CN115505757B - Method for recycling lithium and manganese of waste lithium manganate lithium battery positive electrode material by eutectic solvent - Google Patents

Method for recycling lithium and manganese of waste lithium manganate lithium battery positive electrode material by eutectic solvent Download PDF

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CN115505757B
CN115505757B CN202211291010.6A CN202211291010A CN115505757B CN 115505757 B CN115505757 B CN 115505757B CN 202211291010 A CN202211291010 A CN 202211291010A CN 115505757 B CN115505757 B CN 115505757B
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eutectic solvent
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lithium manganate
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CN115505757A (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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    • 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
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    • 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
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    • 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
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Abstract

The invention discloses a method for recycling lithium and manganese of a waste lithium manganate lithium battery anode material by using a eutectic solvent, and relates to the technical field of hydrometallurgy and secondary resource comprehensive recycling. The invention uses choline chloride or guanidine hydrochloride, glycerin and lactic acid according to the mole ratio of 1: (0.5-1): (1-2) 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 anode material leached by the system has the remarkable advantages of low leaching temperature, short leaching time and high leaching efficiency of lithium and manganese.

Description

Method for recycling lithium and manganese of waste lithium manganate lithium battery positive electrode material by 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 which are positive materials of waste lithium manganate lithium batteries by using a eutectic solvent.
Background
In recent years, particularly, a "two-carbon" target has been proposed, and new energy automobiles are becoming strategically emerging industries based on urgent demands for sustainable development and safety of energy. The sales 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 lithium manganate material used as an anode, and the nominal voltage of the lithium manganate battery is 2.5-4.2v, so that the lithium manganate battery is widely used with low cost and good safety. The recovery method of valuable metals in the lithium manganate battery anode material mostly adopts sulfuric acid and nitric acid or sulfuric acid and hydrogen peroxide system to leach, and leaching liquid is precipitated by an alkaline method to obtain manganese-containing precipitate, and then selective precipitation is carried out to obtain a lithium product.
Patent application number CN201310105266.8 discloses a method for recycling lithium manganate battery anode material, wherein the mixture of the lithium manganate battery anode material, a conductive agent and a binder is calcined for 1-3 hours at 1000-1200 ℃; pelletizing, mixing the pelletized mixture with carbonaceous reducing agent, silica and lime in certain weight ratio, and smelting in an electric furnace for 1-3 hr; and (3) acid leaching the slag to obtain a lithium-containing solution, adding a sodium carbonate solution for precipitation, and filtering to obtain lithium carbonate. Patent application number CN201710501343.X discloses a method for recycling waste lithium manganate material, which comprises the steps of reducing and roasting the waste lithium manganate material at 300-1000 ℃, adding water into the waste lithium manganate material subjected to reduction treatment, filtering after the reaction is completed, and separating solid from liquid to obtain lithium hydroxide aqueous solution and crude manganese product; evaporating and crystallizing the lithium hydroxide aqueous solution to obtain a lithium hydroxide product; and (5) carrying out floatation and drying on the obtained crude manganese product to obtain the manganese product. The patent of application number CN201711340291.9 discloses a method for recovering valuable metals in a lithium manganate battery anode material, which comprises the steps of uniformly mixing the lithium manganate battery anode material with a proper amount of carbon powder, carrying out reduction roasting at 800-1300 ℃, adding water into the roasting material to slurry, adding acid to adjust the pH value of the mixed solution to 3.0-6.5, soaking and filtering, and adding soluble carbonate into filtrate to precipitate and recover lithium; and drying the filter cake to obtain the manganese oxide capable of circularly preparing lithium manganate. The method has the defects of large consumption of acid and alkali, 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 currently researched and applied to various fields such as electrocatalysis, metal corrosion removal, organic synthesis, material preparation and the like.
The ZHIHEN XU et al report that the manganese and the lithium in the lithium manganate lithium ion battery are recycled by adopting a microwave-assisted eutectic solvent, the eutectic solvent with the molar ratio of choline chloride to oxalic acid being 1:2 is adopted, the liquid-solid ratio is 6g/0.1g under the assistance of microwaves, the leaching is carried out for 15min at 70 ℃, and the leaching rates of the lithium and the manganese reach 99 percent and 96 percent respectively. However, microwave assist can have a throughput limitation in industrial applications. Therefore, a green recovery system is developed, so that the lithium manganate positive electrode material can be recovered efficiently, and the method has important significance.
Disclosure of Invention
The invention aims to provide a method for recycling lithium and manganese of waste lithium manganate lithium battery anode materials by using a eutectic solvent, so as to solve the problems in the prior art and realize efficient recycling of the lithium manganate anode materials.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides application of a eutectic solvent in recycling lithium and manganese in waste lithium manganate lithium battery anode materials, 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) or guanidine hydrochloride, glycerin and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2) and mixing.
Further, the preparation method of the eutectic solvent comprises the following steps:
choline chloride or guanidine hydrochloride, glycerin 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.
The invention further provides a method for recycling lithium and manganese of a waste lithium manganate lithium battery anode material by using the eutectic solvent, which comprises the following steps:
step 1: choline chloride or guanidine hydrochloride, glycerin and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2) mixing, and then stirring at a constant temperature of 70-90 ℃ for 1-2 hours to obtain a eutectic solvent;
step 2: mixing a lithium manganate anode material with the eutectic solvent, and stirring and leaching at constant temperature;
step 3: and (3) centrifuging the solution obtained in the step (2) to obtain a solution containing lithium and manganese.
Further, the mass volume ratio of the lithium manganate anode material to the eutectic solvent is 1:20 g/mL-1:50 g/mL.
Further, the constant temperature stirring leaching temperature in the step 2 is 70-90 ℃ and the time is 2-6 h.
The invention discloses the following technical effects:
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 the system is used for leaching the lithium manganate anode material, and has the advantages of low leaching temperature, short leaching time and high leaching efficiency of lithium and manganese.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a process flow for recycling lithium and manganese as positive electrode materials of a waste lithium manganate lithium battery by using a eutectic solvent;
FIG. 2 is a graph showing the effect of leaching time on leaching lithium and manganese from a choline chloride, glycerol, and lactic acid eutectic solvent;
FIG. 3 is a graph showing the effect of leaching temperature on the leaching of lithium and manganese from a eutectic solvent of choline chloride, glycerol, and lactic acid;
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;
figure 5 shows the effect of the solid mass to volume ratio of the leachate on the leaching of lithium and manganese by the eutectic solvent of choline chloride, glycerol and lactic acid.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Fig. 1 is a schematic diagram of a process flow for recycling lithium and manganese of a waste lithium manganate lithium battery anode material by using a eutectic solvent.
The invention is described in further detail below with reference to examples:
example 1
(1) Preparation of the eutectic solvent: choline chloride, glycerol and lactic acid were mixed in a ratio of 1:1:1, 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 (the viscosity is 130 mPa.s).
(2) Leaching lithium manganate: 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 1:30g/mL, and reacting for 3h in a constant-temperature water bath at 90 ℃.
(3) Centrifuging the solution obtained in the step (2) at 4000rpm.
(4) And detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of 92.6% and 89.7% of lithium and manganese respectively.
Example 2
(1) Preparation of the eutectic solvent: guanidine hydrochloride, glycerol and lactic acid were mixed according to a ratio of 1:1:1, and mixing and stirring for 2 hours at 80 ℃ by adopting a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (the viscosity is 112 mPa.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 1:20g/mL, and reacting for 2 hours in a constant-temperature water bath at 80 ℃.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of 98.6% and 97.3% of lithium and manganese respectively.
Example 3
(1) Preparation of the eutectic solvent: guanidine hydrochloride, glycerol and lactic acid were mixed according to a ratio of 1:1:2, and mixing and stirring for 1h at 80 ℃ by adopting a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (the viscosity is 96 mPa.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 1:40g/mL, and reacting for 3h in a constant-temperature water bath at 70 ℃.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain the leaching rates of 99.6% and 99.3% of lithium and manganese respectively.
Example 4
(1) Preparation of the eutectic solvent: choline chloride, glycerol and lactic acid were mixed in a ratio of 1:0.5:2, and mixing and stirring for 2 hours at 90 ℃ by adopting a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (the viscosity is 162 mPa.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 1:50g/mL, and reacting for 4 hours in a constant-temperature water bath at 90 ℃.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of 97.4% and 97.1% of lithium and manganese respectively.
Example 5
(1) Preparation of the eutectic solvent: guanidine hydrochloride, glycerol and lactic acid were mixed according to a ratio of 1:0.5:2, and mixing and stirring for 2 hours at 80 ℃ by adopting a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent (the viscosity is 176 mPa.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 1:20g/mL, and reacting for 2 hours in a constant-temperature water bath at 70 ℃.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of 98.8% and 97.3% of lithium and manganese respectively.
Example 6
(1) Preparation of the eutectic solvent: choline chloride, glycerol and lactic acid were mixed in a ratio 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 (the viscosity is 152 mPa.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 1:40g/mL, and reacting for 4 hours in a constant-temperature water bath at 90 ℃.
(3) The solution obtained in the above step was centrifuged at 4000rpm.
(4) And detecting the content of lithium and manganese in the solution obtained by centrifugation, and calculating to obtain leaching rates of 96.3% and 95.8% of lithium and manganese respectively.
(one) effect of leaching time on leaching lithium and manganese from a eutectic solvent of choline chloride, glycerol and lactic acid:
the effect of leaching time on the leaching rate of lithium and manganese when the lithium manganate anode material and the eutectic solvent are stirred and leached at the constant temperature of 90 ℃ according to the mass-volume ratio of 1:20g/mL is shown in figure 2.
Wherein, the preparation of the eutectic solvent is as follows: choline chloride, glycerol and lactic acid were mixed in a ratio of 1:0.5:2, mixing the materials in a molar ratio, and stirring the materials for 1h at 70 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent.
(II) influence of leaching temperature on leaching of lithium and manganese by choline chloride, glycerol and lactic acid eutectic solvents:
the lithium manganate anode material and the eutectic solvent are stirred and leached for 4 hours at constant temperature according to the mass volume ratio of 1:20g/mL, and the influence of leaching temperature on the leaching rate of lithium and manganese is shown in figure 3.
Wherein, the preparation of the eutectic solvent is as follows: choline chloride, glycerol and lactic acid were mixed in a ratio of 1:1:2, mixing the materials in a molar ratio, and stirring the materials for 1h at 80 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent.
(III) influence of leaching temperature on leaching of lithium and manganese by guanidine hydrochloride, glycerin and lactic acid eutectic solvents:
the lithium manganate anode material and the eutectic solvent are stirred and leached for 2 hours at constant temperature according to the mass-volume ratio of 1:20g/mL, and the influence of leaching temperature on the leaching rate of lithium and manganese is shown in figure 4.
Wherein, the preparation of the eutectic solvent is as follows: guanidine hydrochloride, glycerol and lactic acid were mixed according to a ratio of 1:1:2, mixing the materials in a molar ratio, and stirring the materials for 1h at 80 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent.
(IV) the solid mass-volume ratio of the leaching solution affects the leaching of lithium and manganese by the eutectic solvent of choline chloride, glycerol and lactic acid:
the lithium manganate anode material and the eutectic solvent are stirred and leached for 4 hours at the constant temperature of 90 ℃ according to different mass volume ratios, and the influence of the solid mass volume ratio of the leaching liquid on the leaching of lithium and manganese by the choline chloride, glycerol and lactic acid eutectic solvent is shown in figure 5.
Wherein, the preparation of the eutectic solvent is as follows: guanidine hydrochloride, glycerol and lactic acid were mixed according to a ratio of 1:1:2, mixing the materials in a molar ratio, and stirring the materials for 1h at 80 ℃ in a water bath heating mode to obtain a clear and transparent solution, namely the eutectic solvent.
(V) influence of guanidine hydrochloride, glycerol and lactic acid ratio on leaching of lithium and manganese by guanidine hydrochloride, glycerol and lactic acid eutectic solvent:
the lithium manganate anode material and the eutectic solvent are stirred and leached for 2 hours at the constant temperature of 70 ℃ according to the mass-volume ratio of 1:20g/mL, and the influence of the proportion of guanidine hydrochloride, glycerol and lactic acid on the leaching rate of lithium and manganese is shown in Table 1.
Wherein, the preparation of the eutectic solvent is as follows: guanidine hydrochloride, glycerol and lactic acid are mixed according to the mole ratio shown in the table 1, and are mixed and stirred for 1h at 70 ℃ in a water bath heating mode, so that a clear and transparent solution is obtained, 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 the leaching rates of lithium and manganese tend to be balanced when the leaching time exceeds 4 hours; the leaching rate of lithium and manganese increases with the increase of the leaching temperature, and the increasing amplitude of the leaching rate of lithium and manganese decreases when the leaching temperature exceeds 80 ℃; in the test range, the leaching rate of lithium and manganese generally tends to increase along with the increase of the solid volume mass ratio of the leaching solution, but the leaching rate of lithium and manganese does not change greatly along with the increase of the solid volume mass ratio of the leaching solution because the leaching rate of lithium and manganese reaches more than 80 percent.
As can be seen from table 1, the eutectic solvents prepared with different molar ratios of guanidine hydrochloride, glycerol and lactic acid have higher leaching rates for both lithium and manganese in the experimental range.
TABLE 1 influence of guanidine hydrochloride, glycerol and lactic acid ratios on lithium and manganese leaching rates
Guanidine hydrochloride, glycerol and lactic acid molar examples Lithium leaching Rate (%) Leaching rate of manganese (%)
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 invention prepares the mutual-soluble stable eutectic solvent system by using choline chloride/guanidine hydrochloride, glycerol and lactic acid, and the system can leach lithium and manganese in the lithium manganate anode material efficiently, and has the characteristics of simple process, simple and convenient operation and environmental protection.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (3)

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) or guanidine hydrochloride, glycerin and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2) mixing and preparing;
the preparation method of the eutectic solvent comprises the following steps:
choline chloride or guanidine hydrochloride, glycerin 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.
2. The method for recycling lithium and manganese of the waste lithium manganate lithium battery anode material by using the eutectic solvent is characterized by comprising the following steps:
step 1: choline chloride or guanidine hydrochloride, glycerin and lactic acid are mixed according to a molar ratio of 1: (0.5-1): (1-2) mixing, and then stirring at a constant temperature of 70-90 ℃ for 1-2 hours to obtain the eutectic solvent;
step 2: mixing a lithium manganate anode material with the eutectic solvent, and stirring and leaching at constant temperature;
step 3: centrifuging the solution obtained in the step 2 to obtain a solution containing lithium and manganese;
and 2, stirring and leaching at the constant temperature at the temperature of 70-90 ℃ for 2-6 h.
3. The method according to claim 2, wherein the mass to volume ratio of the lithium manganate positive electrode material to the eutectic solvent is 1:20g/mL to 1:50g/mL.
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CN111690813A (en) * 2020-06-22 2020-09-22 南昌航空大学 Method for leaching valuable metals in waste lithium ion batteries by using eutectic solvent
CN112795785A (en) * 2021-02-02 2021-05-14 深圳技术大学 Simple substance nickel cobalt recovery method and separation equipment for ternary lithium ion battery anode material
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CN115161482A (en) * 2022-06-29 2022-10-11 昆明理工大学 Method for recycling valuable metal from NCM ternary positive electrode material
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