CN110777390B - Self-driven electrochemical lithium extraction method based on rocking chair type structure electrode system - Google Patents

Self-driven electrochemical lithium extraction method based on rocking chair type structure electrode system Download PDF

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CN110777390B
CN110777390B CN201911082936.2A CN201911082936A CN110777390B CN 110777390 B CN110777390 B CN 110777390B CN 201911082936 A CN201911082936 A CN 201911082936A CN 110777390 B CN110777390 B CN 110777390B
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纪志永
郭志远
袁俊生
刘杰
赵颖颖
杨凤娟
王军
郭小甫
王士钊
李非
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Hebei University of Technology
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Abstract

The invention belongs to the technical field of electrochemical lithium extraction, and particularly relates to an electrochemical lithium extraction method for realizing high selectivity and low energy consumption extraction of dissolved and stored thin lithium resources based on a rocking chair type structure electrode system. The invention relates to a self-driving electrochemical lithium extraction method based on a rocking chair type structure electrode system, which is characterized in that on the basis of the existing electrochemical lithium extraction method based on the rocking chair type structure electrode system, the self-driving process of electrodes is firstly used for the electrochemical lithium extraction method, the self-driving (even energy recovery) process lithium extraction is carried out by utilizing the self potential difference between the electrodes in different states in the rocking chair type structure electrode system, so that the two electrodes firstly extract lithium by utilizing the smaller self potential difference, and then further extract lithium by applying an external electric field, the energy consumption of the lithium extraction process is effectively reduced, the synchronous improvement of the exchange capacity and the selectivity coefficient of the electrodes on lithium is realized, and the invention has remarkable technical advantages.

Description

Self-driven electrochemical lithium extraction method based on rocking chair type structure electrode system
Technical Field
The invention belongs to the technical field of electrochemical lithium extraction, and particularly relates to an electrochemical lithium extraction method for realizing high selectivity and low energy consumption extraction of a solution state thin lithium resource based on a rocking chair type structure electrode system.
Background
Lithium is the lightest metal in nature, has very active chemical properties, is known as energy metal, and is widely applied to industries such as glass, ceramics, metallurgy, lubricants, refrigerants and the like and the fields such as aviation, national defense, electronics and the like. Especially in recent years, lithium batteries have been widely used due to their advantages of light weight, small size, long service life, high energy density, etc., and especially with the rapid rise and development of emerging industries such as electric vehicles, wind power, nuclear power, etc., the demand for lithium resources has increased day by day and gradually shows a leap-growth. However, because the storage amount of the ore lithium is very limited, and the method for extracting the ore lithium has the defects of high pollution, high energy consumption and the like, the extraction of the lithium resource is gradually shifted from the extraction of the ore lithium to the extraction of the dissolved lithium resource (including underground brine and seawater) represented by salt lake brine. Therefore, how to effectively extract lithium resources from the dissolved lithium resources becomes a current research hotspot.
At present, a mature method for developing the lithium resource in the salt lake is an evaporation precipitation method, the process has the advantages of simplicity in operation and mature technology, but also has the defects of long time consumption, weather influence, low recovery rate, consumption of a large amount of sodium carbonate medicament in the extraction process and the like, and the production cost is greatly increased. In addition, although the lithium resource in the seawater is over ten thousand times of the lithium resource on the land, the concentration is very low, which also becomes a difficulty for the development of the dissolved lithium resource. Aiming at the development and extraction of the dissolved and thin lithium resource, the ion exchange and adsorption method is the focus of research due to the characteristics of high selectivity and low energy consumption. However, the elution process consumes a large amount of acid or oxidant, and the elution process has a certain adverse effect on the structure of the ion sieve. In addition, the problem of granulation of lithium ion sieves further limits their industrial application.
The electrochemical lithium extraction method is a method for realizing the lithium extraction and intercalation process based on a high-selectivity lithium ion sieve method and a low-energy-consumption electrochemical redox method, effectively avoids the use of acid or a strong oxidant, and becomes a new lithium extraction method with great development potential. Researchers have developed the use of lambda-Mn2O4、Li1-XFePO4And LiNi1/3Co1/3Mn1/3O2The like is used as a working electrode, Ag, Zn, polypyrrole (PPy) and the like are used as a lithium extraction system of a counter electrode, but the process needs the lithium intercalation and deintercalation processThe step is carried out, and the lithium extraction efficiency is reduced to a certain extent.
LiFePO is utilized by Zhao Zhong Wei professor team of Zhongnan university4/FePO4The rocking chair type structure electrode system realizes that the extraction and the recovery of lithium are synchronously carried out on different electrodes. Previous research of Zhao Meng Yao, et al, the university of Hebei Industrial university, also developed LiMn with higher lithium extraction efficiency2O4/Li1-xMn2O4An electrode system. The system is favorable for improving the exchange capacity of the electrode to lithium under high operating voltage, but can also cause the selectivity of the electrode to lithium to be reduced and bring about the defect of high energy consumption; although the electrode has better selectivity and lower energy consumption when operated under low voltage, the electrode has lower exchange capacity with lithium, and the efficiency of lithium extraction is low. Namely, the electrode system exhibits a "Trade-off effect" between the exchange capacity and selectivity for lithium. Therefore, the development of a new electrochemical lithium extraction method with high selectivity, high efficiency and low energy consumption has positive significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a self-driven electrochemical lithium extraction method based on a rocking chair type structure electrode system, so as to solve the problems of high energy consumption and a Trade-off effect in the electrochemical lithium extraction process based on the rocking chair type structure electrode system in the prior art.
In order to solve the technical problems, the invention provides a self-driven electrochemical lithium extraction method based on a rocking chair type structure electrode system, which comprises the following steps:
(1) respectively placing a lithium-rich electrode and a lithium-poor electrode of a rocking chair type structure electrode system in isolated recovery liquid and raw material liquid;
(2) carrying out short circuit on the lithium-rich electrode and the lithium-poor electrode or carrying out reaction by externally connecting an electric quantity recovery device, and stopping the reaction when the current is reduced to a certain value;
(3) the lithium-rich electrode and the lithium-poor electrode are respectively connected with the anode and the cathode of a direct current power supply to carry out constant-voltage reaction, and then the lithium-rich electrode and the lithium-poor electrode are taken out and washed, and the positions of the lithium-rich electrode and the lithium-poor electrode are exchanged;
(4) and (4) repeating the operations of the steps (2) to (3) to realize the extraction and enrichment of the lithium resource in the raw material liquid to the lithium in the recovery liquid.
Specifically, the electric quantity recovery device comprises a capacitor.
Specifically, the electrode system with the rocking chair type structure comprises electrode systems consisting of different lithium-containing states of the same electrode material.
Specifically, the electrode system with the rocking chair type structure comprises LiMn2O4/Li1-xMn2O4、LiFePO4/Li1-xFePO4、Li2TiO3/Li2-xTiO3、LiNi1/3Co1/3Mn1/3O2/Li1-xNi1/3Co1/3Mn1/3O2、Li7Ti5O12/Li7-xTi5O12At least one of the electrode systems.
Specifically, the electrode system with the rocking chair type structure is prepared according to the following steps:
mixing the selected lithium ion sieve powder, a conductive agent and a binder, adding a solvent, stirring to obtain emulsion slurry, uniformly coating the emulsion slurry on a current collector, and drying to obtain a required lithium-rich electrode;
connecting the obtained lithium-rich electrode with a positive electrode, connecting an AgCl electrode with a negative electrode, placing the lithium-rich electrode in an electrolyte, introducing constant-voltage direct current, and stopping reaction when the current is as low as 0.1mA to obtain the required lithium-poor electrode.
Specifically, the lithium ion sieve powder comprises LiMn2O4、LiFePO4、Li2TiO3、LiNi1/3Co1/3Mn1/3O2、Li7Ti5O12One or a mixture of several of them.
Specifically, the recovery solution and the raw material solution are separated by a monovalent selective anion exchange membrane.
Specifically, in the step (2), the short-circuit step is stopped until the current is reduced to 0.2-5.0 mA.
Specifically, in the step (3), the operating voltage of the constant voltage reaction is 0.2-1.2V.
Specifically, in the step (3), the constant-voltage reaction step is stopped when the current is reduced to 0.1 mA.
Specifically, in the step (3), the washing step is distilled water washing.
The invention relates to a self-driven electrochemical lithium extraction method based on a rocking chair type structure electrode system, which is characterized in that on the basis of the existing rocking chair type structure electrode system electrochemical lithium extraction method, lithium-rich state electrodes and lithium-poor state electrodes are respectively placed in a recovery solution and an extracting solution which are isolated by an anion exchange membrane, self potential differences between different lithium-containing state electrodes are firstly short-circuited to carry out a self-driven lithium extraction process, then an external electric field driving lithium extraction process is carried out by applying constant voltage potential between the two electrodes, so that lithium removal/lithium insertion of the corresponding electrodes is respectively realized, and then the positions of the two electrodes are exchanged to repeatedly carry out the self-driven process and the external electric field driving process, thereby realizing the selective extraction of lithium resources.
The electrochemical lithium extraction method effectively utilizes the self potential difference between the electrodes in different states to carry out self-driven lithium extraction, effectively avoids the defect that the selectivity of the electrode pair for lithium ions is reduced due to the high potential obtained by adding the direct external voltage and the self potential difference, improves the selectivity and exchange capacity of the electrode pair for lithium, and thus obtains the LiCl solution with higher purity; meanwhile, the potential difference existing between different lithium-containing electrodes is fully utilized, so that the energy waste is reduced, and the energy consumption in the whole electrochemical lithium extraction process is reduced by over 50 percent.
According to the self-driving electrochemical lithium extraction method based on the rocking chair type structure electrode system, the self-driving process of the electrode is used for the electrochemical lithium extraction method for the first time, the self potential difference between the electrodes in different states in the rocking chair type structure system is utilized to extract lithium in the self-driving (even energy recovery) process, so that the electrodes firstly extract lithium by utilizing the smaller self potential difference, and then further extract lithium by applying an external electric field, the energy consumption of the lithium extraction process is effectively reduced, the lithium selectivity coefficient and the exchange capacity of the electrode are improved, and the method has remarkable technical advantages; meanwhile, the whole lithium extraction method avoids the use of chemical agents, only consumes a small amount of clean energy and electric energy, has the advantage of environmental friendliness, and is suitable for industrial popularization.
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In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
fig. 1 is a schematic structural diagram of a "self-driven" lithium extraction device according to the present invention:
FIG. 2 is a graph of current versus time for a version of example 1 of the present invention and a version of comparative example 1, wherein (a) is a version of example 1 and (b) is a version of comparative example 1;
FIG. 3 is a graph showing the change in ion exchange capacity between the embodiment 1 of the present invention and the embodiment of comparative example 1, wherein (a) is the embodiment 1 and (b) is the embodiment of comparative example 1;
FIG. 4 is a graph showing a comparison of unit energy consumption in the embodiment 1 of the present invention and the embodiment of the comparative example 1.
The reference numbers in the figures denote: 1-lithium-rich state electrode, 2-lithium-poor state electrode, 3-raw material liquid chamber, 4-recovery liquid chamber, 5-monovalent selective anion exchange membrane, and 6-single-pole double-throw switch.
Detailed Description
In the following examples of the present invention, the preparation method of the electrode system with the rocking chair structure can be performed by referring to the prior art, such as the corresponding electrode system disclosed in chinese patent CN 107201452A.
In the following examples of the present invention, the lithium electrode after the reaction was characterized by using a D8-Focus X-ray diffractometer, and the change in the concentration of each cation in the recovered solution before and after the reaction was measured by using a TAS-990F atomic absorption spectrophotometer.
In the following embodiment of the present invention, the electrochemical lithium extraction process is performed based on the apparatus shown in fig. 1, and the lithium extraction apparatus shown in fig. 1 comprises a raw material liquid chamber 3 and a recovery liquid chamber 4 separated by a monovalent selective anion exchange membrane 5 (such as ASTOM-ACS), the raw material liquid chamber 3 contains a raw material liquid, the recovery liquid chamber 4 contains a recovery liquid, and the switching between the steps of the "self-driven" lithium extraction process and the external electric field driven lithium extraction process can be switched by a single-pole double-throw switch 6 during the lithium extraction process.
Example 1
The invention relates to a self-driven electrochemical lithium extraction method based on a rocking chair type structure electrode system, which comprises the following steps:
(1) rocking chair type structure electrode system construction
High-temperature solid-phase method for self-producing LiMn2O4Powder of LiMn, to obtain LiMn2O4And carbon black and LA132 binder according to the mass ratio of 8: 1: 1 mixing, adding 50% ethanol solvent, stirring, ultrasonic dispersing for 3min to obtain uniformly dispersed slurry, uniformly coating the slurry on 3.5 × 5cm carbon fiber cloth with a thickness of about 5-6mg/cm2Drying at 70 ℃ for 12h to obtain a lithium-rich electrode;
the obtained lithium-rich LiMn2O4Connecting the electrode with the anode, connecting the AgCl electrode with the cathode, placing the AgCl electrode with the cathode in 0.05mol/L KCl solution for constant-pressure 1.2V reaction, stopping the reaction when the current is reduced to 0.1mA, and obtaining the Li in a poor lithium state1-xMn2O4An electrode;
placing the lithium-rich electrode 1 in the recovery liquid chamber 4, and placing the lithium-poor electrode 2 in the raw material liquid chamber 3; wherein the recovery solution is 0.05mol/L KCl solution, and the raw material solution is 0.05mol/L LiCl and 1.00mol/L MgCl2The mixed solution of (1);
(2) self-driven lithium extraction
Placing a single-pole double-throw switch 6 at a shorts the lithium-rich state electrode 1 and the lithium-poor state electrode 2 and records the current change. Due to the high redox potential of the lithium-poor electrode 2 relative to the lithium-rich electrode 1, electrons are transferred from the lithium-rich electrode 1 to the lithium-poor electrode 2 in an external circuit, lithium ions are selectively absorbed by the lithium-poor electrode 2 in a solution system, the lithium-rich electrode 1 emits the lithium ions at the moment, the reaction is stopped when the current is reduced to 0.2mA, and the reaction is about 1.5h in the self-driving process;
(3) external electric field driven lithium extraction
And after the reaction of the self-driving process is finished, the single-pole double-throw switch 6 is arranged at the position b, the constant voltage is controlled to be 1.0V for operation, and the current change is recorded. At the moment, the lithium-rich electrode 1 is connected with the anode and oxidized to release lithium ions, the lithium-poor electrode 2 is connected with the cathode and reduced to adsorb lithium ions, the reaction is stopped when the current is observed to be reduced to 0.1mA, and the whole reaction is stopped for about 1.5 h; taking out the lithium-rich electrode 1 and the lithium-poor electrode 2, cleaning the lithium-rich electrode 1 and the lithium-poor electrode 2 with distilled water, and then reversing the lithium-rich electrode 1 and the lithium-poor electrode 2, namely placing the lithium-rich electrode 1 in the raw material solution and placing the lithium-poor electrode 2 in the recovery solution;
(4) repeated cycling reaction
And (4) repeating the operations in the steps (2) to (3) to realize the extraction and enrichment of the lithium resource in the raw material liquid into the recovery liquid.
Comparative example 1
The electrochemical lithium extraction method based on the electrode system of the rocking chair structure in the comparative example is the same as that in example 1, except that the self-driving process in the step (2) is not performed.
The ion content of the recovered solution described in example 1 and comparative example 1 was measured by a TAS-990F atomic absorption spectrophotometer, and the change in current during this process is shown in fig. 2. As can be seen from fig. 1 (a), the left area is a self-driving process, the right area is an external electric field constant voltage operation process, each peak value is a current fluctuation during stirring sampling, and the electric quantity in the self-driving process is almost equal to the electric quantity in the external electric field driving process; fig. 2 (b) shows the variation of the operating current with a single external electric field, which is slightly less than the sum of the two portions of the integrated electric quantity in fig. 2 (a).
Mg in the recovered solutions of example 1 and comparative example 12+And Li+The change in switching capacity of (2) is shown in fig. 3. Wherein (a) in FIG. 3 is the change in ion exchange capacity in example 1, and Li was calculated+Has an exchange capacity of 32.72Mg/g, Mg2+The exchange capacity of (A) is 4.05 mg/g; while figure showsLi with a single external field shown in (b) of 3+And Mg2+The exchange capacities of (A) were 29.85mg/g and 6.78mg/g, respectively.
FIG. 4 is a graph comparing the energy consumption per unit for the example 1 scheme and the comparative example 1 scheme, showing that the selectivity coefficient is increased from 301.90 to 554.27 compared to a single external electric field operation (1.0V condition); the unit energy consumption is reduced from 28.33 to 14.09Wh/mol Li, and the electricity consumption is saved by 50.26 percent.
Example 2
The invention relates to a self-driven electrochemical lithium extraction method based on a rocking chair type structure electrode system, which comprises the following steps:
(1) rocking chair type structure electrode system construction
High-temperature solid-phase method for self-producing LiMn2O4Powder of LiMn, to obtain LiMn2O4And carbon black and LA132 binder according to the mass ratio of 8: 1: 1 mixing, adding 50% ethanol solvent, stirring, ultrasonic dispersing for 3min to obtain uniformly dispersed slurry, coating the slurry on 3.5 × 5cm carbon fiber cloth with a thickness of 5-6mg/cm2Drying at 70 ℃ for 12h to obtain a lithium-rich electrode;
the obtained lithium-rich LiMn2O4Connecting the electrode with the anode, connecting the AgCl electrode with the cathode, placing the AgCl electrode with the cathode in 0.05mol/L KCl solution for constant-pressure 0.8V reaction, stopping the reaction when the current is reduced to 0.1mA, and obtaining the Li in a poor lithium state1-xMn2O4An electrode;
placing the lithium-rich electrode 1 in the recovery liquid chamber 4, and placing the lithium-poor electrode 2 in the raw material liquid chamber 3; wherein the recovery solution is 0.05mol/L KCl solution, and the raw material solution is 0.05mol/L LiCl and 1.00mol/L MgCl2The mixed solution of (1);
(2) self-driven lithium extraction
Placing a single-pole double-throw switch 6 at a shorts the lithium-rich state electrode 1 and the lithium-poor state electrode 2 and records the current change. Due to the high redox potential of the lithium-poor electrode 2 relative to the lithium-rich electrode 1, electrons are transferred from the lithium-rich electrode 1 to the lithium-poor electrode 2 in an external circuit, lithium ions are selectively adsorbed by the lithium-poor electrode 2 in a solution system, the lithium-rich electrode 1 emits lithium ions, the reaction is stopped when the current is reduced to 0.2mA, and the reaction is about 1.5h in the self-driving process;
(3) external electric field driven lithium extraction
And after the reaction of the self-driving process is finished, the single-pole double-throw switch 6 is arranged at the position b, the constant voltage is controlled to be 0.8V for operation, and the current change is recorded. At the moment, the lithium-rich electrode 1 is connected with the anode and oxidized to release lithium ions, the lithium-poor electrode 2 is connected with the cathode and reduced to adsorb lithium ions, the reaction is stopped when the current is observed to be reduced to 0.1mA, and the whole reaction is stopped for about 1.5 h; taking out the lithium-rich electrode 1 and the lithium-poor electrode 2, cleaning the lithium-rich electrode 1 and the lithium-poor electrode 2 with distilled water, and then reversing the lithium-rich electrode 1 and the lithium-poor electrode 2, namely placing the lithium-rich electrode 1 in the raw material solution and placing the lithium-poor electrode 2 in the recovery solution;
(4) repeated cycling reaction
And (4) repeating the operations in the steps (2) to (3) to realize the extraction and enrichment of the lithium resource in the raw material liquid into the recovery liquid.
Comparative example 2
The electrochemical lithium extraction method based on the electrode system of the rocking chair type structure in the comparative example is the same as that of example 2, except that the self-driving process in the step (2) is not performed.
Detecting the ion content in the recovery liquid by adopting a TAS-990F atomic absorption spectrophotometer, and calculating to obtain an electrode pair Li+Has an exchange capacity of 30.92Mg/g, Mg2+The exchange capacity of (A) is 4.61 mg/g; comparative example 2 Single external electric field Condition Li+And Mg2+The exchange capacities of (A) were 27.94mg/g and 4.62mg/g, respectively. Compared with a single external electric field operation process (0.8V condition), the selectivity coefficient is increased from 414.26 to 460.05, the unit energy consumption is reduced from 22.76 to 9.32Wh/mol Li, and the power consumption is saved by 59.05%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (8)

1. A self-driven electrochemical lithium extraction method based on an electrode system with a rocking chair type structure is characterized by comprising the following steps:
(1) respectively placing a lithium-rich electrode and a lithium-poor electrode of a rocking chair type structure electrode system in isolated recovery liquid and raw material liquid;
the rocking chair type structure electrode system comprises an electrode system consisting of different lithium-containing states of the same electrode material;
the rocking chair type structure electrode system comprises LiMn2O4/Li1-xMn2O4、LiFePO4/Li1-xFePO4、Li2TiO3/Li2- xTiO3、LiNi1/3Co1/3Mn1/3O2/Li1-xNi1/3Co1/3Mn1/3O2、Li7Ti5O12/Li7-xTi5O12At least one of an electrode system;
(2) carrying out short circuit on the lithium-rich electrode and the lithium-poor electrode or carrying out reaction by externally connecting an electric quantity recovery device, and stopping the reaction when the current is reduced to a certain value;
(3) the lithium-rich electrode and the lithium-poor electrode are respectively connected with the anode and the cathode of a direct current power supply to carry out constant-voltage reaction, and then the lithium-rich electrode and the lithium-poor electrode are taken out and washed, and the positions of the lithium-rich electrode and the lithium-poor electrode are exchanged;
(4) and (4) repeating the operations of the steps (2) to (3) to realize the extraction and enrichment of the lithium resource in the raw material liquid to the lithium in the recovery liquid.
2. The self-driven electrochemical lithium extraction method based on the rocking chair type electrode system in claim 1, wherein the rocking chair type electrode system is prepared according to the following steps:
mixing the selected lithium ion sieve powder, a conductive agent and a binder, adding a solvent, stirring to obtain emulsion slurry, uniformly coating the emulsion slurry on a current collector, and drying to obtain a required lithium-rich electrode;
connecting the obtained lithium-rich electrode with a positive electrode, connecting an AgCl electrode with a negative electrode, placing the lithium-rich electrode in an electrolyte, introducing constant-voltage direct current, and stopping reaction when the current is as low as 0.1mA to obtain the required lithium-poor electrode.
3. The self-driven electrochemical lithium extraction method based on the rocking chair type electrode system of claim 2, wherein the lithium ion sieve powder comprises LiMn2O4、LiFePO4、Li2TiO3、LiNi1/3Co1/3Mn1/3O2、Li7Ti5O12One or a mixture of several of them.
4. The self-driven electrochemical lithium extraction method based on the rocking chair type electrode system is characterized in that the recovery solution and the raw material solution are separated by a monovalent selective anion exchange membrane.
5. The method for electrochemically extracting lithium in a self-driven manner based on the electrode system in the rocking chair type structure according to claim 4, wherein in the step (2), the short-circuiting step is stopped until the current drops to 0.2-5.0 mA.
6. The method for electrochemically extracting lithium in a self-driven manner based on an electrode system in a rocking chair type structure according to claim 5, wherein in the step (3), the operating voltage of the constant-voltage reaction is 0.2-1.2V.
7. The method for electrochemically extracting lithium by means of 'self-driving' based on an electrode system with a rocking chair type structure according to claim 6, characterized in that in the step (3), the constant-voltage reaction step is stopped until the current is reduced to 0.1 mA.
8. The self-driven electrochemical lithium extraction method based on the rocking chair type electrode system in the claim 7, wherein in the step (3), the washing step is distilled water washing.
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