CN106848469A - A kind of method that valuable metal is reclaimed in the material from waste lithium ion cell anode - Google Patents

Abstract

A kind of method the invention discloses valuable metal is reclaimed in material from waste lithium ion cell anode, the method is waste and old lithium ion battery to be discharged, is disassembled, and sub-elects anode pole piece；The anode pole piece carries out pyrolysis degumming, isolates collector and active material；The active material mixes with chlorate, carries out chloridising roasting；Chloridising roasting solid product carries out water logging and goes out, and obtains the leachate containing valuable metal ions.Being leached this method avoid traditional waste lithium ion cell anode material metal needs the defect of a large amount of inorganic bronsted lowry acids and bases bronsted lowries of consumption in removal process, and process is simple, with low cost, environment-friendly, with great industrial applications value.

Description

A method for recovering valuable metals from waste lithium-ion battery cathode materials

technical field

The invention relates to a method for recycling waste batteries, in particular to a method for efficiently recovering valuable metals from waste lithium ion battery positive electrode materials through a chlorination roasting method, and belongs to the field of renewable resources.

Background technique

With the rapid development of lithium-ion batteries, lithium-ion batteries have occupied the portable consumer electronics market, and continue to expand their market territory to new energy electric vehicles and smart grids. In 2015, the total output of lithium-ion batteries in China was 47.13Gwh, of which, the output of consumer lithium-ion batteries was 23.69Gwh, accounting for 50.26%; the output of power batteries was 16.9Gwh, accounting for 36.07%; the output of energy storage lithium-ion batteries was 1.73Gwh, accounting for 3.67% . As the market expands, the demand for lithium-ion batteries continues to increase, which brings about a series of problems, the most important of which is the recycling and disposal of used lithium-ion batteries. It is estimated that by 2020, the demand for power lithium-ion batteries will reach 125Gwh, and the amount of scrap will reach 2.2Gwh, about 500,000 tons; by 2023, the amount of scrapped will reach 101Gwh, about 1.16 million tons.

At present, the commonly used cathode materials for lithium-ion batteries on the market mainly include lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, nickel-cobalt-manganese ternary cathode materials, and lithium iron phosphate. There have been researches at home and abroad on the recovery of valuable metals such as Ni, Co, and Mn in positive electrode materials. The method widely used at present is to add the positive electrode active material into sulfuric acid, nitric acid, hydrochloric acid and use hydrogen peroxide as the reducing agent to leach the valuable metals in the active material. This "strong acid + reducing agent" method can effectively recover valuable metal ions, and the reducing agent such as hydrogen peroxide can reduce the high-valent metal ions in the active material to a low-valent state, which is conducive to improving the leaching rate. However, this method needs to consume a large amount of inorganic acid in the recycling process, and a large amount of alkali needs to be added for acid-base neutralization in the subsequent treatment and utilization process, which is costly, requires high equipment, and is easy to cause environmental pollution, which is not in line with the current green development. idea. Chinese patent (CN101519726A) discloses a method for recovering valuable metals from waste lithium-ion batteries by roasting, which is mainly aimed at the recovery of cobalt, copper, and lithium in cobalt lithium oxide positive electrode materials. Roasting at 500-850°C for degumming, mixing with concentrated sulfuric acid and sulfate, and performing secondary roasting to convert metals such as copper and cobalt into water-soluble sulfate, and then re-precipitating lithium to extract and recover copper and cobalt. Although this method obtains a higher metal recovery rate, it uses a higher proportion of concentrated sulfuric acid, which has no advantage over acid leaching, high acid consumption, high cost, low safety, and is not conducive to environmental protection; and this method is only for cobalt acid. Lithium-based positive electrode materials are recycled, which is difficult to adapt to the recovery of nickel and manganese in lithium nickelate, lithium manganate, and nickel-cobalt-manganese ternary positive electrode materials. Therefore, it is of great significance to develop a low-cost, environmentally friendly, and adaptable technology to recover valuable metals from spent lithium-ion battery cathode materials.

Contents of the invention

For the defects existing in the prior art, the purpose of the present invention is to propose a method for realizing the efficient recovery of valuable metal ions such as manganese, cobalt, nickel in the positive electrode material of waste lithium-ion batteries; the method overcomes the need to consume a large amount of It has the advantages of simple process, environmental friendliness, and low cost, and has great industrial application prospects.

In order to achieve the above technical purpose, the present invention provides a method for recovering valuable metals from waste lithium-ion battery cathode materials, the method is to discharge and disassemble the waste lithium-ion batteries, and sort out the positive pole pieces; Pyrolysis and degumming of the positive pole piece to separate the current collector and active material; the active material is mixed with chloride salt, and then chlorinated and roasted at a temperature of 300°C to 600°C; the chlorinated roasted solid product is leached with water to obtain Leaching solution of valent metal ions.

In the technical scheme of the present invention, the key lies in the use of chlorination roasting, that is, at a suitable temperature, by means of the action of chloride salts, the components contained in the positive electrode active material of the lithium ion battery are fully converted into gas phase or solid phase chlorides, Realize the separation and enrichment of valuable metals and other components, and the chlorides of metals such as manganese, cobalt and nickel contained in the lithium ion positive electrode active material are usually easily soluble in water, so the valuable metals can be leached by using water at room temperature ion.

In a preferred scheme, the mass ratio of the chloride salt to the active substance is (1-2):1. Too low a chloride salt content will not fully chlorinate the metals and will result in some metals being difficult to leach.

More preferably, the chloride salt includes at least one of ammonium chloride, calcium chloride, sodium chloride and potassium chloride. Most preferred is ammonium chloride. Compared with other chloride salts, ammonium chloride can realize the chlorination conversion of metals in lithium ion positive electrode active materials at relatively low temperature.

In a preferred solution, the active material includes at least one of lithium cobaltate, lithium nickelate, lithium manganate, and nickel-cobalt-manganese ternary positive electrode materials. Valuable metals such as manganese, cobalt, nickel and the like contained in the positive electrode active material of the lithium ion battery that simultaneously contain manganese, cobalt, nickel, etc. can be converted into water-soluble metal salts by the method of chlorination roasting.

In a preferred scheme, the time for the chlorination roasting is 20-40 minutes.

In a preferred scheme, the leaching conditions are as follows: the temperature is normal temperature, and the leaching time is 20-40 minutes.

In a preferred solution, the thermal degumming conditions are as follows: the temperature is 350-450° C., and the time is 1-3 hours.

In the technical solution of the present invention, the waste lithium ion battery is fully discharged in salt water, and the discharge time is generally 4 to 6 hours, so as to avoid safety problems in the subsequent treatment process.

In the technical solution of the present invention, the waste lithium ion battery is physically disassembled, and the positive pole piece is sorted out.

Compared with the prior art, the beneficial effects brought by the technical solution of the present invention:

1) The technical scheme of the present invention, the key is to adopt the method for chlorination roasting, by adopting chloride salt as roasting auxiliary agent, lithium cobaltate, lithium nickelate, lithium manganate, nickel cobalt manganese lithium ternary positive electrode material etc. The manganese, nickel and cobalt in the lithium-ion battery are all converted into water-soluble chloride salts, which realizes the efficient recovery of valuable metals in the positive electrode material of lithium-ion batteries, completely avoids the use of inorganic acids and bases, and greatly reduces the amount of valuable metals. The recovery cost is low, and it is environmentally friendly, safe, and has great industrial application prospects.

2) The technical scheme of the present invention can realize the simultaneous processing of lithium-ion battery cathode materials such as lithium cobaltate, lithium nickelate, lithium manganate, nickel-cobalt-manganese-lithium ternary cathode materials, without classification operation, and realize the production of manganese-cobalt-nickel At the same time, efficient recovery is beneficial to industrial production.

3) The technical solution of the present invention not only recovers the valuable metals in the positive electrode material, but also realizes the separate recovery of the current collector, and the recovery benefit is large.

4) The chlorination roasting method of the present invention has low roasting temperature, short time and low energy consumption, and the roasted product can be leached by water, avoiding the consumption of a large amount of inorganic acids and alkalis and possible environmental pollution in the process of recycling and leaching of traditional waste batteries, The process is simple, cheap and efficient.

Description of drawings

[Fig. 1] is a process flow diagram of the present invention.

detailed description

In summary, although the present invention has been described in detail through specific embodiments, those skilled in the art should understand that the above-mentioned embodiments are only descriptions of preferred embodiments of the present invention, rather than protection scope of the present invention. Any changes that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention are within the protection scope of the present invention.

Example 1

Take waste nickel-cobalt-manganese ternary lithium-ion batteries as an example. The discarded LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ternary lithium-ion battery assembled in the laboratory was placed in salt water and discharged for 5 hours, then physically disassembled, the battery cell was taken out, and the positive pole piece was separated . The positive electrode piece was baked at 400° C. for 2 hours in a muffle furnace, the positive electrode current collector was recovered, and the positive electrode active material was collected. Take 1000g of the collected positive electrode active material and weigh 1200g of ammonium chloride, mix the two evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 25min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 85.2%, 82.5%, and 99.2%, respectively.

Example 2

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 1000g of ammonium chloride, mix them evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 30min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 84.3%, 78.1%, and 99.1%, respectively.

Example 3

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 2000g of ammonium chloride, mix the two evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 30min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 88.4%, 85.3%, and 99.7%, respectively.

Example 4

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 1200g of ammonium chloride, mix them evenly, place them in a muffle furnace at 500°C, and chlorinate and roast for 20min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 84.6%, 82.1%, and 99.3%, respectively.

Example 5

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 1000g of sodium chloride, mix them evenly, place them in a muffle furnace at 600°C, and chlorinate and roast for 35min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 81.5%, 73.7%, and 99.2%, respectively.

Example 6

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 1000g of sodium chloride, mix the two evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 30min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 60.2%, 49.2%, and 74.2%, respectively.

Example 7

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 1200g of calcium chloride, mix them evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 30min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 66.2%, 53.9%, and 79.3%, respectively.

Comparative Example 1

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 400g of ammonium chloride, mix the two evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 30min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 51.3%, 48.1%, and 76.4%, respectively.

Comparative Example 2

The acquisition of the positive electrode active material is as described in Example 1. Take 1000g of the collected positive electrode active material and weigh 600g of ammonium chloride, mix the two evenly, place them in a muffle furnace at 400°C, and chlorinate and roast for 30min. Finally, the obtained calcined sand is poured into a sufficient amount of aqueous solution, and leached for 30 minutes at room temperature. The concentrations of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ in the solution were tested by ICP, and the leaching rates of Ni ²⁺ , Co ²⁺ , and Mn ²⁺ were 63.6%, 54.2%, and 84.2%, respectively.

Claims (8)

1. A method for reclaiming valuable metals from waste lithium-ion battery cathode materials, characterized in that: waste lithium-ion batteries are discharged, disassembled, and the positive pole piece is sorted out; the positive pole piece is subjected to pyrolysis degumming , separating the current collector and the active material; the active material is mixed with a chloride salt, and chlorinated and roasted at a temperature of 300°C to 600°C; the solid product of the chlorinated roasted is subjected to water leaching to obtain a leaching solution containing valence metal ions. 2. The method for recovering valuable metals from waste lithium ion battery anode materials according to claim 1, characterized in that: the mass ratio of the chloride salt to the active material is (1-2):1. 3. The method for reclaiming valuable metals from waste lithium-ion battery cathode materials according to claim 1 or 2, characterized in that: said chloride salts include ammonium chloride, calcium chloride, sodium chloride, chloride at least one of potassium. 4. The method for recovering valuable metals from waste lithium ion battery cathode materials according to claim 3, characterized in that: the chloride salt is ammonium chloride. 5. The method for recovering valuable metals from waste lithium-ion battery anode materials according to claim 1, wherein the active material includes lithium cobaltate, lithium nickelate, lithium manganate, nickel-cobalt-manganese ternary At least one of the positive electrode materials. 6. The method for recovering valuable metals from waste lithium ion battery anode materials according to claim 1, characterized in that: the chlorination roasting time is 20-40 minutes. 7. The method for recovering valuable metals from waste lithium-ion battery cathode materials according to claim 1, characterized in that: the leaching conditions are: the temperature is normal temperature, and the leaching time is 20-40 minutes. 8 . The method for recovering valuable metals from waste lithium-ion battery anode materials according to claim 1 , characterized in that the pyrolysis and degumming conditions are as follows: temperature is 350-450° C., and time is 1-3 hours.