CN115505757A - Method for recycling lithium and manganese of anode materials of waste lithium manganate lithium batteries through eutectic solvent - Google Patents

Method for recycling lithium and manganese of anode materials of waste lithium manganate lithium batteries through eutectic solvent Download PDF

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CN115505757A
CN115505757A CN202211291010.6A CN202211291010A CN115505757A CN 115505757 A CN115505757 A CN 115505757A CN 202211291010 A CN202211291010 A CN 202211291010A CN 115505757 A CN115505757 A CN 115505757A
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lithium
eutectic solvent
manganese
leaching
lithium manganate
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CN115505757B (en
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王威
刘红召
柳林
曹耀华
王洪亮
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Zhengzhou Institute of Multipurpose Utilization of Mineral Resources CAGS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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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Abstract

The invention discloses a method for recovering lithium and manganese of a waste lithium manganate lithium battery cathode material by using a eutectic solvent, and relates to the technical field of hydrometallurgy and comprehensive recovery of secondary resources. The invention comprises the following steps of mixing choline chloride or guanidine hydrochloride, glycerol and lactic acid according to the molar ratio of 1: (0.5-1): and (1) preparing a ternary eutectic solvent system, wherein the obtained eutectic solvent system has the advantages of low viscosity, low cost and the like, and the lithium manganate positive electrode material leached by the system has the remarkable advantages of low leaching temperature, short leaching time and high lithium and manganese leaching efficiency.

Description

Method for recycling lithium and manganese of waste lithium manganate lithium battery positive material through eutectic solvent
Technical Field
The invention relates to the technical field of hydrometallurgy and comprehensive recovery of secondary resources, in particular to a method for recovering lithium and manganese of a waste lithium manganate lithium battery positive material by using a eutectic solvent.
Background
In recent years, particularly, since the goal of "dual carbon" is proposed, new energy automobiles are a strategic emerging industry based on the urgent needs for energy sustainable development and safety. The sales volume of new energy automobiles is rapidly increased, and the demand of power batteries is greatly increased.
The lithium manganate battery is a battery with a positive electrode made of a lithium manganate material, has a nominal voltage of 2.5-4.2v, and is widely used due to low cost and good safety. Most of valuable metal recovery methods in the anode material of the lithium manganate battery adopt sulfuric acid and nitric acid or sulfuric acid and hydrogen peroxide systems for leaching, and after a leachate is precipitated by an alkaline method to obtain a manganese-containing precipitate, a lithium product is obtained by selective precipitation.
The patent with the application number of CN201310105266.8 discloses a method for recycling a lithium manganate battery anode material, wherein a mixture of the lithium manganate anode material, a conductive agent and a binder is calcined at 1000-1200 ℃ for 1-3h; then pelletizing, uniformly mixing the pelletized mixture with a carbonaceous reducing agent, silica and lime according to a certain weight ratio, and then smelting in an electric furnace for 1-3h; acid leaching slag to obtain lithium-containing solution, adding sodium carbonate solution for precipitation, and filtering to obtain lithium carbonate. The patent of application number CN201710501343.X discloses a method for recovering and treating waste lithium manganate material, which comprises the steps of reducing and roasting the waste lithium manganate material at the temperature of 300-1000 ℃, adding water into the reduced waste lithium manganate material, filtering after complete reaction, and performing solid-liquid separation to obtain a lithium hydroxide aqueous solution and a crude manganese product; evaporating and crystallizing the lithium hydroxide aqueous solution to obtain a lithium hydroxide product; and carrying out flotation and drying on the obtained rough manganese product to obtain a manganese product. The patent with the application number of CN201711340291.9 discloses a method for recovering valuable metals in a lithium manganate battery anode material, the method comprises the steps of uniformly mixing the lithium manganate battery anode material with a proper amount of carbon powder, carrying out reduction roasting at the temperature of 800-1300 ℃, adding acid into the roasted material after pulping, adjusting the pH value of the mixed solution to 3.0-6.5, soaking and filtering, and adding soluble carbonate into the filtrate to precipitate and recover lithium; and drying the filter cake to obtain the manganese oxide capable of preparing the lithium manganate circularly. The method has the defects of large acid and alkali consumption, difficult control of product purity, complex process and the like.
The eutectic solvent has the advantages of excellent solubility, simple preparation, difficult volatilization and the like, and is researched and applied to a plurality of fields of electrocatalysis, metal corrosion removal, organic synthesis, material preparation and the like at present.
The ZHIWEN XU and the like report that manganese and lithium in a lithium manganate lithium ion battery are recycled by adopting a microwave-assisted eutectic solvent, the liquid-solid ratio of the eutectic solvent to choline chloride to oxalic acid is 6g/0.1g, the eutectic solvent is leached for 15min at 70 ℃ under the assistance of microwaves, and the leaching rates of the lithium and the manganese respectively reach 99 percent and 96 percent. However, microwave-assisted systems have a problem of limited throughput in industrial applications. Therefore, an environment-friendly recovery system is developed, the high-efficiency recovery of the lithium manganate cathode material is realized, and the method has important significance.
Disclosure of Invention
The invention aims to provide a method for recovering lithium and manganese from waste lithium manganate lithium battery positive electrode materials by using a eutectic solvent, so as to solve the problems in the prior art and realize high-efficiency recovery of the lithium manganate positive electrode materials.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides an application of a eutectic solvent in recovering lithium and manganese in a waste lithium manganate lithium battery cathode material, wherein the eutectic solvent is prepared from choline chloride, glycerol and lactic acid according to a molar ratio of 1: (0.5-1): (1-2) mixing and preparing or mixing guanidine hydrochloride, glycerol and lactic acid according to a molar ratio of 1: (0.5-1): (1-2) mixing and preparing.
Further, the preparation method of the eutectic solvent is as follows:
choline chloride or guanidine hydrochloride, glycerol and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2), and then stirring for 1-2 h at the constant temperature of 70-90 ℃ to obtain the eutectic solvent.
The invention further provides a method for recovering lithium and manganese of the anode material of the waste lithium manganate lithium battery by using the eutectic solvent, which comprises the following steps:
step 1: choline chloride or guanidine hydrochloride, glycerol and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2), and then stirring for 1-2 hours at a constant temperature of 70-90 ℃ to obtain a eutectic solvent;
step 2: mixing the lithium manganate positive electrode material with the eutectic solvent, and stirring and leaching at constant temperature;
and step 3: and (3) centrifuging the solution obtained in the step (2) to obtain a solution containing lithium and manganese.
Furthermore, the mass volume ratio of the lithium manganate positive electrode material to the eutectic solvent is 1.
Further, the temperature of the constant-temperature agitation leaching in the step 2 is 70-90 ℃, and the time is 2-6 h.
The invention discloses the following technical effects:
the method utilizes the ternary eutectic solvent system prepared from choline chloride/guanidine hydrochloride, glycerol and lactic acid, has the advantages of low viscosity, low cost and the like, and has the advantages of low leaching temperature, short leaching time and high lithium and manganese leaching efficiency when being used for leaching the lithium manganate cathode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of a process flow for recovering lithium and manganese from waste lithium manganate lithium battery positive electrode materials by using a eutectic solvent according to the present invention;
FIG. 2 is the effect of leaching time on leaching lithium and manganese from choline chloride, glycerol and lactic acid eutectic solvent;
FIG. 3 is the effect of leaching temperature on the leaching of lithium and manganese from choline chloride, glycerol and lactic acid eutectic solvent;
FIG. 4 is a graph showing the effect of leaching temperature on leaching lithium and manganese from guanidine hydrochloride, glycerol and lactic acid eutectic solvents;
FIG. 5 shows the effect of the mass-to-solid ratio of the leach solution on the lithium and manganese leaching of choline chloride, glycerol and lactic acid eutectic solvent.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
FIG. 1 is a schematic diagram of a process flow for recovering lithium and manganese from waste lithium manganate lithium battery positive electrode materials by using a eutectic solvent.
The present invention will be described in further detail with reference to the following examples:
example 1
(1) Preparation of eutectic solvent: mixing choline chloride, glycerol and lactic acid according to the proportion of 1:1:1, and mixing and stirring for 1h at 70 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely a eutectic solvent (with the viscosity of 130mPa.s).
(2) Lithium manganate leaching: and (2) adding the lithium manganate positive electrode material of the waste lithium battery into the eutectic solvent prepared in the step (1), wherein the mass volume ratio of the added lithium manganate positive electrode material to the eutectic solvent is 1.
(3) Centrifuging the solution obtained in the step (2) at the speed of 4000rpm.
(4) And (3) detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of the lithium and the manganese of 92.6% and 89.7% respectively.
Example 2
(1) Preparation of eutectic solvent: guanidine hydrochloride, glycerol and lactic acid were mixed in a ratio of 1:1:1, and mixing and stirring for 2 hours at 80 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (the viscosity is 112mPa.s).
(2) Leaching lithium manganate: adding the lithium manganate positive electrode material of the waste lithium battery into the prepared eutectic solvent, wherein the mass volume ratio of the added lithium manganate positive electrode material to the eutectic solvent is 1.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And (4) detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of the lithium and the manganese which are respectively 98.6% and 97.3%.
Example 3
(1) Preparation of eutectic solvent: guanidine hydrochloride, glycerol and lactic acid were mixed in a ratio of 1:1:2, and mixing and stirring for 1h at 80 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely a eutectic solvent (the viscosity is 96mPa.s).
(2) Lithium manganate leaching: adding the lithium manganate positive electrode material of the waste lithium battery into the prepared eutectic solvent, wherein the mass volume ratio of the added lithium manganate positive electrode material to the eutectic solvent is 1.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And (3) detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of the lithium and the manganese of 99.6% and 99.3% respectively.
Example 4
(1) Preparation of eutectic solvent: mixing choline chloride, glycerol and lactic acid according to the proportion of 1:0.5:2, and mixing and stirring for 2 hours at 90 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (the viscosity is 162mPa.s).
(2) Lithium manganate leaching: adding the lithium manganate positive electrode material of the waste lithium battery into the prepared eutectic solvent, wherein the mass volume ratio of the added lithium manganate positive electrode material to the eutectic solvent is 1.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And (3) detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of the lithium and the manganese which are respectively 97.4% and 97.1%.
Example 5
(1) Preparation of eutectic solvent: guanidine hydrochloride, glycerol and lactic acid were mixed in a ratio of 1:0.5:2, and mixing and stirring for 2 hours at 80 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (with the viscosity of 176mPa.s).
(2) Lithium manganate leaching: adding the lithium manganate positive electrode material of the waste lithium battery into the prepared eutectic solvent, wherein the mass volume ratio of the added lithium manganate positive electrode material to the eutectic solvent is 1.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And (4) detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of the lithium and the manganese which are respectively 98.8% and 97.3%.
Example 6
(1) Preparation of eutectic solvent: mixing choline chloride, glycerol and lactic acid according to the proportion of 1:0.5:2, and mixing and stirring for 1h at 70 ℃ by adopting a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (with the viscosity of 152mPa.
(2) Lithium manganate leaching: adding the lithium manganate positive electrode material of the waste lithium battery into the prepared eutectic solvent, wherein the mass volume ratio of the added lithium manganate positive electrode material to the eutectic solvent is 1.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And (3) detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of the lithium and the manganese which are respectively 96.3% and 95.8%.
(one) influence of leaching time on leaching lithium and manganese from choline chloride, glycerol and lactic acid eutectic solvent:
when the lithium manganate positive electrode material and the eutectic solvent are leached according to the mass volume ratio of 1.
Wherein, the eutectic solvent is prepared as follows: mixing choline chloride, glycerol and lactic acid according to the proportion of 1:0.5:2, and mixing and stirring for 1h at 70 ℃ by adopting a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent.
(II) influence of leaching temperature on leaching lithium and manganese from choline chloride, glycerin and lactic acid eutectic solvent:
and (3) stirring and leaching the lithium manganate cathode material and the eutectic solvent for 4 hours at a constant temperature according to a mass volume ratio of 1.
Wherein, the eutectic solvent is prepared as follows: mixing choline chloride, glycerol and lactic acid according to the proportion of 1:1:2, and mixing and stirring for 1h at 80 ℃ in a water bath heating mode to obtain a clear transparent solution, namely the eutectic solvent.
(III) influence of leaching temperature on leaching lithium and manganese by guanidine hydrochloride, glycerin and lactic acid eutectic solvent:
and (3) stirring and leaching the lithium manganate positive electrode material and a eutectic solvent for 2 hours at a constant temperature according to a mass-volume ratio of 1.
Wherein the eutectic solvent is prepared as follows: guanidine hydrochloride, glycerol and lactic acid were mixed in a ratio of 1:1:2, and mixing and stirring for 1h at 80 ℃ in a water bath heating mode to obtain a clear transparent solution, namely the eutectic solvent.
(IV) influence of solid-solid mass ratio of the leaching solution on leaching lithium and manganese in choline chloride, glycerin and lactic acid eutectic solvent:
the lithium manganate positive electrode material and the eutectic solvent are stirred and leached for 4 hours at the constant temperature of 90 ℃ according to different mass-to-volume ratios, and the influence of the leaching liquid-solid mass-to-volume ratio on leaching of lithium and manganese by the choline chloride, glycerol and lactic acid eutectic solvent is shown in figure 5.
Wherein the eutectic solvent is prepared as follows: guanidine hydrochloride, glycerol and lactic acid were mixed in a ratio of 1:1:2, and mixing and stirring for 1h at 80 ℃ in a water bath heating mode to obtain a clear transparent solution, namely the eutectic solvent.
(V) the influence of the ratio of guanidine hydrochloride, glycerol and lactic acid on leaching lithium and manganese by the eutectic solvent of guanidine hydrochloride, glycerol and lactic acid:
the lithium manganate cathode material and the eutectic solvent are stirred and leached for 2 hours at a constant temperature of 70 ℃ according to a mass volume ratio of 1.
Wherein, the eutectic solvent is prepared as follows: guanidine hydrochloride, glycerol and lactic acid are mixed according to the molar ratio in the table 1, and are mixed and stirred for 1 hour at 70 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent.
It can be seen from fig. 2 to 5 that the leaching rates of lithium and manganese increase with the increase of the leaching time, but when the leaching time exceeds 4 hours, the leaching rates of lithium and manganese tend to be balanced; the leaching rates of lithium and manganese increase with the increase of the leaching temperature, and when the leaching temperature exceeds 80 ℃, the increase range of the leaching rates of lithium and manganese is reduced; in the test range, the leaching rates of lithium and manganese are increased integrally along with the increase of the solid-to-solid volume mass ratio of the leaching solution, but the leaching rates of lithium and manganese are not changed greatly along with the increase of the solid-to-liquid volume mass ratio because the leaching rates of lithium and manganese reach more than 80 percent.
As can be seen from Table 1, in the test range, eutectic solvents with different molar ratios of guanidine hydrochloride, glycerol and lactic acid have higher leaching rates for lithium and manganese.
TABLE 1 Effect of guanidine hydrochloride, glycerol and lactic acid ratios on lithium and manganese Leaching rates
Guanidine hydrochloride, glycerol and lactic acid molar example Lithium extraction Rate (%) Manganese leaching rate (%)
1:1:1 98.6 97.3
1:1:1.5 98.8 98.1
1:1:2 99.2 98.6
1:0.5:2 98.8 97.6
The method is characterized in that choline chloride/guanidine hydrochloride, glycerol and lactic acid are prepared to obtain a mutual-soluble stable eutectic solvent system, the system can efficiently leach lithium and manganese in the lithium manganate anode material, and the method has the characteristics of simple process, simplicity and convenience in operation, greenness and environmental friendliness.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (5)

1. The application of the eutectic solvent in recycling lithium and manganese in the anode material of the waste lithium manganate lithium battery is characterized in that the eutectic solvent is prepared from choline chloride, glycerol and lactic acid according to a molar ratio of 1: (0.5-1): (1-2) mixing and preparing or mixing guanidine hydrochloride, glycerol and lactic acid according to a molar ratio of 1: (0.5-1): (1-2) mixing and preparing.
2. The use according to claim 1, characterized in that the eutectic solvent is prepared as follows:
choline chloride or guanidine hydrochloride, glycerol and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2), and then stirring for 1-2 hours at a constant temperature of 70-90 ℃ to obtain the eutectic solvent.
3. A method for recovering lithium and manganese from waste lithium manganate lithium battery anode materials by using a eutectic solvent is characterized by comprising the following steps:
step 1: choline chloride or guanidine hydrochloride, glycerol and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2), and then stirring for 1-2 hours at a constant temperature of 70-90 ℃ to obtain the eutectic solvent;
and 2, step: mixing the lithium manganate positive electrode material with the eutectic solvent, and stirring and leaching at constant temperature;
and step 3: and (3) centrifuging the solution obtained in the step (2) to obtain a solution containing lithium and manganese.
4. The method according to claim 3, wherein the mass volume ratio of the lithium manganate positive electrode material to the eutectic solvent is 1.
5. The method as claimed in claim 3, wherein the temperature of the constant temperature agitation leaching in the step 2 is 70-90 ℃ and the time is 2-6 h.
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CN115961141A (en) * 2023-02-01 2023-04-14 中国地质科学院郑州矿产综合利用研究所 Eutectic solvent and preparation method and application thereof

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