CN113422122B - Solid electrolyte-based waste battery lithium resource recovery method - Google Patents
Solid electrolyte-based waste battery lithium resource recovery method Download PDFInfo
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Abstract
The invention discloses a waste battery lithium resource recovery method based on solid electrolyte, which is driven by an external electric field, and can extract Li embedded in an anode electrode by the high selectivity of LLZTO+And recovered as LiOH with collection of H2. In addition, the P3HT modification of the surface of the LLZTO successfully expands the using performance of the LLZTO in the aqueous solution, and not only prevents H between water and the LLZTO+/Li+And exchange and is beneficial to extracting lithium resources from waste batteries. Based on the condition, the strategy proves that lossless, repeatable and high-purity lithium resource recovery can be realized from various waste lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of waste battery recycling, in particular to a waste battery lithium resource recycling method based on solid electrolyte.
Background
Lithium, which is the lightest metal in nature, has high electrochemical activity, has the lowest oxidation-reduction potential (-3.045V vs standard hydrogen electrode) and the highest theoretical specific capacity (3870mAh/g) compared with other solid elements, and has become an important energy material in the industrial field, such as batteries, nuclear fusion, aircraft products, ceramic glass, lubricants and cement. To our knowledge, lithium exists in two forms in nature, as lithium carbonate (Li) 2CO3) In the form of spodumene and lepidolite+) Present in salt lakes, brines and seawater. However, the extraction of lithium from ore has high requirements on quality and cost, while brine and seawater contain many impurities and have low lithium concentration. In recent years, with global spread of electric vehicles, demand for lithium resources has rapidly increased. It is predicted that the global market in 2023 will demand lithium resources far beyond its reserves, and therefore, there is an urgent need to develop and utilize secondary lithium resources to cope with the increasing demand. On the other hand, in the coming years, global Lithium Ion Batteries (LIBs) will enter a large-scale decommissioning phase. It is expected that 2025 annual LIBs scrapped will exceed 900 million tons and the production value will reach $ 237.2 billion. Considering that the average service life of the power battery is 4-6 years, the lithium content (5-7 wt%) in the anode material is much higher than that of brine and seawater, and the waste battery is considered as a future energy sourceThe most promising secondary lithium resource is used.
However, only 5% of the spent lithium batteries are recovered in the world, and the recovery rate of lithium is less than 1%. Worse yet, most industrial processes focus on the recovery of cobalt and nickel, except for the recovery of lithium, which is involved by the companies TOXCO and accuec GmbH. To date, LIBs recovery strategies have been hydrometallurgy, pyrometallurgy, biometallurgy, and mixing (combining hydrometallurgy and pyrometallurgy). Hydrometallurgical techniques rely primarily on acid/base leaching to recover nickel, cobalt, lithium from spent LIBs, but the use of base and acid leaching produces large volumes of spent liquor to be treated, whereas the lithium recovery process is usually in the last step, which inevitably results in low lithium concentrations (0.5-3g/L) and high impurities. In addition, the pyrometallurgical method is the most frequently used method in industry at present due to short time and easy scale-up, but still faces the problem of lithium loss in slag phase. At the same time, the energy consumption of high-temperature treatment is high, and the electrolyte and other components in the electrode are converted into CO through combustion 2And other harmful components such as P2O5Secondary pollution will be caused. Furthermore, the biological metallurgy is a mineral biological oxidation process assisted by microorganisms, in which bacteria are difficult to culture, and the slow kinetic rate and low pulp density are its fatal weaknesses. Therefore, a high-purity pollution-free recovery strategy of lithium resources in waste LIBs is a key problem to be solved urgently in the current energy field.
Disclosure of Invention
The invention aims to provide a method for recovering waste battery lithium resources based on solid electrolyte, aiming at the problems in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for recovering waste battery lithium resources based on solid electrolyte comprises the following specific steps:
s1, preparing the LLZTO waterproof ceramic tube: dissolving a certain mass of P3HT powder in an organic solvent in a fume hood, wherein the proportion of the P3HT powder to the organic solvent is 10-30mg/ml, sealing and stirring to prepare a modified solution, then soaking the LLZTO ceramic tube in the modified solution for 5min, placing the soaked LLZTO ceramic tube in a vacuum drying oven for drying, and forming a waterproof coating on the surface of the LLZTO after drying;
S2, in a glove box, wetting the electrode plates of the taken out waste batteries by lithium ion electrolyte for later use;
s3, uniformly winding the wetted electrode slice prepared in the step S2 on the outer surface of the LLZTO waterproof ceramic tube in the glove box, sealing the LLZTO waterproof ceramic tube wound with the positive plate in a stainless steel shell, taking out the glove box, and connecting the stainless steel shell tightly contacted with the positive plate into the positive polarity end of the charging machine;
s4, injecting deionized water into the LLZTO waterproof ceramic tube to serve as an initial solution for enriching lithium ions, introducing an inert electrode (a platinum electrode, a carbon rod and the like) into the deionized water in the LLZTO waterproof ceramic tube, and connecting the inert electrode to the negative end of the charge and discharge machine;
s5, due to the existence of the voltage between the inert electrode in the positive plate and the deionized water, the LiFePO of the LLZTO waterproof ceramic tube from the anode side4Extraction of Li from electrode plate+Associated with FePO4Forming; at the same time, deionized water is electrolyzed to OH at the cathode-And H+Ions, OH-With extracted Li+Bonding in a cathode solution to generate LiOH; at the same time, H+The ions pick up electrons from the external circuit, resulting in H2Gas generation and recovery to drive Li of electrode sheet +Transmitting the anode into a cathode chamber through the LLZTO waterproof ceramic tube body for enrichment to form LiOH reaction liquid; cutting off the power supply when the voltage change curvature (dV/ds) between the positive plate and the deionized water is instantly increased; at this time, the LLZTO waterproof ceramic tube is enriched with Li+The LiOH reaction solution is recovered, so that the recovery of lithium resources in the electrode plate of the lithium ion battery is completed; the overall reaction equation for the process is as follows:
anode (+): LiFePO4-e-→FePO4+Li+
A cathode (-): 2Li++2e-+2H2O→2LiOH+H2
And (3) total reaction:
further, in step S1, the organic solvent is selected from any one of carbon disulfide and chloroform.
Further, in step S2, the lithium ion electrolyte is a mixture of 1M (1mol/L) lithium hexafluorophosphate dissolved in ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1.
The principle of the invention is as follows: the invention constructs a LiFePO4、LiCoO2And LiNi0.5Co0.2Mn0.3O2And the like, waste lithium ion batteries and green and high-purity lithium resource recovery technology. In the invention, under the drive of an external electric field, the high selectivity of LLZTO can extract Li embedded in an anode electrode+And recovered as LiOH with collection of H2. In addition, the P3HT modification of the surface of the LLZTO successfully expands the using performance of the LLZTO in the aqueous solution, and not only prevents H between water and the LLZTO +/Li+And exchanging and facilitating the extraction of lithium resources from waste batteries. Based on the condition, the strategy proves that lossless, repeatable and high-purity lithium resource recovery can be realized from various waste lithium ion batteries.
The invention has the beneficial effects that: the invention improves the lithium recovery efficiency of the waste battery on the premise of reducing the total energy consumption, and provides a waste lithium resource recovery design strategy based on the modified LLZTO solid electrolyte for the first time, and the design can realize the enrichment of LiOH at low cost while blocking interfering ions. At the same time, this lithium recovery strategy also involves clean energy H2The generation of the green energy, the collection and the utilization of the green energy can effectively compensate the cost consumption in the lithium resource recovery process. In addition, the modification of P3HT on the surface of the LLZTO ceramic tube effectively expands the application of the LLZTO in aqueous solution, and is beneficial to extracting Li from waste lithium batteries+. In general, the lithium recovery strategy is different from the traditional waste battery recovery strategy, is environment-friendly and energy-saving, and can recover lithium resources in advance to ensure the lithium recovery efficiency without any waste battery recovery strategyAffecting other precious metal recovery, this process is completely different from traditional recovery strategies, such as hydrometallurgical and pyrometallurgical processes, with obvious advantages: 1) the structural integrity of the electrode can be kept to the maximum extent, so that other noble metals can be recovered in other modes in the following process; 2) the recovery mode is environment-friendly, chemical substances such as acid, alkali and the like are not used, the high-purity lithium hydroxide can be recovered, and H is realized simultaneously 2Enriching; 3) byproduct H2The profit of the method can well make up the cost in the lithium resource recovery process, so that the strategy has good profitability and application prospect. The present invention therefore leads to the development of a promising process to ensure the future energy use of lithium supply.
Drawings
FIG. 1 is a schematic diagram of a lithium ion extraction process of the present invention.
FIG. 2 is a graph showing the effect of P3HT before and after modification of LLZTO ceramic tube.
Fig. 3 is a graph of a lithium iron phosphate electrode in a particular application of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are not to be construed as limiting the present invention.
Example 1
As shown in fig. 1, the method for recovering lithium resources from waste batteries based on solid electrolyte in this embodiment includes the following specific steps:
s1, preparing a LLZTO waterproof ceramic tube: dissolving a certain mass of P3HT powder in a carbon disulfide solution in a fume hood, wherein the ratio of the P3HT powder to the carbon disulfide solution is 12mg/ml, sealing and stirring to prepare a modified solution, then soaking the LLZTO ceramic tube in the modified solution for 5min, placing the soaked LLZTO ceramic tube in a vacuum drying oven for drying, and forming a waterproof coating on the surface of the LLZTO after drying;
S2, in a glove box, wetting the electrode plates of the taken out waste batteries with lithium ion electrolyte for later use, wherein the lithium ion electrolyte is formed by dissolving 1M lithium hexafluorophosphate in ethylene carbonate and diethyl carbonate in a volume ratio of 1:1 and mixing;
s3, uniformly winding the wetted electrode slice prepared in the step S2 on the outer surface of the LLZTO waterproof ceramic tube in the glove box, sealing the LLZTO waterproof ceramic tube wound with the positive plate in a stainless steel shell, taking out the glove box, and connecting the stainless steel shell tightly contacted with the positive plate into the positive polarity end of the charging machine;
s4, injecting deionized water into the LLZTO waterproof ceramic tube to serve as an initial solution for enriching lithium ions, introducing an inert electrode (a platinum electrode, a carbon rod and the like) into the deionized water in the LLZTO waterproof ceramic tube, and connecting the inert electrode to the negative end of the charge and discharge machine;
s5, due to the existence of the voltage between the anode plate and the inert electrode in the deionized water, the LiFePO of the LLZTO waterproof ceramic tube from the anode side4Extraction of Li from electrode sheet+Accompanied by FePO4Forming; at the same time, deionized water is electrolyzed to OH at the cathode-And H+Ions, OH-With extracted Li +Bonding in a cathode solution to generate LiOH; at the same time, H+The ion picks up electrons from the external circuit, resulting in H2Gas generation and recovery to drive Li of electrode sheet+Transmitting the anode into a cathode chamber through an LLZTO waterproof ceramic tube body for enrichment to form LiOH reaction liquid; cutting off the power supply when the voltage change curvature (dV/ds) between the positive plate and the deionized water is instantly increased; at this time, the LLZTO waterproof ceramic tube is enriched with Li+The LiOH reaction solution is recovered, so that the recovery of lithium resources in the electrode plate of the lithium ion battery is completed; the overall reaction equation for the process is as follows:
anode (+): LiFePO4-e-→FePO4+Li+
A cathode (-): 2Li++2e-+2H2O→2LiOH+H2
And (3) total reaction:
example 2
The method for recovering the waste battery lithium resource based on the solid electrolyte comprises the following specific steps:
s1, preparing a LLZTO waterproof ceramic tube: dissolving a certain mass of P3HT powder in a chloroform solution in a fume hood, wherein the proportion of the P3HT powder to the chloroform solution is 22mg/ml, sealing and stirring to prepare a modified solution, then soaking the LLZTO ceramic tube in the modified solution for 5min, placing the soaked LLZTO ceramic tube in a vacuum drying oven for drying, and forming a waterproof coating on the surface of the LLZTO after drying;
S2, in a glove box, wetting the electrode plates of the taken out waste batteries with lithium ion electrolyte for standby, wherein the lithium ion electrolyte is formed by dissolving 1M lithium hexafluorophosphate in ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1;
s3, uniformly winding the wetted electrode slice prepared in the step S2 on the outer surface of the LLZTO waterproof ceramic tube in the glove box, sealing the LLZTO waterproof ceramic tube wound with the positive plate in a stainless steel shell, taking out the glove box, and connecting the stainless steel shell tightly contacted with the positive plate into the positive polarity end of the charging machine;
s4, injecting deionized water into the LLZTO waterproof ceramic tube to serve as an initial solution for lithium ion enrichment, introducing an inert electrode (a platinum electrode, a carbon rod and the like) into the deionized water in the LLZTO waterproof ceramic tube, and connecting the inert electrode to the negative electrode end of the charge and discharge machine;
s5, due to the existence of the voltage between the inert electrode in the positive plate and the deionized water, the LiFePO of the LLZTO waterproof ceramic tube from the anode side4Extraction of Li from electrode plate+Associated with FePO4Forming; at the same time, deionized water is electrolyzed to OH at the cathode-And H+Ions, OH-With extracted Li +Bonding in a cathode solution to generate LiOH; at the same time, H+The ions pick up electrons from the external circuit, resulting in H2Gas generation and recovery to drive Li of electrode sheet+Transmitting the anode into a cathode chamber through an LLZTO waterproof ceramic tube body for enrichment to form LiOH reaction liquid; when in useCutting off the power supply when the voltage change curvature (dV/ds) between the positive plate and the deionized water is instantly increased; at this time, the LLZTO waterproof ceramic tube is enriched with Li+The LiOH reaction solution is recovered, so that the recovery of lithium resources in the electrode plate of the lithium ion battery is completed; the overall reaction equation for the process is as follows:
anode (+): LiFePO4-e-→FePO4+Li+
A cathode (-): 2Li++2e-+2H2O→2LiOH+H2
And (3) total reaction:
as shown in fig. 2, the present invention modifies the existing LLZTO ceramic tube by using an organic solvent containing P3HT, and fig. 2 shows the effect of the LLZTO ceramic tube before and after modification on the present invention, wherein:
(a) SEM image of bare LLZTO after two weeks immersion in deionized water, scale bar 5 μm, inset is the dynamic contact angle of LLZTO with deionized water.
(b) EDS images of bare LLZTO two weeks after immersion in water, scale bar 5 μm.
(c) The schematic diagram of H +/Li + ion exchange between bare LLZTO and deionized water, combined with the detection results in FIG. 2 (a, b), illustrates that bare LLZTO has serious corrosion problem in water.
(d) SEM image of the P3HT modified LLZTO after being immersed in water for two weeks, the scale bar is 5 μm, and the inset shows the dynamic contact angle of the P3HT modified LLZTO and deionized water.
(e) EDS images of P3HT modified LLZTO two weeks after immersion in water, scale bar 5 μm.
(f) A schematic representation of the absence of ion exchange problems of P3HT modified LLZTO with water demonstrates that P3HT modified LLZTO can completely avoid corrosion by water.
(g) After soaking LLZTO and LLZTO @ P3HT, the Li + concentration varied in the different solutions. It is demonstrated that the P3HT modified LLZTO has less Li + dissolution problem in deionized water or LiCl aqueous solution.
(h) The lithium ion recovery system of naked LLZTO, LLZTO @ P3HT corresponds to Li + conductivity in working environment at 50 ℃ and 25 ℃.
(i) Raman spectra of bare LLZTO exposed to air, bare LLZTO immersed in deionized water, LLZTO @ P3HT exposed to air, and immersed in deionized water. It is demonstrated that P3HT can well prevent LLZTO from being oxidized in air to form Li2CO3, and prevent LLZTO from being corroded in deionized water.
The application of the embodiment in the waste lithium iron phosphate electrode battery is shown in fig. 3, wherein: 3mL of deionized water is placed in the U-shaped LLZO ceramic; and in the iron shell, an electrolyte wetted LiFePO4 electrode plate (4cm multiplied by 1.5cm, unit specific capacity 150mAh/g) is arranged in the ring wall. After the device is assembled, the cathode is connected to the negative pole of the charge-discharge machine, the iron shell is connected to the positive pole of the charge-discharge machine, constant current charging is carried out, and the charging is stopped when the voltage rises to a certain value. The voltage change recorded by the test system is shown in the figure, and the energizing capacity, namely the electron conduction capacity, recorded by the instrument is 15.3 mAh. ICP is used for representing the content change of each element before and after the experiment of the deionized water solution and the LiFePO4 electrode sheet, and the diagram shows that the Fe element is not detected in the deionized water in the U-shaped tube. Meanwhile, the content of lithium element in the LiFePO4 electrode sheet is reduced from 89ppm to 9ppm, and the content of lithium element in deionized water is increased from 0 to 1364ppm, thereby proving the selective permeability of the LLZO electrolyte material to lithium ions and the barrier property to other ions. On the other hand, the lithium content of the LiFePO4 electrode sheet decreased by 80ppm, which was substantially equal to the theoretical decrease (87ppm) calculated from the capacity. In addition, the XRD characterization of the electrode sheet before and after the experiment also corresponds to the phase change from LiFePO4 to FePO4 before and after lithium extraction, which indicates that the lithium resource recovery system of the waste battery based on the "lithium-rich electrode (anode) | garnet solid electrolyte | deionized water solution" is feasible in principle design.
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 as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (3)
1. A method for recovering lithium resources of waste batteries based on solid electrolyte is characterized by comprising the following steps: the method comprises the following specific steps:
s1, preparing the LLZTO waterproof ceramic tube: dissolving a certain mass of P3HT powder in an organic solvent in a fume hood, wherein the proportion of the P3HT powder to the organic solvent is 10-30 mg/ml, sealing and stirring to prepare a modified solution, then soaking the LLZTO ceramic tube in the modified solution for 5min, placing the soaked LLZTO ceramic tube in a vacuum drying oven for drying, and forming a waterproof coating on the surface of the LLZTO after drying;
s2, in a glove box, wetting the electrode plates of the taken out waste batteries by lithium ion electrolyte for later use;
s3, uniformly winding the wetted electrode slice prepared in the step S2 on the outer surface of the LLZTO waterproof ceramic tube in the glove box, then sealing the LLZTO waterproof ceramic tube wound with the positive electrode slice in a stainless steel shell, taking out the glove box, and then connecting the stainless steel shell which is tightly contacted with the positive electrode slice into the positive polarity end of the charging and discharging machine;
S4, injecting deionized water into the LLZTO waterproof ceramic tube to serve as an initial solution for enriching lithium ions, introducing an inert electrode into the deionized water in the LLZTO waterproof ceramic tube, and connecting the inert electrode to the negative electrode end of the charge and discharge machine;
s5, due to the existence of the voltage between the inert electrode in the positive plate and the deionized water, the LiFePO of the LLZTO waterproof ceramic tube from the anode side4Extraction of Li from electrode plate+Associated with FePO4Forming; at the same time, deionized water is electrolyzed to OH at the cathode-And H+Ions, OH−With extracted Li+Bonding in a cathode solution to generate LiOH; at the same time, H+The ions pick up electrons from the external circuit, resulting in H2Gas generation and recovery to drive Li of electrode sheet+Transmitting the anode into a cathode chamber through an LLZTO waterproof ceramic tube body for enrichment to form LiOH reaction liquid; when the voltage change curvature between the positive plate and the deionized water is instantly increased, the device is cut offA power source; at this time, the LLZTO waterproof ceramic tube is enriched with Li+The LiOH reaction solution is recovered, so that the recovery of lithium resources in the electrode plate of the lithium ion battery is completed; the overall reaction equation for the process is as follows:
2. the solid electrolyte based method for recycling lithium resources from spent batteries according to claim 1, characterized in that: in step S1, the organic solvent is selected from carbon disulfide or chloroform.
3. The solid electrolyte based method for recycling lithium resources from spent batteries according to claim 1, characterized in that: in step S2, the lithium ion electrolyte is prepared by dissolving 1M lithium hexafluorophosphate in ethylene carbonate and diethyl carbonate at a volume ratio of 1:1 and mixing.
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