CN112645362B - Method for preparing lithium carbonate by electrochemical extraction of lithium from chloride type lithium-containing brine - Google Patents
Method for preparing lithium carbonate by electrochemical extraction of lithium from chloride type lithium-containing brine Download PDFInfo
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Abstract
The invention relates to a method for directly preparing lithium carbonate by electrochemical extraction of lithium from chloride type lithium-containing brine. The method comprises the steps that chloride type lithium-containing brine is used as electrolyte, a lithium ion sieve electrode and a chloride ion capturing electrode are respectively used as positive and negative electrodes to form a primary battery, and lithium ions in the brine are inserted into the lithium ion sieve by primary battery discharge; the lithium salt recovery solution is used as electrolyte, a lithium ion sieve electrode and an inert electrode which are used for inserting lithium ions are respectively used as an anode and a cathode to construct an electrolytic cell, and the electrolytic cell is charged to remove the lithium ions into the lithium salt recovery solution; repeating the steps of inserting lithium and removing lithium, increasing the temperature when the concentration of lithium salt in the lithium salt recovery solution is close to saturation, and separating out lithium carbonate by utilizing the characteristic that the solubility of the lithium carbonate decreases along with the increase of the temperature. The method can directly obtain high-purity lithium carbonate, can co-produce important chemical raw materials such as hydrogen, chlorine and the like, has low production cost and is easy to realize industrialization.
Description
Technical Field
The invention relates to a method for directly preparing lithium carbonate by electrochemical extraction of lithium from chloride type lithium-containing brine, and belongs to the technical field of extraction and utilization of lithium resources.
Background
Along with the popularization of intelligent electronic equipment, lithium ion batteries are widely used for various electronic equipment such as mobile phones, computers, cameras and the like; the development of new energy electric vehicles expands the application field of lithium ion batteries and increases the market demand of lithium ion batteries. Therefore, development of lithium resources is needed to provide high-quality low-cost battery-grade lithium carbonate raw materials for lithium ion batteries.
Lithium resources are divided into two main categories, namely ore lithium resources and brine lithium resources. Compared with the production of lithium salt by taking ore as raw material, the energy consumption and the cost for producing lithium salt by taking brine as raw material are low, so that the main way for obtaining lithium salt in recent years is changed from ore lithium resource to brine lithium resource. However, the composition of lithium-containing brine such as salt lake brine, seawater and the like is complex, and the lithium is difficult to selectively extract because of the plurality of anions and cations. Therefore, various lithium extraction methods have been developed, including precipitation, solvent extraction, ion exchange adsorption, membrane separation, carbonization, calcination leaching, electrochemical methods, and the like.
The electrochemical lithium extraction method has the advantages of energy conservation, environmental protection, simple operation and the like, can obviously improve the extraction efficiency of lithium ions, and is widely paid attention to in recent years. In document (1) chinese invention patent publication No. CN105600807a, yang Wensheng et al disclose a method of electrochemically extracting lithium salt from high magnesium-to-lithium ratio brine. However, electrochemical extraction of lithium from chloride-type lithium-containing brine typically results in lithium chloride LiCl, which is further converted to lithium carbonate Li 2 CO 3 Or lithium hydroxide LiOH can be used as a battery raw material. Battery grade Li 2 CO 3 The chlorine ion content is more severe, such as less than 30ppm according to industry standard YS/T582-2013, thus converting LiCl into battery grade Li 2 CO 3 The process is complex and the cost is high. If battery grade Li can be directly prepared from brine by electrochemical method 2 CO 3 Has important scientific significance and commercial value.
Disclosure of Invention
The invention aims to provide a method for directly preparing lithium carbonate by electrochemical lithium extraction from chloride type lithium-containing brine, which has the following working principle: the method comprises the steps of taking chloride type lithium-containing brine as electrolyte solution, respectively taking a lithium ion sieve electrode and a chloride ion capturing electrode as positive and negative electrodes to form a primary battery, and embedding lithium ions in the brine into the lithium ion sieve by discharging the primary battery; the lithium salt recovery solution is taken as electrolyte solution, a lithium ion sieve electrode and an inert electrode which are used for inserting lithium ions are respectively taken as an anode and a cathode to construct an electrolytic cell, the electrolytic cell is charged to remove the lithium ions into the lithium salt recovery solution, the lithium ion sieve electrode is regenerated, and hydrogen is separated from the inert electrode; the metal chloride solution is taken as electrolyte solution, a capturing electrode for capturing chloride ions and an inert electrode are respectively taken as a cathode and an anode to form an electrolytic cell, and the chloridion captured by the capturing electrode is charged in the electrolytic cellRemoving ions, regenerating a chloride ion capturing electrode, and separating out chlorine gas on an inert electrode; the regenerated lithium ion sieve electrode and the chlorine ion capturing electrode can be recombined into a primary battery, the steps of inserting lithium and removing lithium are repeated, when the concentration of lithium salt in the lithium salt recovery solution is close to saturation, the temperature is increased, lithium carbonate precipitation is separated out by utilizing the characteristic that the solubility of lithium carbonate is reduced along with the temperature increase, and the precipitation is leached and dried to obtain a lithium carbonate product; introducing carbon dioxide CO into the solution from which the lithium carbonate precipitate is separated 2 The bicarbonate solution can be obtained and can be recycled as lithium salt recovery solution. In lambda-MnO 2 The working principle of extracting lithium from a primary battery and regenerating the two electrodes is shown in figure 1 by taking the lithium ion sieve electrode as an anode and taking the active carbon AC chloride ion capturing electrode as a cathode. The method comprises the following specific process steps:
(1) The method comprises the steps of taking chloride type lithium-containing brine as electrolyte solution, respectively taking a lithium ion sieve electrode and a chloride ion capturing electrode as positive and negative electrodes to form a primary battery, discharging the primary battery by using theoretical current (0.1-0.5C multiplying power) of the lithium ion sieve for 2-10 h to fully intercalate lithium ions in the brine into the lithium ion sieve, and capturing chloride ions in the brine by the chloride ion capturing electrode; wherein the chloride type lithium-containing brine refers to one of salt lake brine or evaporating concentrated solution thereof, seawater or evaporating concentrated solution thereof and brine containing LiCl; the lithium ion sieve electrode is spinel LiMn 2 O 4 Or olivine type LiFePO 4 lambda-MnO obtained by electrochemical delithiation of initial electrode composed of electrode active material 2 Or FePO 4 An electrode, the initial electrode is made of spinel LiMn 2 O 4 Or olivine type LiFePO 4 One of the electrode active materials, one of the acetylene black or conductive graphite conductive additives and one of the polytetrafluoroethylene PTFE or polyvinylidene fluoride PVDF binder are mixed according to a certain proportion and coated on a current collector to obtain the electrode active material, wherein the current collector is one of a titanium net or a nickel net, the mass percentages of the electrode active material, the conductive additives and the binder are respectively 80-90%, 5-10% and 5-10% except the current collector, and the sum of the mass percentages of the electrode active material, the conductive additives and the binder is 100%; the chloridion capturing electrode is a silver Ag electrode, an active carbon AC electrode and polypyrroleOne of a pyrrole py electrode or a polyaniline PANI electrode; the chloride ion capturing electrode is prepared by mixing one of active substances such as Ag powder, active carbon AC, polypyrrole Ppy or polyaniline PANI, one of acetylene black or conductive graphite conductive additive and one of polytetrafluoroethylene PTFE or polyvinylidene fluoride PVDF binder according to a certain proportion and coating the mixture on a current collector; wherein the current collector is one of a titanium mesh or a nickel mesh, except the current collector, the mass percentages of the electrode active material, the conductive additive and the binder are respectively 80-90%, 5-10% and 5-10%, and the sum of the mass percentages of the three is 100%.
(2) Taking lithium salt recovery solution as electrolyte solution, respectively taking a lithium ion sieve electrode and an inert electrode which are intercalated with lithium ions in the step (1) as an anode and a cathode to form an electrolytic cell, charging the electrolytic cell by theoretical current (0.2-1.0C multiplying power) for removing all lithium ions by a lithium ion sieve for 1-5 h, removing the lithium ions into the lithium salt recovery solution, regenerating the lithium ion sieve electrode, and simultaneously separating out hydrogen on the cathode of the inert electrode; wherein the lithium salt recovery solution is sodium bicarbonate NaHCO 3 Or potassium bicarbonate KHCO 3 One of the aqueous solutions has a concentration of 0.1-0.7 mol/L; the inert electrode is one of a titanium mesh, a titanium-coated metal mesh, a carbon rod, a platinum mesh or a platinum sheet.
(3) Taking a metal chloride solution as an electrolyte solution, wherein a capture electrode and an inert electrode for capturing chloride ions in the step (1) are respectively taken as a cathode and an anode to form an electrolytic cell, the electrolytic cell is charged by the same current in the step (2), the chloride ions captured by the capture electrode are removed, the chloride ion capture electrode is regenerated, and meanwhile, chlorine is separated out from the anode of the inert electrode; wherein the metal chloride solution is one of sodium chloride NaCl solution and potassium chloride KCl solution, and the concentration is 0.5-1.0 mol/L; the inert electrode is one of a titanium mesh, a titanium-coated metal mesh, a carbon rod, a platinum mesh or a platinum sheet.
(4) And (3) reconstructing a primary battery by using the regenerated lithium ion sieve electrode in the step (2) and the regenerated chloride ion capturing electrode in the step (3) as positive and negative electrodes respectively, repeating the steps (1) to (3), repeatedly using the lithium salt recovery solution in the step (2), wherein the concentration of lithium ions is continuously increased, increasing the temperature to 60-90 ℃ when the concentration of lithium salts in the lithium salt recovery solution is close to saturation, keeping the temperature for 30-120 minutes, precipitating lithium carbonate precipitate by utilizing the characteristic that the solubility of lithium carbonate is reduced along with the temperature increase, leaching the precipitate by deionized water, and drying at 200-300 ℃ to obtain a lithium carbonate product.
(5) Introducing carbon dioxide CO into the solution from which the lithium carbonate precipitate is separated in the step (4) 2 The obtained bicarbonate solution can be used as a lithium salt recovery solution for recycling; wherein the bicarbonate is sodium bicarbonate NaHCO 3 Or potassium bicarbonate KHCO 3 One of them.
Lithium carbonate Li prepared by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and ion chromatography 2 CO 3 Elemental content in the sample, li 2 CO 3 Content of>99%, chloride ion content<20ppm, no SO was detected 4 2- Anions and Mg 2+ ,Ca 2+ ,K + ,Na + And (3) carrying out plasma, wherein the obtained lithium carbonate meets the index requirement of battery-grade lithium carbonate.
The method of the invention has the characteristics and advantages that: (1) The method of the invention can directly obtain Li 2 CO 3 Conversion to Li with LiCl 2 CO 3 Compared with the method, the method can avoid the interference of chloride ions in LiCl, and is favorable for obtaining high-purity battery grade Li with low chloride ion content 2 CO 3 The process is simple and the cost is low; (2) The lithium ion sieve electrode and the chloride ion capturing electrode can be recycled, and sodium bicarbonate NaHCO (NaHCO) 3 Or potassium bicarbonate KHCO 3 The lithium salt recovery solution can be recycled; (3) The method releases electric energy in the lithium extraction process, and consumes electric energy in the regeneration process of the lithium ion sieve electrode and the chloride ion capturing electrode, and the released electric energy can be used for the electric energy consumption of electrode regeneration; (4) The method of the invention can produce hydrogen, chlorine and other important chemical raw materials as byproducts in the electrode regeneration process; in conclusion, the method is low in production cost and environment-friendly.
Drawings
FIG. 1 shows the structure of lambda-MnO 2 The lithium ion sieve electrode is used as an anode, and the active carbon AC chloride ion capturing electrode is used as a cathode to form a primary battery for extracting lithiumAnd a working principle schematic diagram for regenerating the two electrodes.
Detailed Description
Example 1
(1) 16g of spinel lithium manganate LiMn is weighed 2 O 4 Mixing 2g of acetylene black conductive agent and 2g of polyvinylidene fluoride PVDF binder (PVDF is dissolved in N-methyl pyrrolidone to form suspension with the mass fraction of 4 wt%) uniformly to form slurry, coating the slurry on a titanium mesh current collector, drying in a vacuum oven at 75 ℃ for 12h to obtain LiMn 2 O 4 An electrode, wherein the electrode is used as an anode, a titanium net is used as a cathode, and NaHCO with the concentration of 0.6mol/L 3 The solution is used as electrolyte solution to construct an electrolytic cell, and is charged to 1.1V (vs. Ag/AgCl) at 0.5C multiplying power to obtain lambda-MnO 2 A lithium ion sieve electrode; weighing 16g of active carbon AC, 2g of acetylene black conductive agent and 2g of polyvinylidene fluoride PVDF binder (PVDF is dissolved in N-methyl pyrrolidone to form suspension with the mass fraction of 4 wt%) and uniformly mixing to form slurry, coating the slurry on a titanium mesh current collector, and drying the slurry in a vacuum oven at 75 ℃ for 12 hours to obtain an active carbon AC chloride ion capturing electrode; with lambda-MnO as described above 2 The lithium ion sieve electrode and the active carbon AC chloride ion capturing electrode are respectively used as an anode and a cathode, the Qinghai Website Ji-Naai salt lake brine is used as an electrolyte solution to construct a primary cell, the primary cell is discharged to 0.3V (vs. Ag/AgCl) at a rate of 0.5C, and lithium ions in the salt lake brine are intercalated into lambda-MnO 2 In the lithium ion sieve, chloride ions in salt lake brine are captured by an active carbon AC capture electrode.
(2) lambda-MnO intercalated with lithium ions in the step (1) 2 The lithium ion sieve electrode is used as an anode, the titanium net is used as a cathode, and NaHCO with the concentration of 0.6mol/L is used as a cathode 3 The solution is used as electrolyte solution to construct an electrolytic cell, the electrolytic cell is charged at 0.5C multiplying power, the charging cut-off voltage is 1.1V (vs. Ag/AgCl), and lithium ions are separated to NaHCO 3 LiHCO formation in solution 3 And further form Li 2 CO 3 ,λ-MnO 2 And regenerating the lithium ion sieve electrode, and simultaneously separating out hydrogen on the titanium mesh cathode.
(3) And (3) taking the active carbon AC electrode for capturing chloride ions in the step (1) as a cathode, taking a titanium mesh as an anode, taking NaCl solution with the concentration of 0.5mol/L as an electrolyte solution to construct an electrolytic cell, charging for 2 hours at the rate of 0.5C, removing the chloride ions from the active carbon electrode, regenerating the active carbon AC chloride ion capturing electrode, and separating out chlorine on the titanium mesh anode.
(4) lambda-MnO regenerated in step (2) 2 The lithium ion sieve electrode and the active carbon AC chloride ion capturing electrode regenerated in the step (3) are respectively used as positive and negative electrodes to reconstruct a primary cell, the steps (1) - (3) are repeated, and NaHCO in the step (2) 3 The lithium salt recovery solution is repeatedly used for a plurality of times, wherein the concentration of lithium ions is continuously increased until NaHCO 3 And when the concentration of lithium salt in the solution is close to saturation, the temperature is increased to 90 ℃ and the temperature is kept constant for 30 minutes, lithium carbonate precipitates are separated out by utilizing the characteristic that the solubility of lithium carbonate is reduced along with the temperature increase, and the precipitates are leached by deionized water and dried at 300 ℃ to obtain a lithium carbonate product. ICP-AES and ion chromatography test Li 2 CO 3 The purity was 99.3% and the chloride ion content was 18ppm.
(5) Introducing carbon dioxide CO into the solution from which the lithium carbonate precipitate is separated in the step (4) 2 Obtaining NaHCO 3 The solution can be recycled as a lithium salt recovery solution.
Example 2
(1) 18g of olivine LiFePO was weighed 4 Uniformly mixing 1gKS-6 conductive graphite and 1g Polytetrafluoroethylene (PTFE) binder (suspension prepared by 5wt% of PTFE) to form slurry, coating the slurry on a nickel screen current collector, and drying the slurry in a vacuum oven at 90 ℃ for 8 hours to obtain LiFePO 4 An electrode, wherein the electrode is used as an anode, a platinum net is used as a cathode, and KHCO with the concentration of 0.2mol/L is used as an anode 3 The solution is used as electrolyte solution to construct an electrolytic cell, and is charged to 1.1V (vs. Ag/AgCl) at a rate of 0.2C to obtain FePO 4 A lithium ion sieve electrode; weighing 18g of silver Ag powder, 1g of KS-6 conductive graphite and 1g of polytetrafluoroethylene PTFE binder (the PTFE is prepared into a suspension with the mass fraction of 5 wt%), uniformly mixing to form slurry, coating the slurry on a nickel screen current collector, and drying the slurry in a vacuum oven at 90 ℃ for 8 hours to obtain a silver Ag chloride ion capturing electrode; with FePO as described above 4 The lithium ion sieve electrode and the silver Ag chloride ion capturing electrode are respectively used as an anode and a cathode, the concentrated seawater in Bohai Bay is used as an electrolyte solution to construct a primary cell, the primary cell is discharged to 0.3V (vs. Ag/AgCl) at the rate of 0.1C, and lithium ions in the concentrated seawater are intercalatedInto FePO 4 In the lithium ion sieve, chloride ions in the seawater are captured by the silver Ag capture electrode.
(2) FePO intercalated with lithium ions in the step (1) 4 The lithium ion sieve electrode is used as an anode, the platinum net is used as a cathode, and KHCO with the concentration of 0.2mol/L is used as a cathode 3 The solution is used as electrolyte solution to construct an electrolytic cell, the electrolytic cell is charged at 0.2C multiplying power, the charging cut-off voltage is 1.1V (vs. Ag/AgCl), and lithium ions are separated to KHCO 3 LiHCO formation in solution 3 And further form Li 2 CO 3 ,FePO 4 And regenerating the lithium ion sieve electrode, and simultaneously separating out hydrogen on the platinum mesh cathode.
(3) And (3) using the silver Ag electrode for capturing chloride ions in the step (1) as a cathode, using a platinum net as an anode, using KCl solution with the concentration of 0.7mol/L as an electrolyte solution to construct an electrolytic cell, charging for 5h at the rate of 0.2C, removing the chloride ions from the silver Ag electrode, regenerating the silver Ag chloride ion capturing electrode, and separating out chlorine on the platinum net anode.
(4) FePO regenerated in step (2) 4 The lithium ion sieve electrode and the silver Ag chloride ion capturing electrode regenerated in the step (3) are respectively used as positive and negative electrodes to reconstruct a primary cell, the steps (1) - (3) are repeated, and KHCO is performed in the step (2) 3 The lithium salt recovery solution is repeatedly used for a plurality of times, wherein the concentration of lithium ions is continuously increased, and KHCO is treated 3 And when the concentration of lithium salt in the solution is close to saturation, the temperature is increased to 60 ℃ and the temperature is kept constant for 120 minutes, lithium carbonate precipitates are separated out by utilizing the characteristic that the solubility of lithium carbonate is reduced along with the temperature increase, and the precipitates are leached by deionized water and dried at 200 ℃ to obtain a lithium carbonate product. ICP-AES and ion chromatography test Li 2 CO 3 The purity was 99.5% and the chloride ion content was 12ppm.
(5) Introducing carbon dioxide CO into the solution from which the lithium carbonate precipitate is separated in the step (4) 2 Obtaining KHCO 3 The solution can be recycled as a lithium salt recovery solution.
Example 3
(1) 17g of spinel lithium manganate LiMn is weighed 2 O 4 Mixing 2g of acetylene black conductive agent and 1g of polyvinylidene fluoride PVDF binder (PVDF is dissolved in N-methyl pyrrolidone to form suspension with mass fraction of 4 wt%) uniformly to form slurryThe material is coated on a titanium mesh current collector and dried for 6 hours in a vacuum oven at 100 ℃ to obtain LiMn 2 O 4 An electrode, wherein the electrode is used as an anode, a stainless steel mesh coated with titanium is used as a cathode, and NaHCO with the concentration of 0.4mol/L is used as a cathode 3 The solution is used as electrolyte solution to construct an electrolytic cell, and is charged to 1.1V (vs. Ag/AgCl) at a rate of 1.0C to obtain lambda-MnO 2 A lithium ion sieve electrode; weighing 17g of polypyrrole Ppy, 2g of acetylene black conductive agent and 1g of polyvinylidene fluoride PVDF binder (PVDF is dissolved in N-methyl pyrrolidone to form suspension with the mass fraction of 4 wt%) and uniformly mixing to form slurry, coating the slurry on a titanium mesh current collector, and drying the slurry in a vacuum oven at 100 ℃ for 6 hours to obtain a polypyrrole Ppy chloride ion capturing electrode; with lambda-MnO as described above 2 Lithium ion sieve electrode and polypyrrole Ppy chloride ion capturing electrode are respectively used as positive and negative electrodes, a primary cell is constructed by taking chloride type factory waste saline water which has LiCl concentration of about 0.05mol/L and contains various alkali metal and alkaline earth metal ions as electrolyte solution, the primary cell is discharged to 0.3V (vs. Ag/AgCl) at a rate of 0.3C, and lithium ions in the saline water are intercalated into lambda-MnO 2 In the lithium ion sieve, chloride ions in the brine are captured by the polypyrrole Ppy capture electrode.
(2) lambda-MnO intercalated with lithium ions in the step (1) 2 The lithium ion sieve electrode is used as an anode, a stainless steel mesh coated with titanium is used as a cathode, and NaHCO with the concentration of 0.4mol/L is used as a cathode 3 The solution is used as electrolyte solution to construct an electrolytic cell, the electrolytic cell is charged at a rate of 1.0C, the charging cut-off voltage is 1.1V (vs. Ag/AgCl), and lithium ions are extracted to NaHCO 3 LiHCO formation in solution 3 And further form Li 2 CO 3 ,λ-MnO 2 And regenerating the lithium ion sieve electrode, and simultaneously separating out hydrogen on the stainless steel mesh cathode coated with titanium.
(3) And (3) taking the polypyrrole Ppy electrode for capturing chloride ions in the step (1) as a cathode, taking the stainless steel mesh coated with titanium as an anode, taking NaCl solution with the concentration of 0.2mol/L as an electrolyte solution to construct an electrolytic cell, charging for 1.2h at the rate of 1.0C, removing the chloride ions from the polypyrrole Ppy electrode, regenerating the polypyrrole Ppy chloride ion capturing electrode, and simultaneously separating out chlorine gas from the anode of the stainless steel mesh coated with titanium.
(4) lambda-MnO regenerated in step (2) 2 Lithium ion sieve electrode and stepThe polypyrrole Ppy chloride ion capturing electrode regenerated in the step (3) is used as a positive electrode and a negative electrode to reconstruct a primary cell respectively, the steps (1) to (3) are repeated, and NaHCO in the step (2) 3 The lithium salt recovery solution is repeatedly used for a plurality of times, wherein the concentration of lithium ions is continuously increased until NaHCO 3 And when the concentration of lithium salt in the solution is close to saturation, the temperature is increased to 80 ℃ and the temperature is kept constant for 60 minutes, lithium carbonate precipitates are separated out by utilizing the characteristic that the solubility of lithium carbonate is reduced along with the temperature increase, and the precipitates are leached by deionized water and dried at 250 ℃ to obtain a lithium carbonate product. ICP-AES and ion chromatography test Li 2 CO 3 The purity was 99.7% and the chloride ion content was 15ppm.
(5) Introducing carbon dioxide CO into the solution from which the lithium carbonate precipitate is separated in the step (4) 2 Obtaining NaHCO 3 The solution can be recycled as a lithium salt recovery solution.
Claims (8)
1. A method for directly preparing lithium carbonate by electrochemical lithium extraction from chloride type lithium-containing brine, which is characterized by comprising the following steps:
(1) The method comprises the steps of taking chloride type lithium-containing brine as electrolyte solution, respectively taking a lithium ion sieve electrode and a chloride ion capturing electrode as positive and negative electrodes to form a primary battery, discharging the primary battery by using theoretical current of the lithium ion sieve for 2-10 hours and fully embedding lithium ions, embedding the lithium ions in the brine into the lithium ion sieve, and capturing the chloride ions in the brine by the chloride ion capturing electrode;
(2) Taking lithium salt recovery solution as electrolyte solution, respectively taking a lithium ion sieve electrode and an inert electrode which are intercalated with lithium ions in the step (1) as an anode and a cathode to form an electrolytic cell, charging the electrolytic cell by theoretical current for removing all lithium ions from the lithium ion sieve for 1-5 hours, removing the lithium ions into the lithium salt recovery solution, regenerating the lithium ion sieve electrode, and simultaneously separating out hydrogen from the cathode of the inert electrode; wherein the lithium salt recovery solution is sodium bicarbonate NaHCO 3 Or potassium bicarbonate KHCO 3 One of the aqueous solutions has a concentration of 0.1-0.7 mol/L;
(3) Taking a metal chloride solution as an electrolyte solution, respectively taking a capture electrode and an inert electrode for capturing chloride ions in the step (1) as cathodes and anodes to form an electrolytic cell, charging the electrolytic cell by the same current in the step (2), removing the chloride ions captured by the capture electrode, regenerating the chloride ion capture electrode, and separating out chlorine gas on the anode of the inert electrode;
(4) Reconstructing a primary battery by using the regenerated lithium ion sieve electrode in the step (2) and the regenerated chloride ion capturing electrode in the step (3) as positive and negative electrodes respectively, repeating the steps (1) - (3), repeatedly using the lithium salt recovery solution in the step (2), wherein the concentration of lithium ions is continuously increased, increasing the temperature to 60-90 ℃ when the concentration of lithium salt in the lithium salt recovery solution is close to saturation, keeping the temperature for 30-120 minutes, precipitating lithium carbonate precipitate by utilizing the characteristic that the solubility of lithium carbonate is reduced along with the temperature increase, leaching the precipitate by deionized water, and drying at 200-300 ℃ to obtain a lithium carbonate product;
(5) Introducing carbon dioxide CO into the solution from which the lithium carbonate precipitate is separated in the step (4) 2 The bicarbonate solution can be obtained and can be recycled as lithium salt recovery solution.
2. The method according to claim 1, wherein the chloride-type lithium-containing brine in the step (1) is one of salt lake brine or an evaporation concentrate thereof, seawater or an evaporation concentrate thereof, and LiCl-containing brine.
3. The method of claim 1, wherein the lithium ion sieve electrode in step (1) is spinel LiMn 2 O 4 Or olivine type LiFePO 4 lambda-MnO obtained by electrochemical delithiation of initial electrode composed of electrode active material 2 Or FePO 4 An electrode; the initial electrode is made of spinel LiMn 2 O 4 Or olivine type LiFePO 4 Mixing one of electrode active materials, one of acetylene black or conductive graphite conductive additives and one of Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF) binder according to a certain proportion, and coating the mixture on a current collector to obtain the electrode active material; wherein the current collector is one of titanium mesh or nickel mesh, except the current collector, the mass percentages of the electrode active material, the conductive additive and the binder are respectively 80-90%, 5-10% and 5-10%, and the mass percentages of the electrode active material, the conductive additive and the binder are respectivelyThe sum of the percentages is 100%.
4. The method of claim 1, wherein the chloride ion capturing electrode in step (1) is one of a silver Ag electrode, an activated carbon AC electrode, a polypyrrole Ppy, or a polyaniline PANI electrode; the chloride ion capturing electrode is prepared by mixing one of active substances such as Ag powder, active carbon AC, polypyrrole Ppy or polyaniline PANI, one of acetylene black or conductive graphite conductive additive and one of polytetrafluoroethylene PTFE or polyvinylidene fluoride PVDF binder according to a certain proportion and coating the mixture on a current collector; wherein the current collector is one of a titanium mesh or a nickel mesh, except the current collector, the mass percentages of the electrode active material, the conductive additive and the binder are respectively 80-90%, 5-10% and 5-10%, and the sum of the mass percentages of the three is 100%.
5. The method of claim 1, wherein the inert electrode in step (2) is one of a titanium mesh, a titanium coated metal mesh, a carbon rod, a platinum mesh, or a platinum sheet.
6. The preparation method according to claim 1, wherein the metal chloride solution in the step (3) is one of sodium chloride NaCl solution and potassium chloride KCl solution, and the concentration is 0.5-1.0 mol/L.
7. The method of claim 1, wherein the inert electrode in step (3) is one of a titanium mesh, a titanium coated metal mesh, a carbon rod, a platinum mesh, or a platinum sheet.
8. The process of claim 1, wherein in step (5) the bicarbonate is sodium bicarbonate NaHCO 3 Or potassium bicarbonate KHCO 3 One of them.
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