CN111634980A - Conductive support material of electrode plate for lithium extraction by electrochemical de-intercalation method - Google Patents
Conductive support material of electrode plate for lithium extraction by electrochemical de-intercalation method Download PDFInfo
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Abstract
The invention relates to a conductive support material of an electrode plate for extracting lithium by an electrochemical de-intercalation method. The conductive support material of the electrode plate for extracting lithium by the electrochemical de-intercalation method is applied to the electrode, compared with the traditional electrode, the processing is simple, the cost is relatively reduced, the defects in the application of the lithium extraction technology by the electrochemical de-intercalation method in the prior art are overcome, the electrode plate processing procedures are reduced, the cost is reduced, a lot of investment is reduced in industrialization, and compared with the existing electrode plate, the pollution to the environment is reduced, and the cost is relatively reduced.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a conductive support material of an electrode plate for lithium extraction by an electrochemical de-intercalation method.
Background
Aiming at the difficult problem of difficult economic and efficient clean extraction of salt lake brine with high magnesium-lithium ratio, the patent CN102049237A (a lithium iron phosphate ionic sieve for selectively extracting lithium and application thereof) and CN102382984A (a method and a device for separating and enriching lithium from magnesium and lithium in salt lake brine) disclose a method and a device for separating and enriching magnesium and lithium in lithium liquid solution or salt lake brine, respectively coat a positive electrode material (hereinafter, a lithium-rich material) and a delithiated positive electrode material (hereinafter, a delithiated material) of a lithium battery on a conductive substrate to manufacture positive and negative electrode plates (hereinafter, a positive electrode plate and a negative electrode plate) by utilizing the working principle of an aqueous lithium battery, form an electrochemical de-intercalation system by taking salt lake brine or lithium-containing solution as a cathode electrolyte and taking a magnesium-free supporting electrolyte as an anode electrolyte, realize the extraction of lithium resources in the lithium-containing liquid or salt lake, and the method is called as an electrochemical de-intercalation method, the conductive substrate is one of ruthenium-coated titanium mesh, graphite plate, Pt group metal and alloy foil thereof, carbon fiber cloth and graphite paper.
The electrochemical de-intercalation method for extracting lithium is also an oxidation-reduction reaction, namely, the positive and negative electrode plates in the cell body need to be continuously charged positively and reversely, and the electric conductor used by the electrode plates needs to be an inert matrix, namely, the electric conductor does not corrode and dissolve due to oxidation-reduction reaction in the charging and discharging processes. Titanium coated with noble metal is generally used as an electrolytic conductive electrode in the conventional art, and platinum-based titanium electrodes, ruthenium-based titanium electrodes, iridium-titanium electrodes, and the like are included as electrolytic electrodes. But these electrodes are costly to machine and complex in process. There is a need in the art for a metal as an electrical conductor that serves as a support for the coating material and an electrical conductor, that is resistant to corrosion without damage during electrochemical redox processes in which the polarity of the electrode is reversed, and that is inexpensive relative to previous electrodes in their entirety.
Titanium is widely applied to the fields of chlor-alkali, electroplating, electrodeposition and the like due to excellent physical and chemical properties of titanium. The titanium anode for recovering the electroplating wastewater adopts an iridium-tantalum mixed metal oxide coating, a platinum-plating layer and the like, anode plates for recovering copper with different specifications can be designed according to different processes such as the size of a customer electroplating bath, electroplating conditions and the like, and the titanium anode has high electrocatalytic activity and good corrosion resistance. The chlorine alkali industry uses ruthenium-coated titanium as an anode to carry out chlorine evolution reaction. Non-ferrous metal electrodeposition (copper, nickel, cobalt, etc.) also uses pure titanium as the cathode for metal deposition. In industrial production, the coating titanium anode is strictly forbidden to be used in an inverted mode in the using process, once the noble metal oxide coating is used as a cathode, a reduction reaction is generated on the surface, the noble metal oxide coating is easy to be converted into a metal simple substance, the noble metal oxide coating cannot be effectively combined with a titanium base, the coating is peeled off, the anode oxidation is generated on the surface of the electrode when general metal titanium is used as the anode for a long time, a titanium dioxide passivation film is generated, the resistivity of pure titanium dioxide is high, the electron transfer rate on the surface of the electrode is reduced, and.
The titanium ruthenium-coated anode belongs to a chlorine-separating anode, and is generally used in a water environment of hydrochloric acid, electrolytic seawater and electrolytic salt, such as a ruthenium iridium anode, a ruthenium iridium tin anode and the like. The titanium-coated iridium system anode belongs to an oxygen evolution anode, and the common use environment is an acid environment, such as an iridium tantalum anode and an iridium tantalum coating titanium anode. Also, a platinized titanium anode, also called platinized titanium electrode, platinum electrode, platinized anode, etc., is made of titanium as a base material, and a layer of platinum group noble metal is plated on the surface. When the oxide coating is prepared, other alloy elements are added besides the noble metal elements. Auxiliary elements are added into the Ru series coating and the Ir series coating to form binary, ternary and quaternary metal oxides, so that the performance of the titanium anode can be obviously improved.
The electrode plate in the electrochemical de-intercalation method comprises the following steps of: the positive plate is arranged on the side of supporting electrolyte (the lithium ion extraction side), the negative plate is arranged on the side of brine (the lithium ion insertion side), a forward constant current charging process is carried out under the action of an external electric field, the lithium-rich material on the positive plate extracts ions into the supporting electrolyte to obtain a lithium-rich solution, the reaction that the lithium ions in the brine are inserted into the lithium-deficient material occurs on the negative plate side, when the load cannot meet the constant current condition, the constant voltage charging is carried out, until the current is less than a set value, at the moment, the forward half-cycle process is finished, or for the anode side, the lithium extraction process is finished, for the cathode side, the lithium insertion process is finished, and the whole forward process is constant current firstly and then constant voltage. Reversing: the polarity of the voltage applied to the electrode is reversed, that is, the polar plate originally connected to the positive side is changed into the polar plate connected to the negative side at the moment, the polar plate originally connected to the negative side is changed into the polar plate connected to the positive side at the moment, and meanwhile, the external solution is matched to realize the alternate transposition. In the reverse process, compared with the positive process, the positive plate (connected with the negative electrode in the forward direction) is added on the side supporting the electrolyte (the side from which lithium is removed and enriched with lithium), the negative plate (connected with the positive electrode in the forward direction) is added on the side brine (the side from which lithium ions are embedded), and under the action of an external electric field, the positive constant-current charging process is started until the negative half-cycle process is finished. The charging process is the same as before the polarity of the electrode is reversed. The processes are realized by coating a support with a lithium-rich material and a lithium-poor material, leading out the materials through a conductor, and simultaneously, in the charging and discharging process of continuously exchanging the polarity of a power supply, a current collector used by the conductor needs to have the characteristics of no corrosion, long-term use and no pollution to anode lithium-rich liquid and cathode brine. In the conventional concept, titanium is a so-called valve-type metal, which has the property of single-phase current carrier, and is conductive when used as a cathode in an electrolyte, and is influenced by an anode potential when used as an anode, when the anode potential is high to a certain value, oxygen generated on the surface of the titanium and pure titanium form a non-conductive titanium dioxide passivation film to lose the conductivity, and the meaning of the valve is that. Titanium and titanium metal oxide anodes (also called Ti-based dimensional stability anodes) are widely applied to electrochemical engineering such as chlor-alkali industry, hydrometallurgy, organic synthesis, cathodic protection, electrolytic antifouling, industrial electroplating and the like by virtue of stable electrochemical performance and good electrocatalytic activity, are always ideal electrode materials so far, such as ruthenium-series titanium used in chlor-alkali industry and platinum-series titanium electrodes, ruthenium-series titanium metals, iridium-series titanium metals and iridium-tantalum titanium used in electrolysis industry, and have the advantages of long relative processing process, high cost and easy environmental pollution. In the environment of continuous oxidation reaction when ruthenium titanium is coated as an anode in the industries, if ruthenium coating and other treatments are not carried out, a very thick oxidation film can be produced and is not conductive, in the repeated charging and discharging process of lithium extraction by an electrochemical de-intercalation method, because the voltage applied between a positive electrode plate and a negative electrode plate is low, the supporting solution in which the positive electrode plate and the negative electrode plate are positioned is nearly neutral, the surface of an electrode conductor is not easily oxidized by controlling the electrode potential, the oxidation film can not be generated and the electrode is not conductive, while a common pure titanium plate has a very thin natural oxidation film and has very strong conductivity, and researches show that: the anodic polarization current of the titanium sample after anodic oxidation treatment is 100 times lower than that of pure titanium subjected to natural passivation, and practice and theory show that the pure titanium plate can meet the requirements of serving as an electrode conducting and supporting object.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the conductive support material for the electrode plate for extracting lithium by the electrochemical de-intercalation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrode plate in the electrochemical de-intercalation method comprises a positive plate and a negative plate, wherein the positive plate and the negative plate are formed by coating a lithium-rich material and a lithium-deficient material on a support material, and the support material is made of a pure titanium material.
For the electrode plate of the electrochemical de-intercalation method, the traditional electrode plate conductive support material is adopted, the processing is complex, the cost is relatively high, and the defects in the application of the lithium extraction technology of the electrochemical de-intercalation method in the prior art are overcome. Wherein, the coating material is generally selected from lithium iron phosphate or iron phosphate.
Further, the voltage applied between the positive electrode and the negative electrode is less than 1.0V.
In the repeated oxidation-reduction process of the positive electrode and the negative electrode by the electrochemical de-intercalation method, because the voltage applied between the positive electrode and the negative electrode is lower than 1.0V, the supporting solution in which the titanium sample is positioned is nearly neutral, the electrode conductor is not oxidized by controlling the electrode potential, an oxide film formed by oxidation cannot be generated to be non-conductive, a thicker oxide film cannot be generated to be non-conductive, a common pure titanium plate has a very thin natural oxide film and still has very strong conductivity, and the anodic polarization current of the titanium sample subjected to anodic oxidation treatment is 100 times lower than that of pure titanium subjected to natural passivation. Practice and theory show that the pure titanium plate can meet the requirements of serving as an electrode plate for electric conduction and a support.
Further, the supporting material is a titanium mesh.
Furthermore, the thickness of the titanium mesh is 0.1-5 mm.
Furthermore, the thickness of the titanium mesh is 0.8-2 mm.
The preferred titanium mesh in the invention is a mesh titanium mesh with a pore spacing of 3mm by 6mm or 4mm by 6mm, and can also be a titanium mesh with other pore spacings.
Furthermore, at least one reinforcing rib is fixed on the supporting material, and the reinforcing rib is formed by punching a titanium mesh.
Furthermore, the reinforcing ribs are fixedly connected to the titanium net in the vertical or horizontal direction.
Furthermore, the reinforcing ribs are welded on the titanium mesh in the vertical or horizontal direction.
Furthermore, the reinforcing ribs are V-shaped vertical grooves, and the depth of the grooves is less than or equal to 3 mm.
The reinforcing rib of the present invention may have other shapes, and is explained in a V-shape.
Further, the titanium net is polygonal.
Furthermore, the titanium mesh is rectangular or square.
Furthermore, the left side and the right side of the titanium mesh are respectively and symmetrically provided with a plurality of fixing lugs connected with the groove frame body.
Wherein, be provided with first screw hole on the fixed ear, fixed ear pass through first screw and electrolysis trough frame body screwed connection, fixed ear adopts titanium metal to make.
Furthermore, a transition plate connected with an extraction electrode is arranged at the upper end of the titanium mesh.
Further, the transition plate is made of a titanium mesh.
The transition plate is provided with a second screw hole, and the external power supply is connected with the transition plate through the second screw hole and the screw, so that the titanium mesh is electrified.
Compared with the prior art, the invention has the beneficial effects that:
the conductive support material of the electrode plate for extracting lithium by the electrochemical de-intercalation method is applied to the electrode, is simpler to process than the traditional electrode plate, has relatively lower cost, overcomes the defects in the prior art of extracting lithium by the electrochemical de-intercalation method, reduces the electrode plate processing procedures, saves rare metal materials, reduces the project investment cost and improves the social labor production efficiency. The industrialization reduces a lot of investment, compared with the existing polar plate, the pollution to the environment is reduced, and the cost is relatively reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a lithium support network for electrochemical deintercalation according to the invention;
FIG. 2 is a front view of the electrochemical deintercalation method for extracting lithium from a support material by net punching and adding vertical reinforcing ribs.
FIG. 3 is a left side view of an electrochemical deintercalation method of adding vertical ribs to a lithium support web.
FIG. 4 is a top view of an electrochemical deintercalation method of adding vertical ribs to a lithium support web punch.
FIG. 5 is a front view of the electrochemical deintercalation method for extracting lithium from a support material by net punching and adding horizontal reinforcing ribs.
FIG. 6 is a left side view of a lithium support web stamped with horizontal ribs according to an electrochemical deintercalation method of the present invention.
FIG. 7 is a top view of an electrochemical deintercalation method of adding horizontal ribs to a lithium support web punch.
FIG. 8 is a graph showing the comparative change in lithium concentration of cathodes of pure titanium and ruthenium-coated titanium as supporting materials in test example 1 of the present invention.
FIG. 9 is a graph showing a comparison of the embedding capacity of pure titanium and iron phosphate coated ruthenium titanium as a support material in test example 1 of the present invention.
Reference numerals
1-titanium net, 2-fixing ears, 2-1-first screw holes, 3-transition plates, 3-2-second screw holes and 4-reinforcing ribs.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
As shown in fig. 1 and 2, the electrode plate in the electrochemical de-intercalation method includes a positive plate and a negative plate, the positive plate and the negative plate are formed by coating a lithium-rich material and a lithium-deficient material on a conductive support material, the support material is made of a pure titanium material, the support material of the embodiment is a pure titanium mesh with a thickness of 1mm and a hole spacing of 3mm 6mm, the pure titanium mesh is cut into 1 square, two pairs of fixing ears 2 connected with an electrolytic cell frame are symmetrically arranged on the left side and the right side of the titanium mesh 1 respectively, first screw holes 21 are arranged on the fixing ears 2, the fixing ears 2 are connected with the electrolytic cell frame through screws by the first screws 21, and the fixing ears are made of titanium metal. A section of titanium conductor is welded on the inner side of the uppermost edge of the titanium net 1 to serve as a conductor of a lead-out electrode, the transition plate 3 is fixedly connected with the titanium net 1, the lead-out electrode is fixed on the titanium net 1 through the transition plate 3 so as to be conveniently fixed on the frame edge of the electrolytic cell, a second screw hole is formed in the transition plate 3, an external power supply is in screw connection with the transition plate 2 through the second screw hole 31, and therefore the titanium net 1 is electrified.
Further, as shown in fig. 3-7, in order to increase the strength of the mesh electrode and prevent the titanium mesh 1 from deforming left and right, a titanium strip may be welded in the vertical or horizontal direction as the reinforcing rib 4, preferably, one or more V-shaped vertical grooves are punched in the vertical direction, the groove depth is less than 3mm, and the drawings in the present invention are explained by taking one as an example.
Comparative example 1
As shown in fig. 1 and 2, the electrode plate in the electrochemical de-intercalation method comprises a positive plate and a negative plate, wherein the positive plate and the negative plate are formed by coating a lithium-rich material and a lithium-deficient material on a conductive support material, and the support material is made of a ruthenium-coated titanium mesh material.
The process for coating the ruthenium on the titanium mesh comprises the following steps:
(1) substrate pretreatment
Sequentially polishing titanium sheets by using coarse (500 meshes) and fine (2000 meshes) sand paper to remove oxide films on the surfaces of the titanium sheets, and sequentially performing ultrasonic treatment in acetone, ethanol and deionized water for 10 min; preparing oxalic acid etching solution with the mass fraction of 10%, etching the titanium sheet subjected to ultrasonic treatment in the etching solution at the temperature of 90 ℃ for 2 hours to finally obtain a titanium sheet substrate with a rugged surface;
(2) preparation of ruthenium-containing coated anodes
Coating the coating liquid on the surface of the anode substrate treated in the step (1), wherein the deposition amount of the metal oxide is 0.25-0.75 mg/cm2(ii) a Drying the anode substrate coated with the anode coating liquid at 100-120 ℃ for 15-30 min, then sintering at 300-400 ℃ for 20-40 min, and naturally cooling to room temperature; in order to ensure that the active coating is uniformly coated on the surface of the substrate material, the steps of brushing, drying and thermal oxidation are repeatedly carried out for multiple times, and the brushing amount is 0.02mL/cm for each time2Until the mother liquor is used up; sintering the coated film for 2 to 3 hours at the temperature of 300 to 400 ℃ after the last coating is finished to obtain a ruthenium-containing coating anode; preferably, repeating the steps for 2-10 times; the anode coating liquid is characterized in that the solvent is water and comprises the following components in molar weight: RuO20.025mol/L and 0.002mol/L of doped metal salt, wherein the doped metal salt is nitrate of chromium and manganese; containing RuO2Preparing a nano-particle coating solution: in RuCl3Adding NaOH solution with the mass concentration of 20-30% into the water solution, and reacting for 20min at 80-100 ℃, preferably 90 ℃, 2 to obtain the RuO-containing solution2Coating liquid of nano particles; RuCl3In aqueous solution, RuCl3The content of (A) is 0.04 mol/L; RuCl3The volume ratio of the aqueous solution to the NaOH solution is as follows: RuCl3Aqueous solution: 15:1 of NaOH solution; adding a doping metal salt solution into the RuO-containing solution obtained in the step (1)2In the coating liquid of the nano particles, the anode coating liquid can be obtained; in the doped metal salt solution, the content of the doped metal salt is 0.04 mol/L; doped metal salt solution and RuO-containing solution2The volume ratio of the coating liquid of the nano particles is as follows: doping a metal salt solution: containing RuO2The coating solution of the nanoparticles was 1: 15.
The conductive support material for the electrode plate for lithium extraction in the salt lake by the electrochemical desorption method prepared by the comparative example is different from that of example 1 only in that the ruthenium-coated titanium mesh is adopted as the support material, and the preparation method of the ruthenium-coated titanium mesh is as described above.
Test example 1
Cutting 20cm × 17cm of the positive and negative electrode supporting materials prepared in the example 1 and the comparative example 1, respectively carrying out lithium extraction by an electrochemical de-intercalation method, and mixing LiFeP0 according to the weight ratio of 8:1:14The method comprises the steps of uniformly mixing acetylene black and PVDF, adding an N-methyl pyrrolidone (NMP) organic solvent, grinding and adjusting into slurry, coating the slurry on the support material prepared in example 1 and comparative example 1, placing the support material in a vacuum drying oven, vacuumizing, heating to 110 ℃, drying for 12 hours, cooling to obtain a prepared lithium iron phosphate electrode, placing the integral electrode coated with lithium iron phosphate in 1L of NaCl solution with the concentration of 20g/L with foam nickel as a cathode, applying a voltage of 1.0V to two ends of a titanium electrode and the foam nickel for 12 hours, and removing lithium in the lithium iron phosphate coated on the support material to prepare the lithium iron phosphate material of the lithium lack material.
Lithium extraction comparative experiments are carried out by taking lithium iron phosphate composite electrodes coated on two support materials as anodes and prepared lithium-deficient materials as cathodes respectively, adding certain salt lake mixed brine, taking 1.3L of brine mixed as catholyte and 10g/L of NaCl as anolyte (anode 1.2L). The brine solution used had the composition shown in table 1, and the cathodic potential was controlled to be not less than 0.25V with the application of voltage.
TABLE 1 composition of brine used
The electrode using ruthenium coating as a support is subjected to lithium extraction according to the conditions+The concentration of the lithium-rich anode is reduced to 0.3g/L, the concentration of the lithium-rich anode is increased to 1.3g/L, simultaneously, the content of other impurity ions is very low, K, Mg, Ca and SO4 2-The retention rate of B is 90%, and the purity of the obtained anolyte is high.
Correspondingly, the cathode Li with pure titanium as a support is extracted according to the conditions+The concentration of the lithium-rich anode is reduced to 0.28g/L, the concentration of the lithium-rich anode is increased to 1.17g/L, simultaneously, the content of other impurity ions is low, and K, Mg, Ca and SO are added4 2-The retention rate of B is 90%, and the purity of the obtained anolyte is also higher.
The ion content of each cell was analyzed and shown in table 2, the change in the cathode lithium concentration and the intercalation capacity of iron phosphate versus time in fig. 8 and 9.
TABLE 2 Total analysis (g/L) of the anolyte and brine
The analysis shows that the experimental effect of the lithium extraction experiment by adopting pure titanium has no great difference with the comparison of ruthenium-coated titanium, but the lithium extraction experiment by directly adopting pure titanium can greatly reduce the preparation time of the electrode plate, save the cost and improve the production efficiency.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The electrode plate in the electrochemical de-intercalation method comprises a positive plate and a negative plate, wherein the positive plate and the negative plate are formed by coating a lithium battery positive electrode material on a supporting material.
2. The conductive support material for an electrode plate for lithium extraction by electrochemical desorption according to claim 1, wherein the support material is a titanium mesh, preferably, the thickness of the titanium mesh is 0.1-5 mm.
3. The conductive support material for an electrode plate for lithium extraction by electrochemical desorption as claimed in claim 2, wherein the thickness of the titanium mesh is 0.8-2 mm.
4. The conductive support material for the electrode plate for lithium extraction by the electrochemical desorption method as claimed in claim 3, wherein at least one reinforcing rib is further fixed on the support material, and the reinforcing rib is formed by punching a titanium mesh.
5. The conductive support material for an electrode plate for lithium extraction by electrochemical deintercalation as claimed in claim 4, wherein said reinforcing ribs are fixedly connected to the titanium mesh in a vertical or horizontal direction.
6. The conductive support material for an electrode plate for lithium extraction by electrochemical deintercalation as claimed in claim 5, wherein said reinforcing ribs are welded to the titanium mesh in a vertical or horizontal direction.
7. The conductive support material for the electrode plate for lithium extraction by the electrochemical desorption method as claimed in claim 5, wherein the reinforcing ribs are V-shaped vertical grooves, and the groove depth is less than or equal to 3 mm.
8. The conductive support material for an electrode plate for lithium extraction by electrochemical desorption as claimed in any one of claims 2 to 7, wherein said titanium mesh is polygonal, preferably said titanium mesh is rectangular or square.
9. The conductive supporting material of an electrode plate for lithium extraction by an electrochemical desorption method as claimed in claim 1, wherein a plurality of fixing ears connected with the tank frame body are symmetrically arranged on the left side and the right side of the titanium mesh respectively.
10. The conductive supporting material of the electrode plate for lithium extraction by the electrochemical desorption method as claimed in claim 1, wherein the upper end of the titanium mesh is provided with a transition plate for connecting an extraction electrode, preferably, the transition plate is made of titanium mesh.
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| CN115692904A (en) * | 2022-08-24 | 2023-02-03 | 哈尔滨工业大学 | Method for recycling waste lithium ion battery anode material based on SOC regulation and control and application |
| CN115772609A (en) * | 2023-02-13 | 2023-03-10 | 石家庄嘉硕电子技术有限公司 | Electrochemical lithium extraction method and electrochemical lithium extraction system |
| CN116043255A (en) * | 2022-12-29 | 2023-05-02 | 天津科技大学 | Lithium extraction electrode preparation method and lithium extraction device |
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