the invention provides an environment-friendly recovery method of a lithium ion battery anode material, which comprises the steps of physically disassembling and decomposing a battery core of a lithium battery pack to obtain a cathode pole piece soaked with electrolyte, soaking the pole piece in an ammonium persulfate aqueous solution, taking out the pole piece and drying to obtain a lithium pole piece and a lithium-containing solution, and precipitating and filtering the lithium-containing solution by carbon dioxide to obtain lithium carbonate; soaking the dried pole piece in an absolute ethyl alcohol solution of NMP, continuously soaking after ultrasonic oscillation, taking out the pole piece, filtering and drying to obtain a lithium particle-removed pole piece and a metal pole piece; removing lithium particles, CaO and SiO2Uniformly mixing and crushing, feeding the mixed powder into a reaction cavity by using hot air, and removing lithium particles, Cao and SiO2Passing in hot air with a retaining clipThe feeding hole of the corner is conveyed to the position near the plasma gun mouth, the bottom air inlet is in a parallel dislocation state, the introduced powder and the air flow form a rotating air flow in the reaction zone, the powder is melted at the high temperature near the plasma gun mouth, the melted particles float and fully react in the reaction zone and then drip down, the iron silicate/calcium silicate mixed particles are formed after being cooled in the cooling zone, and P replaced by the reaction2O5And introducing deionized water along the gas outlet to obtain a phosphoric acid solution. According to the method provided by the invention, the lithium carbonate, the metal pole piece and the phosphoric acid can be separated out one by one through simple treatment, the whole process is free from acid-base assistance, the method is environment-friendly and simple in process, and meanwhile, the efficiency and the purity of the recovered lithium, phosphorus and metal are high, and the recovery and utilization effect is good.
The invention provides an environment-friendly recovery method of a lithium ion battery anode material, which has the outstanding characteristics and excellent effects compared with the prior art that:
1. according to the invention, the lithium carbonate, the metal pole piece and the phosphoric acid can be separated out by phase through simple treatment, acid-base assistance is not required in the whole process, the method is environment-friendly, and meanwhile, the method is simple in process, high in recovery rate and good in recycling effect.
2. The invention firstly extracts lithium salt through lithium ion spontaneous conduction and divides the lithium salt into metal pole pieces, and then removes lithium particles, CaO and SiO by plasma heat treatment2The high-purity phosphoric acid is extracted by melting and displacement, and in the plasma heat treatment process, the powder is quickly melted into a liquid drop shape and stays in a reaction area under the action of rotating airflow, so that the added powder is fully reacted; meanwhile, the liquid drops melted by the particles are fully reacted through the rotating airflow, so that excessive melting powder is prevented from being accumulated, and the treatment efficiency of the powder and the yield of phosphoric acid are effectively improved.
Drawings
FIG. 1: a process schematic diagram of a plasma processing reaction chamber; wherein, 1 is feed inlet 1, 2 is the nitrogen gas inlet, 3 is feed inlet 2, 4 is the plasma gun, 5 is the reaction zone, 6 is hot-air inlet 1, 7 is hot-air inlet 2, 8 is the cooling space, 9 is the collecting region, 10 is the gas outlet, 11 is the deionized water.
FIG. 2: a top view of the plasma processing reaction chamber; wherein, 12 is a feed inlet 1, 13 is a feed inlet 2, 14 is a hot air inlet 1, 15 is a hot air inlet 2, and 16 is a plasma gun.
FIG. 3: the reaction flow schematic diagram of the lithium ion battery environmental protection recovery method is provided.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Physically disassembling and decomposing a battery core wrapped by a lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in a saturated ammonium persulfate aqueous solution for soaking for 55min, then taking out and drying the cathode pole piece to obtain a lithium pole piece and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP with the mass concentration of 20wt%, then ultrasonically oscillating for 35min, then soaking for 2.5h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) 25kg of the delithiated granules obtained were admixed with 2.5kg of CaO and 75kg of SiO2Mixing uniformly and pulverizing to particle size less than 200 μm, then delivering the pulverized mixed powder into a plasma treatment reaction chamber with 250 deg.C hot air for plasma heat treatment, removing lithium particles and Cao, SiO2The powder is conveyed to the vicinity of a plasma gun port through a feeding port (1 and 3) in hot air, the plasma gun is a nitrogen plasma spray gun, the power of the spray gun is 18kw, the temperature of the gun port is 2300 ℃, bottom air inlets (6 and 7) are in a parallel dislocation state, so that introduced mixed powder and hot air form rotating air flow in a reaction zone (5), the included angle between the feeding port and the furnace pipe wall is 50 degrees, the included angle between the air inlets and the furnace pipe wall is 50 degrees, and the powder is in plasma treatmentMelting at high temperature near the muzzle, allowing the molten particles to float in the reaction zone (5), reacting sufficiently, dripping, cooling in the cooling zone (8) to form iron silicate/calcium silicate mixed particles, and reacting the displaced P2O5Deionized water is introduced along the air outlet (10) to obtain a phosphoric acid solution, so that the recovery of the lithium ion battery anode material is realized;
in the environment-friendly recovery process of the lithium ion battery anode material, the liquid-solid ratio is 120 g/L.
Example 2
(1) Physically disassembling and decomposing a battery core wrapped by a lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in a saturated ammonium persulfate aqueous solution to soak for 52min, then taking out and drying the cathode pole piece to obtain a lithium pole piece and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP with the mass concentration of 15wt%, then ultrasonically oscillating for 32min, then soaking for 2h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) the obtained 22kg of delithiated particles were mixed with 2.2kg of CaO, 90kg of SiO2Mixing uniformly and pulverizing to particle size less than 200 μm, then delivering the pulverized mixed powder into a plasma treatment reaction chamber with 220 deg.C hot air for plasma heat treatment, removing lithium particles and Cao, SiO2The powder is conveyed to the vicinity of a plasma gun port through a feeding port (1 and 3) in hot air, the plasma gun is a nitrogen plasma spray gun, the power of the spray gun is 16kw, the temperature of the gun port is 2250 ℃, bottom air inlets (6 and 7) are in a parallel dislocation state, the fed mixed powder and hot air form a rotating air flow in a reaction zone (5), in the plasma heat treatment, the included angle between the feeding port and the furnace pipe wall is 40 degrees, the included angle between the air inlets and the furnace pipe wall is 40 degrees, the powder is melted at the high temperature in the vicinity of the plasma gun port, the melted particles float and fully react in the reaction zone (5) and then drip, the melted particles are cooled by a cooling zone (8) to form iron silicate/calcium silicate mixed particles, and P replaced by reaction is simultaneously2O5Deionized water is introduced along the air outlet (10) to obtain a phosphoric acid solution, so that the recovery of the lithium ion battery anode material is realized;
in the environment-friendly recovery process of the lithium ion battery anode material, the liquid-solid ratio is 80 g/L.
Example 3
(1) Physically disassembling and decomposing a battery core wrapped by the lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in a saturated ammonium persulfate aqueous solution for soaking for 58min, then taking out and drying the cathode pole piece to obtain a lithium pole piece and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP with the mass concentration of 25wt%, then ultrasonically oscillating for 38min, then soaking for 3h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) 28kg of the delithiated granules obtained were admixed with 2.8kg of CaO and 60kg of SiO2Mixing uniformly and pulverizing to particle size less than 200 μm, then delivering the pulverized mixed powder into a plasma treatment reaction chamber with 280 deg.C hot air for plasma heat treatment, removing lithium particles and Cao, SiO2The powder is conveyed to the vicinity of a plasma gun port through a feeding hole (1 and 3) in hot air, the plasma gun is a nitrogen plasma spray gun, the power of the spray gun is 19kw, the temperature of the gun port is 2350 ℃, bottom air inlets (6 and 7) are in a parallel dislocation state, the fed mixed powder and hot air form a rotating air flow in a reaction zone (5), the included angle between the feeding hole and the furnace pipe wall is 60 degrees and the included angle between the air inlets and the furnace pipe wall is 60 degrees, the powder is melted at the high temperature in the vicinity of the plasma gun port, the melted particles float and fully react in the reaction zone (5) and then drip, the iron silicate/calcium silicate mixed particles are formed after being cooled in a cooling zone (8), and simultaneously P replaced by reaction2O5Deionized water is introduced along the air outlet (10) to obtain a phosphoric acid solution, so that the recovery of the lithium ion battery anode material is realized;
in the environment-friendly recovery process of the lithium ion battery anode material, the liquid-solid ratio is 180 g/L.
Example 4
(1) Physically disassembling and decomposing a battery core wrapped by a lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in a saturated ammonium persulfate aqueous solution for soaking for 50min, then taking out and drying the cathode pole piece to obtain a lithium pole piece and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP with the mass concentration of 10wt%, then ultrasonically oscillating for 30min, then soaking for 2h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) 20kg of the obtained delithiated particles were mixed with 2kg of CaO and 100kg of SiO2Mixing uniformly and pulverizing to particle size less than 200 μm, then delivering the pulverized mixed powder into a plasma treatment reaction chamber with hot air of 200 deg.C for plasma heat treatment, removing lithium particles and Cao, SiO2The powder is conveyed to the vicinity of a plasma gun port through a feeding port (1 and 3) in hot air, the plasma gun is a nitrogen plasma spray gun, the power of the spray gun is 15kw, the temperature of the gun port is 2200 ℃, bottom air inlets (6 and 7) are in a parallel dislocation state, the fed mixed powder and hot air form a rotating air flow in a reaction zone (5), in the plasma heat treatment, the included angle between the feeding port and the furnace pipe wall is 30 degrees, the included angle between the air inlets and the furnace pipe wall is 30 degrees, the powder is melted at the high temperature in the vicinity of the plasma gun port, the melted particles float and fully react in the reaction zone (5) and then drip down, the iron silicate/calcium silicate mixed particles are formed after being cooled by a cooling zone (8), and simultaneously P replaced by reaction2O5Deionized water is introduced along the air outlet (10) to obtain a phosphoric acid solution, so that the recovery of the lithium ion battery anode material is realized;
in the environment-friendly recovery process of the lithium ion battery anode material, the liquid-solid ratio is 50 g/L.
Example 5
(1) Physically disassembling and decomposing a battery core wrapped by a lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in a saturated ammonium persulfate aqueous solution for soaking for 60min, then taking out and drying the cathode pole piece to obtain a lithium pole piece and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP with the mass concentration of 30wt%, then ultrasonically oscillating for 40min, then soaking for 3h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) 30kg of the obtained delithiated particles were mixed with 3kg of CaO and 50kg of SiO2Mixing uniformly and pulverizing to particle size less than 200 μm, then sending the pulverized mixed powder into a plasma treatment reaction chamber with hot air of 300 deg.C for plasma heat treatment, removing lithium particles and Cao, SiO2Conveying the powder material to the vicinity of a plasma gun port through feed inlets (1 and 3) in hot air, wherein the plasma gun is a nitrogen plasma spray gun, the power of the spray gun is 20kw, the temperature of the gun port is 2400 ℃, bottom air inlets (6 and 7) are in a parallel dislocation state, so that the introduced mixed powder material and hot air flow form rotating air flow in a reaction zone (5), in the plasma heat treatment, the included angle between the feed inlet and the furnace pipe wall is 70 degrees, the included angle between the air inlet and the furnace pipe wall is 70 degrees, the powder material is melted at the high temperature in the vicinity of the plasma gun port, the melted particles float and fully react in the reaction zone (5) and then drip down, the melted particles are cooled by a cooling zone (8) to form iron silicate/calcium silicate mixed particles, and P replaced2O5Deionized water is introduced along the air outlet (10) to obtain a phosphoric acid solution, so that the recovery of the lithium ion battery anode material is realized;
in the environment-friendly recovery process of the lithium ion battery anode material, the liquid-solid ratio is 200 g/L.
Comparative example 1
Comparative example 1 referring to the process of patent CN111333046A, an acid solution is used to leach and recycle the positive electrode material of a lithium ion battery.
The test method comprises the following steps:
and (3) testing the recovery effect: with reference to the detection method in GB/T30835-; further referring to detection methods in GB/T2091-2008 'industrial phosphoric acid' and GB/T11075-2013 'lithium carbonate', the impurity rates of the lithium source and the phosphorus source collected in the first step are detected. The test results are shown in table 1.
Table 1:
as can be seen from table 1, the method of comparative example 1, in which acid leaching is used, and aluminum and phosphate radicals are displaced by using iron salts after respective acid and alkali treatments, has low displacement efficiency, requires a large amount of acid and alkali solutions, is not environment-friendly, and has high corrosion to equipment; in the recovery method in examples 1 to 5, the lithium carbonate, the pole piece and the phosphoric acid are separated by phase, and particularly, in the separation process of the phosphoric acid, the efficient continuous separation is realized by the airflow suspension molten liquid, so that the method is simple, the separation efficiency is high, the dephosphorization and delithiation rate is high, and the impurity content is low.
Claims (9)
1. An environment-friendly recovery method of a lithium ion battery anode material is characterized in that the recovery method comprises the steps of soaking a cathode pole piece, which is obtained after a battery core of a lithium battery is disassembled and decomposed, in an ammonium persulfate aqueous solution to obtain a lithium removal pole piece and a lithium-containing solution, then carrying out carbon dioxide precipitation and filtration on the lithium-containing solution to obtain lithium carbonate, soaking the lithium pole piece in an absolute ethyl alcohol solution of NMP to obtain lithium removal particles and metal pole pieces, and then carrying out lithium removal particle and CaO and SiO2Mixing, pulverizing, treating with plasma to obtain iron silicate/calcium silicate mixed granule, and reacting to displace P2O5And introducing deionized water to obtain a phosphoric acid solution. The specific method comprises the following steps:
(1) physically disassembling and decomposing a battery core wrapped by a lithium iron phosphate battery to obtain a cathode pole piece soaked with electrolyte, then placing the cathode pole piece in an ammonium persulfate aqueous solution for soaking for 50-60min, then taking out and drying the cathode pole piece to obtain a lithium pole piece removed and a lithium-containing solution, and then precipitating and filtering the lithium-containing solution by introducing carbon dioxide to obtain lithium carbonate;
(2) soaking the dried lithium-removed pole piece in an absolute ethyl alcohol solution of NMP, then ultrasonically shaking for 30-40min, then soaking for 2-3h, taking out the pole piece, filtering and drying to obtain lithium-removed particles and a metal pole piece;
(3) mixing the obtained lithium-removed particles with CaO and SiO2Mixing uniformly and pulverizing, then feeding pulverized mixed powder into plasma treatment reaction chamber by using hot air to make plasma heat treatment, removing lithium particles and Cao and SiO2Conveying the powder material to the vicinity of a plasma gun mouth through a feeding hole in hot air, wherein a bottom air inlet is in a parallel dislocation state, so that the introduced mixed powder material and hot air form rotating air flow in a reaction zone, the powder material is melted at high temperature in the vicinity of the plasma gun mouth, the melted particles float and fully react in the reaction zone and then drip down, the iron silicate/calcium silicate mixed particles are formed after cooling in a cooling zone, and simultaneously P replaced by reaction2O5And introducing deionized water along the gas outlet to obtain a phosphoric acid solution, thereby realizing the recovery of the lithium ion battery anode material.
2. The environment-friendly recovery method of the lithium ion battery cathode material according to claim 1, wherein the ammonium persulfate aqueous solution in the step (1) is a saturated ammonium persulfate aqueous solution.
3. The environment-friendly recovery method of the lithium ion battery cathode material as claimed in claim 1, wherein the mass concentration of the absolute ethyl alcohol solution of NMP in the step (2) is 10-30 wt%.
4. The environment-friendly recovery method of the lithium ion battery cathode material as claimed in claim 1, wherein in the step (3), in the preparation of the mixed powder, lithium particles, CaO and SiO are removed2The mass ratio of (A) to (B) is 20-30: 2-3: 50-100.
5. The environment-friendly recycling method for lithium ion battery cathode material according to claim 1, wherein the particle size of the crushed mixed powder in the step (3) is less than 200 μm.
6. The environmental-friendly recycling method for lithium ion battery anode material as claimed in claim 1, wherein the temperature of the hot air in the step (3) is 200-300 ℃.
7. The environment-friendly recycling method for lithium ion battery anode material as claimed in claim 1, wherein the plasma gun in the step (3) is a nitrogen plasma spray gun, the spray gun power is 15-20kw, and the muzzle temperature is 2200-2400 ℃.
8. The environment-friendly recovery method of the lithium ion battery cathode material according to claim 1, wherein in the plasma heat treatment in the step (3), an included angle between the feed port and the furnace tube wall is 30-70 degrees, and an included angle between the gas inlet and the furnace tube wall is 30-70 degrees.
9. The environment-friendly recycling method of the lithium ion battery cathode material according to claim 1, wherein in the environment-friendly recycling process of the lithium ion battery cathode material in the steps (1), (2) and (3), the liquid-solid ratio is 50-200 g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114804049A (en) * | 2022-06-13 | 2022-07-29 | 中南大学 | Method for recovering and obtaining high-purity iron phosphate from waste lithium iron phosphate batteries |
| CN115353129A (en) * | 2022-09-27 | 2022-11-18 | 厦门海辰储能科技股份有限公司 | Method for recycling anode material of waste lithium iron phosphate battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114804049A (en) * | 2022-06-13 | 2022-07-29 | 中南大学 | Method for recovering and obtaining high-purity iron phosphate from waste lithium iron phosphate batteries |
| CN114804049B (en) * | 2022-06-13 | 2023-12-12 | 中南大学 | Method for recovering high-purity ferric phosphate from lithium iron phosphate waste batteries |
| CN115353129A (en) * | 2022-09-27 | 2022-11-18 | 厦门海辰储能科技股份有限公司 | Method for recycling anode material of waste lithium iron phosphate battery |
| CN115353129B (en) * | 2022-09-27 | 2023-09-01 | 厦门海辰储能科技股份有限公司 | Method for recycling anode material of waste lithium iron phosphate battery |
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