CN112062143A - Acid-free lithium carbonate preparation method using waste lithium ion battery as raw material - Google Patents
Acid-free lithium carbonate preparation method using waste lithium ion battery as raw material 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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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- 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
Abstract
A method for preparing lithium carbonate without acid by taking a waste lithium ion battery as a raw material relates to a method for recovering lithium carbonate by taking the waste lithium ion battery as the raw material. The invention aims to solve the problems that the pollution gas emission risk is large, the recovery efficiency is low, and the cost is high and difficult to be reduced in the existing process of recovering valuable metals in waste lithium ion batteries by high-temperature metallurgy; the hydrometallurgical recovery of valuable metals in waste lithium ion batteries has the technical problems of high acid-base and reducing agent consumption, serious metal loss in the separation process, difficult subsequent treatment of waste water and liquid, and high environmental load. The invention has selectivity to target metal Li, low regeneration cost, easy operation, low requirement on equipment corrosion prevention, high purity of the recovered lithium carbonate up to 95 percent, high lithium ion recovery rate up to 90 percent and high sodium chloride recovery rate up to 80 percent. The whole process of the invention does not add acid, alkali and reducing agent, does not generate harmful gas, does not discharge waste water and gas into the environment, and does not generate secondary pollution in the recovery process.
Description
Technical Field
The invention relates to a method for recycling lithium carbonate by taking a waste lithium ion battery as a raw material.
Background
The Lithium Ion Battery (LIB) has the advantages of good charging and discharging performance, high working voltage, high energy density, light product mass, long cycle life, good safety and the like, gradually replaces the traditional secondary batteries such as nickel-hydrogen batteries, nickel-cadmium batteries, lead storage batteries and the like from 1990 s, and is widely applied to renewable energy sources such as new energy automobiles, portable electronic and communication products, solar energy and the like as fixed energy storage equipment. The global battery market demand is expected to reach $ 999.8 billion in 2025, and the enormous energy demand will result in the consumption of large amounts of resources at 439.32 billion kilowatts. Because the service life of the lithium ion battery is generally 3-5 years, the problems of environmental pollution and resource waste caused by the waste lithium ion battery are increasingly prominent, and the problem of how to reasonably dispose the waste lithium ion battery is not negligible. The waste lithium ion battery not only contains high-grade lithium, but also contains a large amount of heavy metal elements such as nickel (Ni) and cobalt (Co) manganese (Mn), and toxic organic electrolyte and binder, thereby causing non-negligible influence on human health and ecological environment. The method has the advantages that the method can be used for recycling and harmlessly treating resources such as Co, Ni, Mn, Li, Al, Cu and the like in the waste lithium ion batteries, not only can the pollution of the discarded method for disposing the waste lithium ion batteries to the environment be overcome, but also the limited resources can be recycled, and the method has great economic benefit and great significance in the aspect of environmental protection.
At present, the recovery method of lithium in the anode material of the waste lithium ion battery mainly comprises hydrometallurgy and pyrometallurgy. The hydrometallurgical process has the advantages of low equipment requirement, simple process, convenient operation and relatively high metal recovery rate, but has high yieldThe effective recovery depends on the addition of strong acid, strong base and strong reducing agent, the prior report adopts hydrochloric acid, sulfuric acid, nitric acid, citric acid, malic acid and the like to dissolve the waste lithium ion battery, and acid-containing gas and NO are inevitably generated in the recovery processxWaste gas and waste water with high inorganic acid content and organic acid content cause serious secondary pollution to atmospheric environment and water environment; the dissolving process adopts higher acid concentration and adds reducing agents such as hydrogen peroxide or ammonium persulfate and the like, which has high requirements on the corrosion resistance of the recovery equipment; the subsequent treatment process after dissolution is long, and the cost is increased. The traditional high-temperature metallurgy directly carries out high-temperature incineration on the waste lithium ion battery to obtain metal alloy, a large amount of toxic and harmful gases such as chloride, dioxin and the like are generated in the process, the lithium evaporation loss amount is huge, the equipment requirement is high, and the metal recovery efficiency is low.
Eugonic aldrich et al (patent application No. CN107058742A) propose a method for recovering lithium from waste lithium ion batteries, which comprises the steps of dismantling and crushing the waste lithium ion batteries to obtain battery powder, purifying the acidic solution of the battery powder to obtain a lithium-containing solution, and then adjusting acid, extracting, washing, back-extracting, removing oil, evaporating, cooling, crystallizing, filtering, drying and the like to obtain anhydrous lithium salt. The method needs multiple steps of impurity removal, has complex working procedures, is easy to generate waste residues and waste water, and causes entrainment loss of lithium in different degrees in the links of purification, acid regulation, extraction and the like of the leaching solution, thereby causing low comprehensive recovery rate of the lithium. The invention provides a method for directly regenerating high-purity lithium carbonate from waste lithium ion batteries (patent application number CN201811337738.1), such as Li jin Hui, of Qinghua university, and the like, wherein the method comprises the steps of (1) crushing the waste lithium ion batteries and disassembling the waste lithium ion batteries to obtain lithium-containing positive material particles; (2) putting the lithium-containing positive electrode material particles obtained in the step (1), solid dry ice and zirconia grinding balls into a zirconia ball-milling tank for mechanochemical reaction; (3) and dissolving by using deionized water as a solvent, and then evaporating and crystallizing to obtain a high-purity lithium carbonate product. The invention utilizes solid dry ice to carry out ball milling mechanical reaction, realizes acid-free production, but the excessive release of carbon dioxide in the process causes overlarge pressure of a ball milling tank, and has the safety problem.
In conclusion, valuable metals in the waste lithium ion batteries are recovered through high-temperature metallurgy, the discharge risk of pollutant gases in the process is large, the recovery efficiency is low, and the cost is high and difficult to get down; the hydrometallurgy has the defects of large consumption of acid, alkali and reducing agents, serious metal loss in the separation process, difficult subsequent treatment of waste water and liquid, large environmental load and the like. Therefore, the research and development of a related process and technology which have no acid and alkali investment, no pollution gas emission and high resource recovery rate is a problem worthy of attention and research.
Disclosure of Invention
The invention aims to solve the problems that the pollution gas emission risk is large, the recovery efficiency is low, and the cost is high and difficult to be reduced in the existing process of recovering valuable metals in waste lithium ion batteries by high-temperature metallurgy; the technical problems of high acid-base and reducing agent consumption, serious metal loss in the separation process, difficult subsequent treatment of waste water and waste liquid and high environmental load exist in the hydrometallurgical recovery of valuable metals in the waste lithium ion batteries, and the acid-free preparation method of the lithium carbonate by using the waste lithium ion batteries as the raw materials is provided.
The method for preparing the lithium carbonate without the acid by taking the waste lithium ion battery as the raw material comprises the following steps:
firstly, crushing the anode material of the waste lithium ion battery into powder by using a mechanical crusher, loading the powder of the anode material of the waste lithium ion battery into an alumina crucible, then placing the alumina crucible into a tubular furnace, raising the temperature of the furnace to 500-650 ℃ at a heating rate of 1-10 ℃/min from room temperature, preserving the temperature for 0.5-6 h, then naturally cooling to room temperature (the roasting aims at removing a conductive agent and a binder), and sieving by using a 200-400-mesh sieve to obtain the waste lithium-containing anode material with the granularity of 0.037-0.075 mm;
secondly, putting the waste lithium-containing anode material prepared in the step one and calcium chloride into an agate mortar, grinding for 5-30 min until the two are fully mixed to obtain co-ground powder, putting the co-ground powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, heating the furnace to 400-1000 ℃ at a heating rate of 1-10 ℃/min from room temperature, keeping the temperature for 10-120 min, and naturally cooling to room temperature;
the waste lithium-containing positive electrode prepared in the step oneMaterial with CaCl2The mass ratio of (1) to (5);
thirdly, washing out the product in the alumina crucible roasted in the second step by using deionized water as a solvent, adding the product into a Buchner funnel, adding water for first suction filtration, and recovering the obtained filter residue which is waste residue containing nickel, cobalt and manganese elements;
adding lithium sulfate into the filtrate to remove calcium ions, wherein the mass ratio of the added lithium sulfate to the calcium chloride in the second step is 1 (1-1.25); adding the filtrate from which the calcium ions are removed into a Buchner funnel, adding water for secondary suction filtration, and recovering the obtained filter residue which is waste residue containing calcium sulfate; heating the filtrate obtained by the second suction filtration to 95-98 ℃, preserving heat for 30-120 min, then slowly adding a sodium carbonate aqueous solution, preserving heat for 30-50 min at 95-98 ℃, adding into a Buchner funnel, adding water for third suction filtration, washing the obtained filter residue with hot water for 1-3 times, and drying to obtain high-purity lithium carbonate; crystallizing the filtrate obtained by the third suction filtration in an evaporation crystallizer, and drying the crystal at 50-80 ℃ for 2-3 h to obtain sodium chloride; the crystallization conditions were: the vacuum degree is 0.012MPa to 0.015MPa, and the temperature is 60 ℃ to 80 ℃;
the concentration of the sodium carbonate aqueous solution is 1-3 mol/L;
the volume ratio of the sodium carbonate aqueous solution to the filtrate generated by the second suction filtration is 1 (10-20);
the temperature of hot water for washing filter residue obtained by the third suction filtration is 60-80 ℃.
Compared with the prior art, the method has the advantages of simple flow, low operation cost, selectivity to target metal Li, low regeneration cost, easy operation, low requirement on equipment corrosion resistance, high purity of the recovered lithium carbonate up to 95%, high lithium ion recovery rate up to 90%, high sodium chloride recovery rate up to 80% and high economic value.
The whole process of the invention does not add acid, alkali and reducing agent, does not generate harmful gas, the nickel, cobalt and manganese in the filter residue of the first suction filtration in the step three can be prepared into a precursor or directionally recovered, no waste water and gas is discharged into the environment, and no secondary pollution is generated in the recovery process.
Drawings
FIG. 1 is an XRD pattern;
FIG. 2 is an XPS spectrum.
Detailed Description
The first embodiment is as follows: the embodiment is a method for preparing lithium carbonate without acid by taking a waste lithium ion battery as a raw material, which is specifically carried out according to the following steps:
firstly, crushing the anode material of the waste lithium ion battery into powder by using a mechanical crusher, loading the powder of the anode material of the waste lithium ion battery into an alumina crucible, then placing the alumina crucible into a tubular furnace, raising the temperature of the furnace to 500-650 ℃ at a heating rate of 1-10 ℃/min from room temperature, preserving the temperature for 0.5-6 h, then naturally cooling to room temperature, and sieving by using a 200-400-mesh sieve to obtain the anode material of the waste lithium ion battery with the granularity of 0.037-0.075 mm;
secondly, putting the waste lithium-containing anode material prepared in the step one and calcium chloride into an agate mortar, grinding for 5-30 min until the two are fully mixed to obtain co-ground powder, putting the co-ground powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, heating the furnace to 400-1000 ℃ at a heating rate of 1-10 ℃/min from room temperature, keeping the temperature for 10-120 min, and naturally cooling to room temperature;
the waste lithium-containing positive electrode material prepared in the step one and CaCl2The mass ratio of (1) to (5);
thirdly, washing out the product in the alumina crucible roasted in the second step by using deionized water as a solvent, adding the product into a Buchner funnel, adding water for first suction filtration, and recovering the obtained filter residue which is waste residue containing nickel, cobalt and manganese elements;
adding lithium sulfate into the filtrate to remove calcium ions, wherein the mass ratio of the added lithium sulfate to the calcium chloride in the second step is 1 (1-1.25); adding the filtrate from which the calcium ions are removed into a Buchner funnel, adding water for secondary suction filtration, and recovering the obtained filter residue which is waste residue containing calcium sulfate; heating the filtrate obtained by the second suction filtration to 95-98 ℃, preserving heat for 30-120 min, then slowly adding a sodium carbonate aqueous solution, preserving heat for 30-50 min at 95-98 ℃, adding into a Buchner funnel, adding water for third suction filtration, washing the obtained filter residue with hot water for 1-3 times, and drying to obtain high-purity lithium carbonate; crystallizing the filtrate obtained by the third suction filtration in an evaporation crystallizer, and drying the crystal at 50-80 ℃ for 2-3 h to obtain sodium chloride; the crystallization conditions were: the vacuum degree is 0.012MPa to 0.015MPa, and the temperature is 60 ℃ to 80 ℃;
the concentration of the sodium carbonate aqueous solution is 1-3 mol/L;
the volume ratio of the sodium carbonate aqueous solution to the filtrate generated by the second suction filtration is 1 (10-20);
the temperature of hot water for washing filter residue obtained by the third suction filtration is 60-80 ℃.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the method for obtaining the anode material of the waste lithium ion battery in the first step comprises the following steps: soaking the waste lithium ion battery in a sodium chloride aqueous solution with the mass fraction of 5% -10% at room temperature for 12-72 h of discharge treatment, and then disassembling the waste lithium ion battery to obtain a positive plate; the waste lithium ion battery is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobaltate, lithium nickel manganate, lithium cobalt manganese, ternary nickel cobalt aluminum, lithium-containing alloy cathode, lithium titanate cathode and lithium-containing graphite cathode. The sodium chloride recovered in step three of the present embodiment can be reused in step one. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the method for obtaining the anode material of the waste lithium ion battery in the first step comprises the following steps: collecting the positive leftover materials generated in the manufacturing process of the lithium ion battery to obtain a positive plate; the lithium ion battery is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobaltate, lithium nickel manganate, lithium cobalt manganese, ternary nickel cobalt aluminum, lithium-containing alloy cathode, lithium titanate cathode and lithium-containing graphite cathode. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the present embodiment and toolOne of the first to third embodiments is different: the waste lithium-containing positive electrode material prepared in the step one in the step two and CaCl2The mass ratio of (A) to (B) is 1: 3. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: and in the third step, the temperature of hot water for washing the filter residue obtained by suction filtration for the third time is 80 ℃. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the volume ratio of the sodium carbonate aqueous solution in the third step to the filtrate generated by the second suction filtration is 1: 20. The rest is the same as the fifth embodiment.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the concentration of the sodium carbonate aqueous solution in the third step is 3 mol/L. The rest is the same as the sixth embodiment.
The invention was verified with the following tests:
test one: the test is a method for preparing lithium carbonate without acid by taking a waste lithium ion battery as a raw material, and is specifically carried out according to the following steps:
firstly, crushing the waste lithium ion battery anode material into powder by using a mechanical crusher, loading the waste lithium ion battery anode material powder into an alumina crucible, then placing the alumina crucible into a tubular furnace, raising the temperature of the furnace to 650 ℃ at a heating rate of 10 ℃/min from the room temperature, preserving the temperature for 3 hours, then naturally cooling to the room temperature, and sieving by using a 200-mesh sieve to obtain the waste lithium-containing anode material with the granularity of 0.075 mm;
the method for obtaining the anode material of the waste lithium ion battery comprises the following steps: soaking a scrapped lithium ion battery taking an NCM111 ternary material as a positive electrode in a sodium chloride aqueous solution with the mass fraction of 10% at room temperature for 72h of discharge treatment, and then disassembling the waste lithium ion battery to obtain a positive plate;
secondly, putting the waste lithium-containing positive electrode material prepared in the step one and calcium chloride into an agate mortar, grinding for 30min until the two are fully mixed to obtain co-ground powder, putting the co-ground powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, heating the furnace to 800 ℃ from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 60min, and naturally cooling to room temperature;
the waste lithium-containing positive electrode material prepared in the step one and CaCl2The mass ratio of (A) to (B) is 1: 3;
thirdly, washing out the product in the alumina crucible roasted in the second step by using deionized water as a solvent, adding the product into a Buchner funnel, adding water for first suction filtration, and recovering the obtained filter residue which is waste residue containing nickel, cobalt and manganese elements;
adding lithium sulfate into the filtrate to remove calcium ions, wherein the mass ratio of the added lithium sulfate to the calcium chloride in the second step is 1: 1; adding the filtrate from which the calcium ions are removed into a Buchner funnel, adding water for secondary suction filtration, and recovering the obtained filter residue which is waste residue containing calcium sulfate; heating the filtrate obtained by the second suction filtration to 98 ℃ and preserving heat for 60min, then slowly adding a sodium carbonate aqueous solution, preserving heat for 30min at 98 ℃, adding into a Buchner funnel, adding water for carrying out third suction filtration, washing the obtained filter residue with hot water for 3 times and drying to obtain high-purity lithium carbonate; crystallizing the filtrate obtained by the third suction filtration in an evaporation crystallizer, and drying the crystal at 80 ℃ for 3h to obtain sodium chloride; the crystallization conditions were: the vacuum degree is 0.015MPa, and the temperature is 80 ℃;
the concentration of the sodium carbonate aqueous solution is 3 mol/L;
the volume ratio of the sodium carbonate aqueous solution to the filtrate generated by the second suction filtration is 1: 20;
the temperature of hot water for washing filter residue obtained by the third suction filtration is 80 ℃.
Compared with the prior art, the test has the advantages of simple flow, low operation cost, selectivity to target metal Li, low regeneration cost, easy operation, low requirement on equipment corrosion resistance, high purity of the recovered lithium carbonate up to 95%, high lithium ion recovery rate up to 90%, high sodium chloride recovery rate up to 80% and high economic value.
The whole process of the test does not contain acid, alkali and reducing agent, harmful gas is not generated, the nickel, cobalt and manganese in the filter residue obtained by the first suction filtration in the third step can be prepared into a precursor or directionally recovered, no waste water and gas is discharged into the environment, and no secondary pollution is generated in the recovery process.
FIG. 1 is an XRD diagram, curve 1 is the waste residue containing nickel, cobalt and manganese obtained by the first suction filtration in the third step of test one, and curve 2 is the powder of the anode material of the waste lithium ion battery (unbaked), and it can be seen from the diagram that the (003) peak is obviously weakened before and after leaching, and the (004) peak is shifted to a lower angle, which shows that the content of Li between layers is reduced and the internal lattice structure is changed, corresponding to LiNi1/3Co1/3Mn1/3O2To NiO and Mn2O4Phase transformation.
Fig. 2 is an XPS spectrum, curve 1 is the waste residue containing nickel, cobalt and manganese obtained by the first suction filtration in the third step of the first test, and curve 2 is the powder (unfired) of the anode material of the waste lithium ion battery, and it can be seen from the XPS spectrum that the Li1s binding energy is present or absent before and after the peak leaching at 54.6ev, corresponding to the leaching of Li in the solid phase.
From the XRD and XPS analyses, it can be concluded that most of lithium in the solid phase of the electrode material before and after leaching is leached into the filtrate in the form of Li ions, while Ni, Co, Mn are still present in the solid phase in the form of oxides, thereby achieving efficient selective recovery of Li.
Claims (7)
1. A method for preparing lithium carbonate without acid by taking a waste lithium ion battery as a raw material is characterized in that the method for preparing lithium carbonate without acid by taking the waste lithium ion battery as the raw material is carried out according to the following steps:
firstly, crushing the anode material of the waste lithium ion battery into powder by using a mechanical crusher, loading the powder of the anode material of the waste lithium ion battery into an alumina crucible, then placing the alumina crucible into a tubular furnace, raising the temperature of the furnace to 500-650 ℃ at a heating rate of 1-10 ℃/min from room temperature, preserving the temperature for 0.5-6 h, then naturally cooling to room temperature, and sieving by using a 200-400-mesh sieve to obtain the anode material of the waste lithium ion battery with the granularity of 0.037-0.075 mm;
secondly, putting the waste lithium-containing anode material prepared in the step one and calcium chloride into an agate mortar, grinding for 5-30 min until the two are fully mixed to obtain co-ground powder, putting the co-ground powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, heating the furnace to 400-1000 ℃ at a heating rate of 1-10 ℃/min from room temperature, keeping the temperature for 10-120 min, and naturally cooling to room temperature;
the waste lithium-containing positive electrode material prepared in the step one and CaCl2The mass ratio of (1) to (5);
thirdly, washing out the product in the alumina crucible roasted in the second step by using deionized water as a solvent, adding the product into a Buchner funnel, adding water for first suction filtration, and recovering the obtained filter residue which is waste residue containing nickel, cobalt and manganese elements;
adding lithium sulfate into the filtrate to remove calcium ions, wherein the mass ratio of the added lithium sulfate to the calcium chloride in the second step is 1 (1-1.25); adding the filtrate from which the calcium ions are removed into a Buchner funnel, adding water for secondary suction filtration, and recovering the obtained filter residue which is waste residue containing calcium sulfate; heating the filtrate obtained by the second suction filtration to 95-98 ℃, preserving heat for 30-120 min, then slowly adding a sodium carbonate aqueous solution, preserving heat for 30-50 min at 95-98 ℃, adding into a Buchner funnel, adding water for third suction filtration, washing the obtained filter residue with hot water for 1-3 times, and drying to obtain high-purity lithium carbonate; crystallizing the filtrate obtained by the third suction filtration in an evaporation crystallizer, and drying the crystal at 50-80 ℃ for 2-3 h to obtain sodium chloride; the crystallization conditions were: the vacuum degree is 0.012MPa to 0.015MPa, and the temperature is 60 ℃ to 80 ℃;
the concentration of the sodium carbonate aqueous solution is 1-3 mol/L;
the volume ratio of the sodium carbonate aqueous solution to the filtrate generated by the second suction filtration is 1 (10-20);
the temperature of hot water for washing filter residue obtained by the third suction filtration is 60-80 ℃.
2. The method for preparing lithium carbonate without acid by using the waste lithium ion batteries as raw materials according to claim 1, wherein the method for obtaining the positive electrode materials of the waste lithium ion batteries in the step one comprises the following steps: soaking the waste lithium ion battery in a sodium chloride aqueous solution with the mass fraction of 5% -10% at room temperature for 12-72 h of discharge treatment, and then disassembling the waste lithium ion battery to obtain a positive plate; the waste lithium ion battery is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobaltate, lithium nickel manganate, lithium cobalt manganese, ternary nickel cobalt aluminum, lithium-containing alloy cathode, lithium titanate cathode and lithium-containing graphite cathode.
3. The method for preparing lithium carbonate without acid by using the waste lithium ion batteries as raw materials according to claim 1, wherein the method for obtaining the positive electrode materials of the waste lithium ion batteries in the step one comprises the following steps: collecting the positive leftover materials generated in the manufacturing process of the lithium ion battery to obtain a positive plate; the lithium ion battery is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobaltate, lithium nickel manganate, lithium cobalt manganese, ternary nickel cobalt aluminum, lithium-containing alloy cathode, lithium titanate cathode and lithium-containing graphite cathode.
4. The method for preparing lithium carbonate without acid by using waste lithium ion batteries as raw materials according to claim 1, wherein the waste lithium-containing cathode material prepared in the step one in the step two is mixed with CaCl2The mass ratio of (A) to (B) is 1: 3.
5. The method for preparing lithium carbonate without acid by using the waste lithium ion batteries as raw materials according to claim 1, wherein the temperature of hot water for washing filter residues obtained by suction filtration for the third time in the third step is 80 ℃.
6. The method for preparing lithium carbonate without acid by using the waste lithium ion batteries as raw materials according to claim 1, wherein the volume ratio of the sodium carbonate aqueous solution to the filtrate generated by the second suction filtration in the third step is 1: 20.
7. The method for preparing lithium carbonate without acid by using the waste lithium ion batteries as raw materials according to claim 1, wherein the concentration of the sodium carbonate aqueous solution in the step three is 3 mol/L.
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| CN113415814A (en) * | 2021-06-21 | 2021-09-21 | 南昌航空大学 | Method for selectively recovering lithium from waste lithium ion batteries by using ultralow-temperature roasting |
| CN114024057A (en) * | 2021-11-10 | 2022-02-08 | 湖南金凯循环科技有限公司 | Method for recycling waste nickel cobalt lithium manganate-lithium titanate battery |
| CN114890441A (en) * | 2022-05-16 | 2022-08-12 | 昆明理工大学 | Method for recovering lithium chloride and cobalt oxide from waste lithium cobaltate battery positive plate |
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| CN113415814A (en) * | 2021-06-21 | 2021-09-21 | 南昌航空大学 | Method for selectively recovering lithium from waste lithium ion batteries by using ultralow-temperature roasting |
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| CN114024057B (en) * | 2021-11-10 | 2023-08-04 | 湖南金凯循环科技有限公司 | Recycling method of waste nickel cobalt lithium manganate-lithium titanate battery |
| CN114890441A (en) * | 2022-05-16 | 2022-08-12 | 昆明理工大学 | Method for recovering lithium chloride and cobalt oxide from waste lithium cobaltate battery positive plate |
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