CN110611136A - Method for recovering and preparing cobalt elementary substance from waste lithium battery by molten salt method - Google Patents

Method for recovering and preparing cobalt elementary substance from waste lithium battery by molten salt method Download PDF

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Publication number
CN110611136A
CN110611136A CN201910845827.5A CN201910845827A CN110611136A CN 110611136 A CN110611136 A CN 110611136A CN 201910845827 A CN201910845827 A CN 201910845827A CN 110611136 A CN110611136 A CN 110611136A
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molten salt
iron sheet
cobalt
waste lithium
preparing
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CN110611136B (en
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梁精龙
李慧
张艳博
严红燕
曹卫刚
王乐
蔡宗英
李运刚
徐杰
王子兵
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North China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to the field of solid waste recovery, in particular to a method for recovering and preparing a cobalt simple substance from a waste lithium battery anode material by using a molten salt method, which comprises the following steps: s1, weighing quantitative NaCl and CaCl2And LiCoO2Uniformly mixing and grinding the mixture, and then placing the mixture in a vacuum drying oven to remove water; s2, heating the mixed reagent in a tubular resistance heating furnace; s3, preparing an electrode; s4, placing the electrode in molten salt for electrodeposition; and S5, taking out the cathode iron sheet at room temperature and washing to finally obtain the cobalt simple substance. The method can directly recover simple substance cobalt from the anode material of the waste lithium battery; the equipment is simple and easy to control, the difficulty of the production process is reduced, and meanwhile, the temperature is controlled to be 750 ℃, so that the energy consumption is low and the environmental pollution is small compared with the traditional method; in addition, the salt in the molten salt system is common salt, has no corrosivity, avoids the use of strong acid or strong base, and is safe.

Description

Method for recovering and preparing cobalt elementary substance from waste lithium battery by molten salt method
Technical Field
The invention relates to the field of solid waste recovery, in particular to a method for recovering and preparing a cobalt simple substance from a waste lithium battery positive electrode material by using a molten salt method.
Background
Cobalt is an important raw material for producing heat-resistant alloy, hard alloy, anticorrosive alloy, magnetic alloy and various cobalt salts. But the shortage of cobalt resources in China is low and is less than 4% of the total reserves in the world. The mass fraction of cobalt in the lithium ion battery can reach 15%, the content of cobalt is about 850 times of that of associated cobalt ore and is far higher than that of cobalt mine, and the cobalt resource raw materials are relatively concentrated. In addition, calculated according to the annual discarding of 1 hundred million lithium ion batteries, the recoverable cobalt is about 600 tons, so the method has important significance for recycling the cobalt metal in the waste lithium batteries.
The recovery method mainly comprises dry metallurgy technology and wet metallurgy technology, and some emerging recovery technologies such as biological dissolution method, ion exchange method and the like. The recovery of waste batteries by dry metallurgy technology is mainly to roast a large amount of collected batteries in a high-temperature environment, and reduce metal substances by using organic matters and carbon of the batteries to finally obtain metal alloy. The dry recovery technology has high requirements on equipment, a large amount of waste gas is generated in the recovery process to cause environmental pollution, and the final product is alloy, so that the later separation is not facilitated. The wet recovery process mainly comprises leaching the anode material with acid and alkali to make the valuable metal in the anode material enter the solution in an ionic state, and obtaining the metal simple substance or metal compound through different recovery modes. However, the wet recovery process causes certain corrosion to equipment due to the use of acid and alkali, the recovery cost is high, and the intermediate product has certain harm to human bodies and the environment. The biological metallurgical method utilizes the dissolution of valuable metals by microorganisms, but has low efficiency and is difficult to recover in large quantities. The ion exchange method comprises the steps of selectively adsorbing valuable metals in a solution by using ion exchange resin, eluting the metal ions by using an eluent to enable the valuable metal ions to be gathered in the solution, and finally obtaining a metal product by using methods such as precipitation, organic solvent extraction and the like. However, the adsorption coefficients of different ions are greatly different, so that the operation is complex and the steps are complicated.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a method for recovering and preparing a cobalt simple substance from waste lithium batteries by using a molten salt method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recovering and preparing a cobalt simple substance from waste lithium batteries by using a molten salt method comprises the following steps:
s1, weighing quantitative NaCl and CaCl2And LiCoO2Uniformly mixing and grinding the weighed reagents, and placing the reagents in a vacuum drying oven to remove moisture;
s2, placing the dried mixed reagent into a tubular resistance heating furnace, raising the temperature to 750 ℃ along with the furnace, and keeping the temperature to ensure that LiCoO is constant2Reaching saturated dissolving equilibrium state in the molten salt;
s3, respectively connecting the processed iron sheet and the processed high-purity graphite sheet with a stainless steel rod by using a high-purity nickel wire to prepare electrodes;
s4, placing the manufactured electrode in molten salt to enable the molten salt to just immerse the iron sheet, and placing the high-purity graphite sheet and the iron sheet in parallel and opposite to each other for electrodeposition;
and S5, after the deposition is finished, cooling the electrode to room temperature along with the furnace, taking down the cathode iron sheet, washing the cathode iron sheet by using distilled water under the microwave condition, and drying the cathode iron sheet in vacuum to obtain the cobalt simple substance.
Preferably, the LiCoO in the step S12Origin of originThe waste lithium battery of the mobile phone is obtained by manual disassembly and recovery through a high-temperature sintering method.
Preferably, NaCl and CaCl are used in the step S12In a molar ratio of 1:1, said LiCoO2The amount of the compound is 5 percent by mass.
Preferably, the vacuum drying conditions in step S1 are as follows: drying at 200 deg.C for 12 h.
Preferably, in the step S2, the heating rate is 10 ℃/min, and the temperature is kept at 750 ℃ for 2 h.
Preferably, the processing procedure of the iron sheet in the step S3 is to polish the iron sheet with metallographic abrasive paper from coarse to fine, clean the iron sheet in 10% sodium hydroxide solution under microwave condition for about 5min, remove surface grease sufficiently, soak the iron sheet in dilute hydrochloric acid for 1 ~ 2min, remove the residual oxide layer on the surface, clean the iron sheet with absolute ethyl alcohol and blow-dry the iron sheet for standby.
Preferably, the electrodeposition conditions in the step S4 are such that the current density is 125 ~ 250mA cm at 750 DEG C-2The deposition time was 8 h.
The invention has the beneficial effects that:
the method can directly recover simple substance cobalt from the anode material of the waste lithium battery; the equipment is simple and easy to control, the difficulty of the production process is reduced, and meanwhile, the temperature is controlled to be 750 ℃, so that the energy consumption is low and the environmental pollution is small compared with the traditional method; in addition, the salt in the molten salt system is common salt, has no corrosivity, avoids the use of strong acid or strong base, and is safe.
Drawings
FIG. 1 is an electron microscope image of a product obtained by a method for recovering and preparing a cobalt simple substance from a waste lithium battery by using a molten salt method, which is provided by the invention;
FIG. 2 is a diagram of the detection of the components of a product obtained by the method for recovering and preparing cobalt elementary substance from waste lithium batteries by using a molten salt method;
fig. 3 is an XRD schematic diagram of a product obtained by the method for recovering and preparing cobalt simple substance from waste lithium battery by molten salt method according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Preparing cobalt by a molten salt method, and taking lithium cobaltate obtained by disassembling and recycling mobile phone waste batteries as a raw material. The molten salt system is selected from sodium chloride and calcium chloride binary system, i.e. NaCl-CaCl2-LiCoO2Using an equimolar ratio of NaCl-CaCl2The system can ensure that the system has lower melting point, NaCl and CaCl2Having the lowest melting point at a molar ratio of 1:1, LiCoO2The amount of (b) added is 5% of the total mass.
Proportionally mixing NaCl and CaCl2And LiCoO2Mixing thoroughly, pouring into corundum crucible, heating in resistance furnace, dissolving lithium cobaltate at 750 deg.C, maintaining the temperature of molten salt for 2 hr to obtain LiCoO-containing solution2A dissolution equilibrium state can be achieved.
The technology of the present invention is further explained below with reference to specific preparation processes.
Weighing the mixture by an electronic scale according to a molar ratio of 1:1 analytical reagents NaCl and CaCl2，LiCoO2The mass of the three salts is 5 percent of the total mass, the total mass of all the salts is 150g, the three salts are uniformly mixed and poured into a corundum dry pot, and the corundum dry pot is placed in a vacuum drying oven to be dried for 12 hours at the temperature of 200 ℃ so as to remove residual moisture in the reagent, and then the corundum dry pot is sealed and stored for standby;
heating the dried corundum dry pot filled with the medicine in a resistor, heating a resistor furnace to 750 ℃ to ensure that the raw materials are in a completely molten state, and then preserving the heat of molten salt for 2 hours to ensure that LiCoO is obtained2And (3) reaching the dissolution saturation, introducing flowing argon for atmosphere protection in the whole process under a closed condition, and drying the argon by passing through a gas distillation tower filled with allochroic silica gel before introducing the argon into the furnace. Argon is introduced from an argon inlet at the bottom of the furnace and is discharged from an air outlet at the top of the furnace, and the discharged air is introduced into a solution containing sodium hydroxide, is purified and is discharged into the environment. The upper and lower parts of the furnace are respectively provided with stainless steelThe steel furnace cover ensures the air tightness of the furnace, and in order to prevent the furnace cover from being oxidized in a high-temperature environment, circulating water is introduced into the furnace cover for cooling, so that the service life of the furnace cover is prolonged.
Cooling to room temperature after reaction, and cleaning the product with hot distilled water according to the characteristic that sodium chloride and calcium chloride are easily dissolved in water, and removing residual salt to obtain the iron sheet with the product.
The prepared plated sheet was examined by a JEM-2800 field emission transmission electron microscope as shown in FIG. 1, to obtain an electron micrograph of the surface coating of the sample. As can be seen from fig. 1, the prepared pure cobalt has a good surface and a uniform texture.
As shown in FIG. 2, the prepared plating piece is sent to a field emission transmission electron microscope for component detection, and the existence of Fe and Co elements is mainly detected on the plating piece, so that the method is proved to be feasible.
XRD examination of the composition of the plated piece was carried out as shown in FIG. 3, and it was found that pure cobalt was produced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (7)

1. A method for recovering and preparing a cobalt simple substance from waste lithium batteries by using a molten salt method is characterized by comprising the following steps:
s1, weighing quantitative NaCl and CaCl2And LiCoO2Uniformly mixing and grinding the weighed reagents, and placing the reagents in a vacuum drying oven to remove moisture;
s2, placing the dried mixed reagent in a tubular resistance heating furnace, raising the temperature to 750 ℃ along with the furnace, and keeping the temperature for 2 hours to ensure that LiCoO is obtained2Reaching saturated dissolving equilibrium state in the molten salt;
s3, respectively connecting the processed iron sheet and the processed high-purity graphite sheet with a stainless steel rod by using a high-purity nickel wire to prepare electrodes;
s4, placing the manufactured electrode in molten salt to enable the molten salt to just immerse the iron sheet, and placing the high-purity graphite sheet and the iron sheet in parallel and opposite to each other for electrodeposition;
and S5, after the deposition is finished, cooling the electrode to room temperature along with the furnace, taking down the cathode iron sheet, washing the cathode iron sheet by using distilled water under the microwave condition, and drying the cathode iron sheet in vacuum to obtain the cobalt simple substance.
2. The method as claimed in claim 1, wherein the LiCoO in step S1 is used for recovering and preparing cobalt from waste lithium batteries by molten salt method2Is derived from mobile phone waste lithium batteries and is obtained by manual disassembly and recovery through a high-temperature sintering method.
3. The method for recycling and preparing the elemental cobalt from the waste lithium batteries by the molten salt method as claimed in claim 1, wherein NaCl and CaCl in the step S12In a molar ratio of 1:1, said LiCoO2The amount of the compound is 5 percent by mass.
4. The method for recovering and preparing the elemental cobalt from the waste lithium batteries by using the molten salt method as claimed in claim 1, wherein the vacuum drying conditions in the step S1 are as follows: drying at 200 deg.C for 12 h.
5. The method for recovering and preparing the elemental cobalt from the waste lithium batteries by using the molten salt method as claimed in claim 1, wherein in the step S2, the temperature rise rate is 10 ℃/min, and the temperature is kept at the constant temperature of 750 ℃ for 2 h.
6. The method as claimed in claim 1, wherein the step S3 of processing the iron sheet includes grinding the iron sheet with metallographic sandpaper from coarse to fine, washing the iron sheet with 10% sodium hydroxide solution under microwave conditions for about 5min to remove surface grease, immersing the iron sheet in dilute hydrochloric acid for 1 ~ 2min, removing the residual oxide layer on the surface, washing with absolute ethyl alcohol, and drying.
7. The method as claimed in claim 1, wherein the electrodeposition conditions in step S4 are that the current density is 125 ~ 250 mA-cm at 750 ℃-2The deposition time was 8 h.
CN201910845827.5A 2019-09-09 2019-09-09 Method for recovering and preparing cobalt elementary substance from waste lithium battery by molten salt method Active CN110611136B (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN111705336A (en) * 2020-06-11 2020-09-25 华北理工大学 Method for recovering nickel simple substance from waste lithium battery

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CN111705336A (en) * 2020-06-11 2020-09-25 华北理工大学 Method for recovering nickel simple substance from waste lithium battery

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