MEMBRANE ELECTRODE MATERIAL, ITS PREPARATION METHOD AND APPLICATION IN LITHIUM EXTRACTION BY ADSORPTION-ELECTROCHEMICAL COUPLING TECHNOLOGY

Abstract

This invention provides a membrane electrode material and its preparation method, as well as the application of the material into lithium extraction by adsorption-electrochemical coupling method. The membrane electrode material is described as MnO@C. The preparation steps are as follows: LiMn.sub.2O.sub.4 is firstly obtained by calcining lithium carbonate and manganese carbonate, which is then dispersed in hydrochloric acid solution. After stirring and separating, the solid products are dried to obtain λ-MnO.sub.2. The λMnO.sub.2 is added to the raw material of Mn-MOF-74, and then the Mn-MOF-74 coated λ-MnO.sub.2 can be obtained by hydrothermal reaction. By further calcining Mn-MOF-74 coated λ-MnO.sub.2 in nitrogen atmosphere, the membrane capacitor/electrode material can be obtained as MnO@C. The material is fabricated into an adsorption film electrode plate and assembled into an adsorption-electrochemical coupling lithium extraction device. The pure lithium solution can be obtained in the recovery pool through the combined lithium extraction and lithium recovery process. In this invention, the thickness of the carbon coating layer in the electrode material is adjustable. Adsorption-electrochemical coupling technology takes the advantages of both adsorption and electrochemical lithium intercalation, which can extract and recover lithium resources with high capacity. Thus, this invention not only achieves high-efficiency separation of lithium resources, but also opens up a new way for the extraction of lithium resources.

Claims

1. A preparation method for the membrane electrode material is characterized in the steps as follows: A. The lithium carbonate and manganese carbonate are mixed with the ratio of Li/Mn=0.1˜10. and after calcined at 300˜800° C. for 1˜8 h with the heating rate of 1˜10° C./min, LiMn.sub.2O.sub.4 can be prepared; LiMn.sub.2O.sub.4 is further dispersed in 0.1˜2 mol/L hydrochloric acid solution with the solid-liquid ratio of 1:10˜100; after stirring for 12˜48 h, solid products can be separated and dried to obtain λ-MnO.sub.2; B. MnCl.sub.2.Math.4H.sub.2O and 2,5-dihydroxyterephthalic acid (DHTA) with the molar ratio of 1˜5:1 are dissolved in the mixed solvent, and the raw material solution is obtained by fully mixing; The mixed solvent is prepared with X, ethanol and water with the volume ratio of (2˜20)1:1, wherein X is one or several mixed solutions of acetone, tetrahydrofuran, methanol and N, N-dimethylformamide (DMF); C. The λ-MnO.sub.2 in step A is added into the solution prepared in step B, with the solid content is 5˜50 g/L; after uniform mixing, the solution is then transferred to the reactor, and the reaction is conducted at 80° C.˜180° C. for 1˜48 h; upon cooling to room temperature, the suspension product is centrifuged and filtered; the filter product is washed with DMF solution for three times; at 40˜80° C., after drying for 3˜12 h, the Mn-MOF-74 coated λ-MnO.sub.2 powder can be obtained; D. The powder obtained in step C is further calcined in a tubular furnace under nitrogen atmosphere, with the temperature of 480° C.˜800° C. and the heating rate of 2˜10° C./min; the obtained product is carbon coated at the surface of MnO, described as MnO@C, in which the thickness of carbon layer is 1-5 nm.

2. A membrane electrode material is prepared by the method according to claim 1, and its chemical expression can be described as MnO@C, in which the carbon is coated at the surface of MnO, and the thickness of carbon layer is 1-5 nm.

3. The membrane electrode material in claim 2 can be applied into the extraction of lithium by adsorption-electric coupling method, which is as follows: (1) Preparation of electrode plate: Preparation of activated carbon electrode plate: 0.5 g of activated carbon powder and 0.2 g of polyvinylidene fluoride are mixed; then, 5 mL of DMF is added to make a paste coating on the graphite plate; the plate is dried in vacuum oven at 50° C. overnight, and is fabricated into a 200 μm sheet using a roller press; Preparation of adsorption membrane electrode plate: 0.2 g of polyvinyl alcohol is dissolved into 4 mL of water; then, 0.5 g of MnO@C and 1 mL of glutaraldehyde are added to mix the paste, which is further coated onto the graphite plate and dried. After sprayed with HCl solution on the surface, the sample is dried in vacuum at 60° C. and pressed into a 200 μm sheet, as MnO@C membrane electrode plate; (2) Assemble the electrode plate into the lithium extraction device: The film capacitor unit is assembled according to the order of organic glass plate (upper), adsorption membrane electrode plate, diaphragm, anion exchange membrane, activated carbon electrode plate and organic glass plate (lower), with the electrode area of 100 cm.sup.2; The raw material pool, peristaltic pump, DC regulated power supply, membrane capacitor unit, conductivity meter, computer, test tank and recovery liquid pool are assembled to form an adsorption-electrochemical coupling lithium extraction device. Specifically, the raw material pool is connected with the inlet of the upper plate of the membrane capacitor unit through a peristaltic pump, and the outlet of the lower plate of the membrane capacitor unit is connected with the recovery liquid pool through the test tank; the probe of the conductivity meter is inserted into the test tank. The DC stabilized voltage power supply is connected with the membrane capacitor unit; the conductivity meter and DC stabilized voltage power supply are connected with the computer to set the condition parameters and store the test data; (3) Lithium extraction steps: a. Lithium extraction process: the device runs with the applying voltage at 0.5-2 V; the lithium solution in the raw material pool passes through the peristaltic pump to the membrane capacitor unit, and the lithium ion in the solution migrates to the adsorption membrane electrode plate and adsorbs onto the electrode; at the same time, the chloride ion migrates to the activated carbon electrode plate through the anion exchange membrane; the diaphragm hinders the short circuit of the positive and negative electrodes; the electrochemical reaction (in formula 1) occurs under the action of voltage; formula 1:
MnO+2Li.sup.++2e.sup.−.fwdarw.Mn.sup.0+Li.sub.2O; The conductivity increases with the extension of reaction time and tends to equilibrium gradually, that is, the adsorption capacity reaches the upper limit and the reaction ends; the solution flows back to the recovery liquid pool after reaction, where the lithium ion concentration decreases, and other ion concentrations remain basically unchanged, which can be returned to the raw material pool to continue lithium extraction; The compositions of the lithium solution: Li.sup.+ concentration is 0.0˜100 g/L, Mg.sup.2+ concentration is 0.01˜100 g/L, K.sup.+ concentration is 0.01˜100 g/L, Na.sup.+ concentration is 0.01˜100 g/L, Cl.sup.− concentration is 0.01˜100 g/L, SO.sub.4.sup.2− concentration is 0.01˜100 g/L; b. Lithium recovery process: the deionized water is added into the raw material pool, and the device is operated with an opposite voltage of 0.5˜5 V, that is, the positive and negative electrodes are connected in reverse. The lithium ion adsorbed on the membrane electrode plate is desorbed into water, and the electrochemical reaction of the membrane electrode material (in formula 2) occurs; formula 2:
Mn.sup.0+Li.sub.2O−2e.sup.−.fwdarw.MnO+2Li.sup.+. The conductivity decreases with the extension of operation time, and gradually tends to equilibrium, that is, lithium ion is completely removed from the adsorption electrode, and the reaction is finished; the recovery liquid pool is pure lithium solution, and the MnO@C can be obtained after evaporation and concentration. The product can be directly used to prepare battery-grade lithium carbonate.

Description

DESCRIPTION OF THE FIGURES

[0019] FIG. 1 is the schematic diagram of lithium extraction device with adsorption-electrochemical coupling technology. (1). the raw material pool, (2). the peristaltic pump, (3). the DC regulated power supply, (4). the membrane capacitor unit, (5). the conductivity meter, (6). the computer, (7). the test tank, (8). the recovery liquid pool.

[0020] FIG. 2 is the characterization of the membrane electrode materials in example 1: FIG. 2 (a) XRD and FIG. 2(b) HRTEM profiles.

[0021] FIG. 3 is the change of lithium ion concentration in the test cell in example 1 for

[0022] FIG. 3(a) lithium extraction process and FIG. 3(b) lithium recovery process.

DETAILED EXAMPLES

Example 1

[0023] A. Weighting and mixing 2.9556 g of Li.sub.2CO.sub.3 and 18.392 g of MnCO.sub.3 for calcination at 500° C. for 4 h with the heating rate of 3° C./min; LiMn.sub.2O.sub.4 is prepared; 2.7 g of LiMn.sub.2O.sub.4 is further dispersed in hydrochloric acid solution (120 mL, 0.5 mol/L); after stirred for 24 h, the solid products can be separated and dried to obtain λ-MnO.sub.2;

[0024] B. Weighting 53 mL of DMF, 3.5 mL of ethanol and 3.5 mL of water to prepare the mixed solution. Weighing 2.198 g of MnCl.sub.2.Math.4H.sub.2O and 0.6665 g of DHTA to dissolve them into the mixed solution to obtain the raw material solution of Mn-MOF-74.

[0025] C. Adding 1.5 g of λ-MnO.sub.2 in step A into the 60 mL of Mn-MOF-74 raw material solution prepared in step B; after uniform mixing, the solution is then transferred to the reactor, and the reaction is conducted at 80° C. for 2 h; upon cooling to room temperature, the suspension product is centrifuged and filtered; the filter product is washed with DMF solution for three times; at 40° C., after drying for 12 h, the Mn-MOF-74 coated λ-MnO.sub.2 powder can be obtained;

[0026] D. The powder obtained in step C is further calcined in a tubular furnace under nitrogen atmosphere, with the temperature of 480° C. and the heating rate of 10° C./min; the obtained product is carbon coated at the surface of MnO, described as MnO@C, in which the thickness of carbon layer is 1.59 nm. The XRD and HRTEM profiles for the MnO@C are shown in FIG. 2. MnO@C is further applied into the extraction of lithium by adsorption-electric coupling method, which is as follows:

(1) Preparation of Electrode Plate:

[0027] Preparation of activated carbon electrode plate: 0.5 g of activated carbon powder and 0.2 g of polyvinylidene fluoride are mixed; then, 5 mL of DMF is added to make a paste coating on the graphite plate; the plate is dried in vacuum oven at 50° C. overnight, and is fabricated into a 200 μm sheet using a roller press; Preparation of adsorption membrane electrode plate: 0.2 g of polyvinyl alcohol is dissolved into 4 mL of water; then, 0.5 g of MnO@C and 1 mL of glutaraldehyde are added to mix the paste, which is further coated onto the graphite plate and dried. After sprayed with HCl solution on the surface, the sample is dried in vacuum at 60° C. and pressed into a 200 μm sheet, as MnO@C membrane electrode plate;

(2) Assemble the Electrode Plate into the Lithium Extraction Device:

[0028] The film capacitor unit is assembled according to the order of organic glass plate (upper), adsorption membrane electrode plate, diaphragm, anion exchange membrane, activated carbon electrode plate and organic glass plate (lower), with the electrode area of 100 cm.sup.2;

[0029] The raw material pool, peristaltic pump, DC regulated power supply, membrane capacitor unit, conductivity meter, computer, test tank and recovery liquid pool are assembled to form an adsorption-electrochemical coupling lithium extraction device based on the process in FIG. 1.

(3) Lithium Extraction Steps:

[0030] a. Lithium extraction process: the device runs with the applying voltage at 1.0 V; in the raw material pool, the concentrations are as follows: Li.sup.+:0.05 g/L, Mg.sup.2+:0.633 g/L, K.sup.+:0.1 g/L, Na.sup.+:2 g/L, Cl.sup.−:3.43 g/L; the solution in the raw material pool passes through the peristaltic pump to the membrane capacitor unit, and the lithium ion in the solution migrates to the adsorption membrane electrode plate and adsorbs onto the electrode. There is a small amount of lithium ion in the recovery liquid pool, which can be returned to the raw liquid to continue to extract lithium. The conductivity increases with the running time of the device, and gradually tends to equilibrium. The time to reach equilibrium is 123 s. Through the ICP test, the mass of lithium adsorption is 41.6 mg, and the adsorption capacity is 83.2 mg/g. The change of lithium ion concentration in the test tank during lithium extraction is shown in FIG. 3(a).

[0031] b. Lithium recovery process: the deionized water is added into the raw material pool, and the device is operated with an opposite voltage of 3.5 V, that is, the positive and negative electrodes are connected in reverse. The lithium ion adsorbed on the membrane electrode plate is desorbed into water. The recovery liquid pool is pure lithium solution. The conductivity decreases with the extension of operation time, and gradually tends to equilibrium. Through the ICP test, the mass of desorption lithium is 40.1 mg and the desorption rate is 96.4%. The change of lithium ion concentration in the test tank during lithium recovery is shown in FIG. 3(b).

Example 2

[0032] A. Weighting and mixing 1.4778 g of Li.sub.2CO.sub.3 and 9.196 g of MnCO.sub.3 for calcination at 550° C. for 5 h with the heating rate of 4° C./min; LiMn.sub.2O.sub.4 is prepared; 1.35 g of LiMn.sub.2O.sub.4 is further dispersed in hydrochloric acid solution (60 mL, 0.5 mol/L); after stirred for 26 h, the solid products can be separated and dried to obtain λ-MnO.sub.2;

[0033] B. Weighting 26.5 mL of DMF, 1.8 mL of ethanol and 1.8 mL of water to prepare the mixed solution. Weighing 1.099 g of MnCl.sub.2.Math.4H.sub.2O and 0.333 g of DHTA to dissolve them into the mixed solution to obtain the raw material solution of Mn-MOF-74.

[0034] C. Adding 1.5 g of λ-MnO.sub.2 in step A into the 60 mL of Mn-MOF-74 raw material solution prepared in step B; after uniform mixing, the solution is then transferred to the reactor, and the reaction is conducted at 60° C. for 4 h; upon cooling to room temperature, the suspension product is centrifuged and filtered; the filter product is washed with DMF solution for three times; at 50° C., after drying for 10 h, the Mn-MOF-74 coated λ-MnO.sub.2 powder can be obtained;

[0035] D. The powder obtained in step C is further calcined in a tubular furnace under nitrogen atmosphere, with the temperature of 530° C. and the heating rate of 10° C./min; the obtained product is carbon coated at the surface of MnO, described as MnO@C, in which the thickness of carbon layer is 2.86 nm. MnO@C is further applied into the extraction of lithium by adsorption-electric coupling method.

(1) Preparation of lectrode plate is the same as the example 1.

[0036] (2) Assemble the electrode plate into the lithium extraction device is the same as the example 1.

(3) Lithium Extraction Steps:

[0037] a. Lithium extraction process: the device runs with the applying voltage at 1.2 V; in the raw material pool, the concentrations are as follows: Li.sup.+:0.11 g/L, Mg.sup.2+:1.39 g/L, K.sup.+:0.5 g/L, Na.sup.+:2.5 g/L, Cl.sup.−:4.87 g/L; the reaction time to reach equilibrium is 399 s. Through the ICP test, the mass of lithium adsorption is 25.4 mg, and the adsorption capacity is 50.8 mg/g. [0038] b. Lithium recovery process: the deionized water is added into the raw material pool, and the device is operated with an opposite voltage of 2.5 V, that is, the positive and negative electrodes are connected in reverse. Through the ICP test, the mass of desorption lithium is 24.7 mg and the desorption rate is 97.4%.

Example 3

[0039] A. Weighting and mixing 5.9112 g of Li.sub.2CO.sub.3 and 36.784 g of MnCO.sub.3 for calcination at 600° C. for 6 h with the heating rate of 8° C./min; LiMn.sub.2O.sub.4 is prepared; 5.4 g of LiMn.sub.2O.sub.4 is further dispersed in hydrochloric acid solution (240 mL, 0.5 mol/L); after stirred for 36 h, the solid products can be separated and dried to obtain λ-MnO.sub.2;

[0040] B. Weighting 106 mL of DMF, 7 mL of ethanol and 7 mL of water to prepare the mixed solution. Weighing 4.396 g of MnCl.sub.2.Math.4H.sub.2O and 1.333 g of DHTA to dissolve them into the mixed solution to obtain the raw material solution of Mn-MOF-74.

[0041] C. Adding 1.5 g of λ-MnO.sub.2 in step A into the 60 mL of Mn-MOF-74 raw material solution prepared in step B; after uniform mixing, the solution is then transferred to the reactor, and the reaction is conducted at 40° C. for 6 h; upon cooling to room temperature, the suspension product is centrifuged and filtered; the filter product is washed with DMF solution for three times; at 60° C., after drying for 8 h, the Mn-MOF-74 coated λ-MnO.sub.2 powder can be obtained;

[0042] D. The powder obtained in step C is further calcined in a tubular furnace under nitrogen atmosphere, with the temperature of 580° C. and the heating rate of 10° C./min; the obtained product is carbon coated at the surface of MnO, described as MnO@C, in which the thickness of carbon layer is 3.01 nm. MnO@C is further applied into the extraction of lithium by adsorption-electric coupling method.

(1) Preparation of electrode plate is the same as the example 1.
(2) Assemble the electrode plate into the lithium extraction device is the same as the example 1.

(3) Lithium Extraction Steps:

[0043] a. Lithium extraction process: the device runs with the applying voltage at 0.8 V; in the raw material pool, the concentrations are as follows: Li.sup.+:0.05 g/L, Mg.sup.2+:6.33 g/L, K.sup.+:1 g/L, Na.sup.+:3 g/L, Cl.sup.−:8.08 g/L; the reaction time to reach equilibrium is 387 s. Through the ICP test, the mass of lithium adsorption is 29.8 mg, and the adsorption capacity is 59.6 mg/g. [0044] b. Lithium recovery process: the deionized water is added into the raw material pool, and the device is operated with an opposite voltage of 2.8 V, that is, the positive and negative electrodes are connected in reverse. Through the ICP test, the mass of desorption lithium is 28.8 mg and the desorption rate is 96.8%.

Example 4

[0045] A. Weighting and mixing 4.4334 g of Li.sub.2CO.sub.3 and 27.588 g of MnCO.sub.3 for calcination at 650° C. for 8 h with the heating rate of 10° C./min; LiMn.sub.2O.sub.4 is prepared; 4.05 g of LiMn.sub.2O.sub.4 is further dispersed in hydrochloric acid solution (180 mL, 0.5 mol/L); after stirred for 48 h, the solid products can be separated and dried to obtain λ-MnO.sub.2;

[0046] B. Weighting 79.5 mL of DMF, 5.3 mL of ethanol and 5.3 mL of water to prepare the mixed solution. Weighing 3.297 g of MnCl.sub.2.Math.4H.sub.2O and 0.999 g of DHTA to dissolve them into the mixed solution to obtain the raw material solution of Mn-MOF-74.

[0047] C. Adding 1.5 g of λ-MnO.sub.2 in step A into the 60 mL of Mn-MOF-74 raw material solution prepared in step B; after uniform mixing, the solution is then transferred to the reactor, and the reaction is conducted at 100° C. for 2 h; upon cooling to room temperature, the suspension product is centrifuged and filtered; the filter product is washed with DMF solution for three times; at 50° C., after drying for 12 h, the Mn-MOF-74 coated λ-MnO.sub.2 powder can be obtained;

[0048] D. The powder obtained in step C is further calcined in a tubular furnace under nitrogen atmosphere, with the temperature of 630° C. and the heating rate of 10° C./min; the obtained product is carbon coated at the surface of MnO, described as MnO@C, in which the thickness of carbon layer is 3.59 nm. MnO@C is further applied into the extraction of lithium by adsorption-electric coupling method.

(1) Preparation of electrode plate is the same as the example 1.
(2) Assemble the electrode plate into the lithium extraction device is the same as the example 1.

(3) Lithium Extraction Steps:

[0049] a. Lithium extraction process: the device runs with the applying voltage at 1.1 V; in the raw material pool, the concentrations are as follows: Li.sup.+:1.5 g/L, Mg.sup.2+:18.99 g/L, K.sup.+:1.5 g/L, Na.sup.+:5 g/L, Cl.sup.−:16.73 g/L; the reaction time to reach equilibrium is 123 s. Through the ICP test, the mass of lithium adsorption is 31.6 mg, and the adsorption capacity is 63.2 mg/g. [0050] b. Lithium recovery process: the deionized water is added into the raw material pool, and the device is operated with an opposite voltage of 3.5 V, that is, the positive and negative electrodes are connected in reverse. Through the ICP test, the mass of desorption lithium is 30.1 mg and the desorption rate is 95.3%.

Example 5

[0051] A. Weighting and mixing 5.172 g of Li.sub.2CO.sub.3 and 32.186 g of MnCO.sub.3 for calcination at 500° C. for 4 h with the heating rate of 3° C./min; LiMn.sub.2O.sub.4 is prepared; 4.725 g of LiMn.sub.2O.sub.4 is further dispersed in hydrochloric acid solution (204 mL, 0.5 mol/L); after stirred for 24 h, the solid products can be separated and dried to obtain λ-MnO.sub.2;

[0052] B. Weighting 90 mL of DMF, 6 mL of ethanol and 6 mL of water to prepare the mixed solution. Weighing 3.737 g of MnC12.4H20 and 1.133 g of DHTA to dissolve them into the mixed solution to obtain the raw material solution of Mn-MOF-74.

[0053] C. Adding 1.5 g of λ-MnO.sub.2 in step A into the 60 mL of Mn-MOF-74 raw material solution prepared in step B; after uniform mixing, the solution is then transferred to the reactor, and the reaction is conducted at 120° C. for 1 h; upon cooling to room temperature, the suspension product is centrifuged and filtered; the filter product is washed with DMF solution for three times; at 50° C., after drying for 12 h, the Mn-MOF-74 coated λ-MnO.sub.2 powder can be obtained;

[0054] D. The powder obtained in step C is further calcined in a tubular furnace under nitrogen atmosphere, with the temperature of 530° C. and the heating rate of 10° C./min; the obtained product is carbon coated at the surface of MnO, described as MnO@C, in which the thickness of carbon layer is 4.857 nm. MnO@C is further applied into the extraction of lithium by adsorption-electric coupling method.

(1) Preparation of electrode plate is the same as the example 1.
(2) Assemble the electrode plate into the lithium extraction device is the same as the example 1.

(3) Lithium Extraction Steps:

[0055] a. Lithium extraction process: the device runs with the applying voltage at 1.1 V; in the raw material pool, the concentrations are as follows: Li.sup.+:1.5 g/L, Mg.sup.2+:19.99 g/L, K.sup.+:1.5 g/L, Na.sup.+:5 g/L, Cl.sup.−:16.73 g/L; the reaction time to reach equilibrium is 270 s. Through the ICP test, the mass of lithium adsorption is 35.7 mg, and the adsorption capacity is 71.4 mg/g. [0056] b. Lithium recovery process: the deionized water is added into the raw material pool, and the device is operated with an opposite voltage of 3.5 V, that is, the positive and negative electrodes are connected in reverse. Through the ICP test, the mass of desorption lithium is 34.4 mg and the desorption rate is 96.5%.