CN105331819A - Method for recycling Co3O4 from positive electrode material of waste lithium cobalt oxide battery - Google Patents

Abstract

The invention discloses a method for recycling Co3O4 from a positive electrode material of a waste lithium cobalt oxide battery. By means of an organic acid leaching method, the positive electrode material of the waste lithium cobalt oxide battery is obtained through separation, operation is simple, and the separation rate reaches more than 98%. Meanwhile, in the leaching process, the pollution to the environment is reduced by selecting organic acid. Zero pollution to the environment is achieved in the process of obtaining Co3O4 through spraying sintering, and operation is simple and feasible. An obtained product is stable in chemical property, the material performance is superior, and the product can serve as an electronic material and can also be widely applied to catalysts and oxidizing agents and applied to manufacturing cobalt salt, enamel pigment and the like.

Description

Method for recovering Co3O4 from waste lithium cobalt oxide battery cathode material

technical field

The invention belongs to the field of recycling positive electrode materials of waste lithium cobalt oxide batteries, and in particular relates to a method for recovering Co3O4 from the positive electrode materials of waste lithium cobalt _oxide batteries _.

Background technique

Today, with the continuous development of lithium-ion batteries, their applications are becoming more and more extensive. Due to the advantages of high charging voltage, large specific energy, long cycle life, good safety performance, no pollution, no memory effect, and small self-discharge, lithium-ion batteries have been widely used in the field of portable electronic products, including mobile phones, notebook computers, cameras , digital cameras, medical equipment, etc. The widespread use of lithium-ion batteries will inevitably bring a large number of waste batteries. Waste lithium-ion batteries contain a variety of inorganic and organic compounds, which will cause serious pollution to the environment when exposed to the environment. Therefore, recycling waste lithium-ion batteries has positive practical significance for reducing environmental pollution and reusing resources.

However, waste lithium-ion batteries contain a large amount of expensive metal cobalt, and my country has a shortage of cobalt resources. The metal recovery rate in the production process is low, the process is complicated, and the production cost is high. If the cobalt resources in the waste lithium-ion batteries can be recycled, it is of great significance both in terms of environmental protection and resource recycling. Among them, the oxide Co ₃ O ₄ is widely used and can be used for catalysts, Oxidants, cobalt salts, enamel pigments, etc., are of great value for their recovery and preparation.

At present, the recovery technology of waste lithium-ion battery cathode materials is mainly divided into two processes: one is the separation and leaching process. CN101280357B discloses an acid leaching extraction process for recycling waste lithium batteries, mainly using sulfuric acid, hydrogen peroxide and the like for leaching. CN1688065A points out that the obtained waste battery material is leached with hydrogen peroxide or sodium thiosulfate as a reducing agent under acidic conditions, and then cobalt is precipitated with sodium hydroxide as a precipitating agent. CN103757399A discloses a method for treating waste lithium batteries using a combined leaching method of sulfuric acid and nitric acid. The second is the calcination preparation process. CN101673859A discloses a method for recovering lithium cobaltate from waste lithium-ion batteries. The first calcination forms a xerogel, and the second calcination forms a lithium cobaltate electrode material. After CN104103870A undergoes separation, leaching and ball milling, lithium and cobalt are separated to obtain cobalt oxalate and lithium carbonate respectively. CN102751549A discloses a method for finally obtaining a ternary composite positive electrode material by using nickel-cobalt-manganese carbonate ternary precursor and separated waste materials to regulate.

Judging from the disclosed prior art, the following problems still exist in the field of waste lithium-ion battery recycling: one is the leaching part, most of which use inorganic strong acids such as sulfuric acid, hydrochloric acid, nitric acid, etc., which will cause secondary pollution to the surrounding environment, And the energy consumption is large; the second is the calcination preparation process, which produces toxic and harmful gases during the calcination process, causing dust and heavy metal pollution.

Contents of the invention

In order to achieve the above purpose, the present invention provides a method for recovering Co ₃ O ₄ from waste lithium cobaltate battery cathode materials with high separation rate, low environmental pollution and excellent performance of recovered materials.

The present invention provides a kind of method that reclaims Co ₃ O ₄ from waste and old lithium cobalt oxide battery anode material, and it comprises the following steps:

Step _A , disassemble the waste LiCoO2 battery, take out the positive electrode sheet, soak in an organic solvent for 10-60 minutes, the solid-liquid ratio is 1:5-1:15, filter and separate the current collector, and dry to obtain a black solid;

Step B, adding organic acid and H ₂ O ₂ solution to the black solid obtained in Step A, controlling the solid-liquid ratio at 5-20 g/l, stirring and leaching at 30-90°C for 1-5 hours, and filtering to obtain cobalt-containing filtrate;

Step C, adding the corresponding cobalt ion extractant to the filtrate obtained in step B, and extracting to obtain a cobalt ion complex;

Step D, bubbling oxygen into the cobalt ion complex obtained in step C, roasting at 600-1300° C., 180-300 MPa to obtain Co ₃ O ₄ which is deacidified and recovered in the form of powder.

The beneficial effects of the method for reclaiming Co from waste lithium cobalt _oxide battery positive electrode materials provided by the present invention O _The method is:

(1) The present invention uses an organic acid leaching method to separate and obtain the positive electrode material of the waste lithium cobalt oxide battery, which is simple to operate and has a separation rate as high as 98% or more; meanwhile, the organic acid used in the leaching process reduces environmental pollution.

(2) The process of obtaining Co ₃ O ₄ by spray roasting in the present invention has zero pollution to the environment, and the operation is simple and easy. The obtained product has stable chemical properties and excellent material performance. It can not only be used as electronic materials, but also widely used in catalysts , oxidant, manufacture cobalt salt, enamel pigment, etc.

Description of drawings

Fig. 1 is a flow chart of the method for recovering Co ₃ O ₄ from waste lithium cobalt oxide battery cathode materials according to the present invention.

Fig. 2 is a characteristic diagram of the morphology of Co ₃ O ₄ recovered by the method of the present invention.

detailed description

As shown in Figure ₁ , the present invention provides a kind of method that reclaims Co3O4 from waste lithium cobalt _oxide battery cathode material, and it comprises the following steps:

Step _A , disassemble the waste LiCoO2 battery, take out the positive electrode sheet, soak in an organic solvent for 10-60 minutes, the solid-liquid ratio is 1:5-1:15, filter and separate the current collector, and dry to obtain a black solid;

Step B, adding organic acid and H ₂ O ₂ solution to the black solid obtained in Step A, controlling the solid-liquid ratio at 5-20 g/l, stirring and leaching at 30-90°C for 1-5 hours, and filtering to obtain cobalt-containing filtrate;

Step C, adding the corresponding cobalt ion extractant to the filtrate obtained in step B, and extracting to obtain a cobalt ion complex;

Step D, bubbling oxygen into the cobalt ion complex obtained in step C, roasting at 600-1300° C., 180-300 MPa to obtain Co ₃ O ₄ which is deacidified and recovered in the form of powder.

Preferably, the soaking process in step A is combined with ultrasonic and mechanical stirring for 10-60 minutes.

Preferably, the organic solvent in step A includes dimethylformamide, N-methylpyrrolidone, dimethylacetamide or dimethylsulfoxide.

Preferably, the organic acid in step B includes citric acid, acetic acid, oxalic acid, formic acid, maleic acid or ascorbic acid, and the dosage is 30-50 g/l.

Preferably, in step B, the volume fraction of the H ₂ O ₂ solution is 0.1-2%, and the amount used is 1.2-2 mole multiples of LiCoO ₂ .

Preferably, the cobalt ion extractant described in step C includes tertiary carbon carboxylic acid Versatic911, two (2-hydroxy-5-octyl) benzylamine, 2-ethylhexyl tri (octyl-decyl) alkyl tertiary amine, Di(2-ethylhexyl)phosphate or mono-2-ethylhexyl ethylhexylphosphate.

Preferably, step D is carried out in a roasting furnace, and oxygen gas is blown through and blown in air.

The present invention will be further described in detail below in conjunction with specific embodiments. Of course, the described embodiments are only some of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are all Belong to the protection scope of the present invention.

Example 1

The waste LiCoO ₂ battery was manually broken and disassembled, and the positive electrode sheet was taken out. Soak the above-mentioned positive electrode sheet in NMP solution, stir it mechanically for 10 min at room temperature with a solid-to-liquid ratio (g/ml) of 1:5, filter and dry to collect the black powder therein.

Take the black powder obtained in the separation stage, add citric acid for leaching, the acid consumption is 30g/l, add H ₂ O ₂ with a volume fraction of 1% according to the molar ratio 1:1.5, and the solid-liquid ratio is controlled at 10g/l. Stir and leach at 30°C for 5 hours, and filter to obtain a cobalt-containing filtrate.

Add tertiary carbon carboxylic acid Versatic911 to the filtrate and extract for 1 hour to obtain relatively pure Co ion complex.

After extraction, the cobaltate leaching liquid is sent into the roasting furnace through a pneumatic feeding device, and air is blown in. The temperature of the heating area of the roasting furnace is controlled at 600 ° C, and the negative pressure on the top of the furnace is controlled at 280 MPa. The Co ₃ O ₄ obtained by roasting It is recovered in the form of powder after deacidification treatment.

Example 2

The waste LiCoO ₂ battery was manually broken and disassembled, and the positive electrode sheet was taken out. Soak the above-mentioned positive electrode sheet in DMF solution, with a solid-to-liquid ratio (g/ml) of 1:15 at room temperature, with mechanical stirring for 30 minutes, filter and dry to collect the black powder therein.

Take the black powder obtained in the separation stage, add acetic acid for leaching, the amount of acid is 50g/l, add H ₂ O ₂ with a volume fraction of 1% in a molar ratio of 1:2, and control the solid-liquid ratio at 20g/l, at 60 Stir and leach for 3 hours at °C, and filter to obtain a cobalt-containing filtrate.

Add bis(2-hydroxy-5-octyl)benzylamine to the filtrate and extract for 1 hour to obtain relatively pure Co ion complex.

After extraction, the cobaltate leaching liquid is sent to the roasting furnace through a pneumatic feeding device, and air is blown in. The temperature of the heating area of the roasting furnace is controlled at 1000 ° C, and the negative pressure on the top of the furnace is controlled at 280 MPa. The Co ₃ O ₄ obtained by roasting It is recovered in the form of powder after deacidification treatment.

Fig. 2 is a characteristic diagram of the morphology of Co ₃ O ₄ recovered by the method of the present invention. It can be seen from Fig. 2 that the Co ₃ O ₄ powder has uniform particle size, less impurity phase, less particle agglomeration, and stable performance.

Claims (7)

1. a kind of reclaiming Co from waste and old lithium cobalt oxide battery anode material ₃ O ₄ method, it may further comprise the steps: Step _A , disassemble the waste LiCoO2 battery, take out the positive electrode sheet, soak in an organic solvent for 10-60 minutes, the solid-liquid ratio is 1:5-1:15, filter and separate the current collector, and dry to obtain a black solid; Step B, adding organic acid and H ₂ O ₂ solution to the black solid obtained in Step A, controlling the solid-liquid ratio at 5-20 g/l, stirring and leaching at 30-90°C for 1-5 hours, and filtering to obtain cobalt-containing filtrate; Step C, adding the corresponding cobalt ion extractant to the filtrate obtained in step B, and extracting to obtain a cobalt ion complex; Step D, bubbling oxygen into the cobalt ion complex obtained in step C, roasting at 600-1300° C., 180-300 MPa to obtain Co ₃ O ₄ which is deacidified and recovered in the form of powder. 2. The method for recovering Co ₃ O ₄ from waste lithium cobaltate battery positive electrode materials according to claim 1, characterized in that: in the step A, the soaking process is combined with ultrasonic and mechanical stirring for 10-60 minutes. 3. as claimed in claim 1 from waste lithium cobaltate battery cathode material recovery Co ₃ O _The method is characterized in that: in the described step A, the organic solvent comprises dimethylformamide, N-methylpyrrolidone, Dimethylacetamide or dimethylsulfoxide. 4. The method for reclaiming Co from waste lithium cobalt oxide battery cathode materials as claimed in claim 1 ₃ O _The method is characterized in that: in the step B, the organic acid comprises citric acid, acetic acid, oxalic acid, formic acid, maleic acid Or ascorbic acid, the dosage is 30-50g/l. 5. The method for recovering Co ₃ O ₄ from the positive electrode material of waste lithium cobalt oxide battery as claimed in claim 1, characterized in that: in step B, the volume fraction of H ₂ O ₂ solution is 0.1-2%, and the dosage is LiCoO ₂ 1.2 to 2 molar multiples of . 6. as claimed in claim 1 from waste lithium cobaltate battery cathode material recovery Co ₃ O _The method is characterized in that: the cobalt ion extraction agent described in the step C comprises tertiary carbon carboxylic acid Versatic911, two (2- Hydroxy-5-octyl)benzylamine, 2-ethylhexyltris(oct-decyl)alkyl tertiary amine, di(2-ethylhexyl)phosphate or mono-2-ethylhexyl ethylhexylphosphate . 7. The method for recovering Co ₃ O ₄ from waste lithium cobalt oxide battery positive electrode materials as claimed in claim 1, characterized in that: step D is carried out in a roasting furnace, and oxygen is blown through and blown in the form of air.