CN113337735B - Nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources - Google Patents
Nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources Download PDFInfo
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Abstract
The invention relates to a nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of a dissolved lithium resource. The electrode material of the membrane electrode comprises an encapsulation layer derived from a lithium ion sieve and a nitrogen-containing polymer. The nitrogen-containing polymer monomer is pyrrole, aniline, acrylonitrile, amide, ethylene imine, dopamine and urethane. In the preparation, a two-stage polymerization mode is adopted, namely low-temperature prepolymerization and room-temperature polymerization, and different feed ratios of 1: 0.1-1: 10 and high temperature and N at 200-700 ℃ are adjusted2And (3) calcining in the environment to obtain the uniform and complete carbon-encapsulated lithium ion sieve electrode material, and preparing the carbon-encapsulated lithium ion sieve membrane electrode for enriching the dissolved lithium resources. The novel lithium ion sieve membrane electrode obtained by the invention has higher lithium extraction rate, lithium ion selectivity and stable cycle capacity in complex coexisting ions and low-grade lithium raw material liquid.
Description
Technical Field
The invention belongs to the technical field of electrochemical lithium extraction, and particularly relates to a membrane electrode material for electrochemical extraction of a dissolved lithium resource and a preparation method thereof.
Background
The lithium metal has the advantages of high specific heat, high conductivity and high chemical activity, and has a great significance in the fields of energy, materials, medical treatment, chemical industry, aerospace, national defense and the like. With the advent of the information age and the green economy age, clean lithium ion batteries with light weight, small volume and high energy density have been widely developed and applied. Meanwhile, the rapidly developing lithium battery industry also makes the market demand for lithium resources grow in a leap manner. At present, lithium resources are mainly derived from terrestrial lithium ores, and although the current terrestrial lithium ores can still meet the market demand, a single terrestrial lithium resource cannot meet the huge demand of the future market for the lithium resources in the long term. In addition, high energy consumption and environmental pollution accompanied with land lithium mine exploitation are caused, and the difficulty in later-stage environmental improvement is high. Therefore, the development of diversified lithium resource exploitation methods will be the mainstream of future lithium resource development. Wherein, the extraction of the dissolved lithium resources represented by seawater and brine has the advantages of low energy consumption, no pollution and huge reserves, and has great development potential. However, the lithium resources in the dissolved state also have the problems of low taste and complex coexisting ion environment, so the development of an efficient extraction method of the dissolved lithium resources has a very important significance for the development and utilization of the dissolved lithium resources.
At present, the development methods of the dissolved lithium resource mainly comprise a precipitation method, a solvent extraction method, an adsorbent method, an electrodialysis method and an electrochemical method. Among them, the precipitation method is simple in operation but cannot be used in a solution system with a high magnesium-lithium ratio, the solvent extraction method is high in product purity but high in cost, and the electrodialysis method is difficult to realize effective separation between monovalent ions. Therefore, the adsorbent method has unique advantages aiming at a seawater and brine system with low lithium grade and a complex coexisting ion environment, and has higher lithium ion selectivity even in the seawater and brine system based on the unique ion screening performance, but the traditional adsorbent method also has the problems of long adsorption time and large consumption of acid in the elution process, so that the further industrial application of the traditional adsorbent method is limited.
The electrochemical method is a development of the conventional adsorbent method. Based on the driving of an external electric field, the intercalation and deintercalation rate of lithium ions is enhanced, and the use of acidic and oxidative eluents is avoided. Currently, researchers have extensively studied electrode materials represented by lithium manganate, lithium titanate, lithium iron phosphate and ternary lithium battery materials, but the application of the electrode materials in the field of electrochemical lithium extraction is limited to a certain extent due to poor electrical conductivity of the electrode materials, atomic dissolution loss in the redox process and inherent defects of the Jhan-Teller effect.
Disclosure of Invention
The invention aims to provide a novel lithium ion sieve electrode material for electrochemical extraction of dissolved lithium resources and a preparation method of a membrane electrode thereof aiming at the defects in the prior art. The invention adopts a nitrogenous polymer as a carbon-coated precursor, and the preparation process adopts a two-stage polymerization mode, namely low-temperature prepolymerization and room-temperature polymerization, and adopts different feed ratios with the adjustment interval of 1: 0.1-1: 10 and high temperature, N and N of 200-700 DEG C2And (3) calcining in the environment to obtain the uniform and complete carbon-encapsulated lithium ion sieve electrode material, and preparing the carbon-encapsulated lithium ion sieve membrane electrode for enriching dissolved lithium resources. The novel lithium ion sieve membrane electrode obtained by the invention has higher lithium extraction rate, lithium ion selectivity and stable cycle capacity in complex coexisting ions and low-grade lithium raw material liquid.
The technical scheme of the invention is as follows:
a nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources is disclosed, wherein the electrode material of the membrane electrode comprises a main material and a nitrogen-doped carbon packaging material; the mass ratio of the lithium ion sieve forming the main material to the nitrogen-doped carbon-packaged nitrogen-containing monomer is 1: 0.1-1: 10;
The encapsulation layer derived from the nitrogen-containing polymer is coated on the crystal surface of the positive electrode material and is in positive correlation with the mass ratio of the lithium ion sieve to the nitrogen-containing monomer;
the thickness of the packaging layer derived from the nitrogen-containing polymer is 1-100 nm.
The lithium ion sieve material is a lithium manganate lithium ion sieve, a lithium titanate lithium ion sieve or a ternary lithium ion sieve; in particular Li2TiO3、LiMn2O4、Li(NiCoMn)O2Or LiFePO4；
The nitrogen-doped carbon package is: the three-dimensional in-situ nitrogen-doped carbon packaging layer is derived from an in-situ polymerized nitrogen-containing polymer, wherein the nitrogen-containing polymer monomer comprises any one or more of five-membered ring nitrogen-containing monomers, six-membered ring nitrogen-containing monomers and acyclic nitrogen-containing monomers,
the nitrogen-containing polymer monomer is pyrrole, aniline, acrylonitrile, amide, ethylene imine, dopamine and urethane,
the preparation method of the nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of the dissolved lithium resource comprises the following steps:
(1) dispersing a lithium ion sieve material in the mixed solution A, adding a nitrogen-containing monomer, ultrasonically dispersing for 0.1-5 h, then dropwise adding an initiator ammonium persulfate solution at the temperature of-10 ℃ under vigorous stirring, wherein the reaction temperature is-10 ℃, and the reaction time is 0.1-5 h;
Wherein the lithium ion sieve material is one of a lithium manganate lithium ion sieve, a lithium titanate lithium ion sieve or a ternary lithium ion sieve; the mixed solution A consists of ethanol and water, and the volume ratio of ethanol: water is 1: 0.1-1: 10; the mass ratio of the lithium ion sieve material: water is 1: 50-1: 200; the mass ratio of the lithium ion sieve material: a nitrogen-containing monomer at a ratio of 1:0.1 to 1: 10; the molar weight ratio of the initiator ammonium persulfate to the nitrogen-containing monomer is 1: 0.5-1: 2;
the solvent of the initiator ammonium persulfate solution is the same as the component of the mixed solution A, and the concentration range of the initiator solution is 4.2775 mg/mL-42.775 mg/mL.
The nitrogen-containing monomer is pyrrole, aniline, acrylonitrile, amide, ethylene imine, dopamine or urethane;
the rotating speed of the violent stirring is 500 r/min-2000 r/min; the stirring time is 0.1 h-10 h;
specifically, the optimal feeding range of the feeding amount is that the mass ratio of the lithium ion sieve material is as follows: the nitrogen-containing monomer is 1: 0.130-0.140.
(2) Then, moving the reactor to 15-30 ℃ for continuous reaction for 0.1-18 h, carrying out vacuum filtration to obtain solid powder, washing filter residues until the filtrate is colorless, and drying in a vacuum drying oven overnight; the obtained solid powder is an electrode material intermediate encapsulated by the nitrogenous polymer; placing the intermediate in a crucible, heating to 200-700 ℃ in a tubular furnace, and calcining for 0.1-10 h; obtaining solid powder, namely the nitrogen-doped carbon packaging lithium ion sieve material;
And the filter residue washing mode is that the filter residue is washed by absolute ethyl alcohol and deionized water repeatedly until the filtrate is colorless, and then the filter residue is washed for 1-10 times. The drying mode is vacuum drying at 1-100 ℃;
the heating rate is 1-10 ℃/min.
(3) Adding the nitrogen-doped carbon-packaged lithium ion sieve material, acetylene black and a binder into the mixed solution B for mixing, uniformly coating the obtained slurry on the surface of carbon cloth, and drying overnight to obtain a nitrogen-doped carbon-packaged lithium ion sieve membrane electrode;
the coating amount of the slurry on the carbon cloth is 5-8 mg/cm2；
Specifically, in the step (3), the lithium ion sieve material is the nitrogen-doped carbon-encapsulated lithium ion sieve prepared by the method, and the lithium ion sieve material is mixed with acetylene black and a binder in a mass ratio of 1:1: 1-10: 1: 1. The mixed solution B is ethanol and deionized water in a volume ratio of 1: 0.1-1: 10, and the mass ratio of the ethanol and the deionized water to the total mass of the solid is 1: 1-5: 1.
The mixing mode is that magnetic stirring is firstly carried out for 0.1-10 hours, and then ultrasonic dispersion is carried out for 0.1-1 hour. The drying mode is vacuum drying at 25-100 ℃.
The binder is LA132, PDFE or PVDF.
The nitrogen-doped carbon-packaged lithium ion sieve membrane electrode is applied to electrochemical enrichment of dissolved lithium resources.
The method specifically comprises the following steps:
(1) connecting the obtained nitrogen-doped carbon-packaged lithium ion sieve membrane electrode with a positive electrode, connecting an AgCl electrode with a negative electrode, applying a constant voltage of 0.1-1.0V in a KCl solution of 0.01-1.00 mol/L until the current is reduced to 0.1mA, and at the moment, obtaining the nitrogen-doped carbon-packaged lithium ion sieve membrane electrode in a lithium-poor state; then connecting the anode with the cathode of a stabilized voltage supply;
in addition, the nitrogen-doped carbon-packaged lithium manganate lithium ion sieve membrane electrode is connected with the anode of a stabilized voltage power supply to form a rocking chair type lithium extraction system;
(2) connecting the prepared lithium-rich nitrogen-doped carbon-packaged lithium manganate membrane electrode with a constant-voltage power supply anode, placing the lithium-rich nitrogen-doped carbon-packaged lithium manganate membrane electrode with a constant-voltage power supply anode in a recovery solution, and placing the lithium-poor nitrogen-doped carbon-packaged lithium manganate membrane electrode with a constant-voltage power supply cathode in a raw material solution;
wherein the raw material liquid is Li+In the presence of a single solution or a mixed solution in which ions coexisting with other ions specifically include Ca2+、Na+、K+、Mg2+One or more of the cations are equal; the concentration of lithium ions in the raw materials is 20-500 mg/L;
the recovery solution is a cation solution, and the cation is Li+、Ca2+、K+、Na+、Mg2+One or more of (a); the concentration range of cations in the cation solution is 20-2000 mg/L;
(3) applying a constant voltage of 0.1-1.0V until the electrode capacity is saturated (the current is reduced to 0.1mA), and stopping;
Also comprises the following steps: taking out the electrode after the step (3) is finished, cleaning, then, exchanging the positions of the two electrodes, continuously applying the same constant voltage, and repeating the steps (2) - (3), thus realizing the Li+Enrichment from the feed solution to the recycle solution.
The invention has the substantive characteristics that:
the three-dimensional in-situ coated nitrogen-doped carbon packaging electrode material is obtained based on simple pyrrole monomer in-situ polymerization and high-temperature calcination, the specific crystal structure of the main crystal of the three-dimensional in-situ coated nitrogen-doped carbon packaging electrode material is not changed in the coating and high-temperature calcination processes, the lithium ion has high selectivity, and the crystal size reduction, the unit cell parameter increase and the crystallinity increase are carried out in the reaction process provided by the invention. In addition, the uniform and complete nitrogen-doped carbon packaging layer is prepared by in-situ polymerization of nitrogen-containing monomers, is different from common inorganic carbon, has a regular and rigid structure and high mechanical strength and conductivity, can effectively improve the problems of poor conductivity and poor cyclicity of the lithium manganate electrode, and further improves the lithium manganate electrode material. Meanwhile, by combining a rocking chair type electrode system, the lithium extraction performance of the lithium manganate electrode material is expected to be further improved, and the electrochemical extraction efficiency of the dissolved lithium resources is improved.
The precursor of the material carbon package is a nitrogen-containing conductive polymer with a conjugated condition. The matrix material is any lithium ion battery electrode material (such as any one of a titanium anode material, a manganese anode material and a ternary lithium battery anode material), and has the characteristics of simple preparation and no need of other special treatment; the obtained material is the same crystal substance with different crystal morphologies (such as LiMn)2O4Either of spinel type and layered structure, which is used for the preparation of the relevant membrane electrode material of the present invention, and the other electrode host material, as well), has a "specific crystal structure", i.e., no change occurs under the electrode system of the present invention, whereas it is difficult to ensure the effects of the present invention if a crystal change occurs.
The invention has the beneficial effects that:
the membrane electrode formed by the nitrogen-doped carbon-packaged lithium ion sieve electrode material can realize the high-efficiency enrichment of the dissolved lithium resource from the raw material liquid to the recovery liquid under the action of an external electric field, and the enrichment performance is greatly improved on the basis of the original lithium ion sieve. The crystal form of the main material of the nitrogen-doped carbon-packaged lithium ion sieve is not changed in the processes of coating and high-temperature calcination, and the main material has high selectivity on lithium ions, and the crystal size is reduced, the unit cell parameters are increased and the crystallinity is increased in the processes of coating and high-temperature reaction. Meanwhile, the nitrogen-containing polymer derived carbon packaging layer forms a uniform and complete nitrogen-doped carbon packaging layer on the surface of the lithium ion sieve in the coating and high-temperature processes, the packaging layer is made of nitrogen-containing polymer instead of inorganic carbon, and compared with common inorganic carbon, the packaging layer has a regular and rigid structure and high mechanical strength and conductivity.
Compared with the prior art, the nitrogen-doped carbon packaging lithium ion sieve disclosed by the invention has the advantages that the carbon packaging layer is used as the buffer layer, so that the rapid capacity reduction caused by the dissolution loss of transition metal elements (Mn and Ti) and the Jhan-teller effect is effectively inhibited, the polarization phenomenon of a membrane electrode is reduced, the rate capability of an electrode is improved, and the sieve has higher initial charge-discharge capacity which is about 119.22mAh/g (at most, can reach 119.22 mAh/g). Meanwhile, the carbon package is used as a conductive layer, so that the transmission rate of electrons and ions is effectively improved, the electronic and ionic conductivity of the lithium ion sieve matrix is enhanced, and the lithium extraction rate of the membrane electrode is further improved by about 49%. In addition, based on crystal refinement in the high-temperature calcination process, the lithium extraction performance is effectively optimized. In addition, the increase of unit cell parameters enlarges the crystal face spacing of the lithium ion sieve crystal, properly widens the lithium ion channel, enhances the competitiveness of lithium ions and improves the selectivity of the membrane electrode to the lithium ions. In conclusion, the nitrogen-doped carbon-packaged lithium ion sieve membrane electrode provided by the invention can realize high-efficiency extraction of lithium resources in a working environment with complex coexisting ions and low-grade lithium concentration.
Drawings
In order to make the content of the invention easier to be clearly understood, the invention is further described in detail by taking the nitrogen-doped carbon-encapsulated lithium ion sieve membrane electrode material prepared based on polypyrrole and lithium manganate as an example and combining with the accompanying drawings, wherein,
fig. 1 is a schematic diagram of a preparation process of the electrode material and a working schematic diagram of a membrane electrode according to the present invention, in which fig. 1a is a schematic diagram of a preparation process of a nitrogen-doped carbon-packaged lithium manganate electrode material, and fig. 1b is a schematic diagram of an electrochemical lithium extraction process of a nitrogen-doped carbon-packaged lithium manganate membrane electrode;
FIG. 2 is a schematic diagram of a strong mechanism of the nitrogen-doped carbon-packaged lithium manganate membrane electrode of the present invention;
fig. 3 is an electron microscope image of a nitrogen-doped carbon-encapsulated lithium manganate electrode material obtained by the method of example 1 and comparative example 1, wherein fig. 3a is a calcined product, i.e., a nitrogen-doped carbon-encapsulated lithium manganate electrode material, and fig. 3b is an uncalcined intermediate, i.e., a nitrogen-containing polymer-encapsulated lithium manganate electrode material;
fig. 4 shows X-ray diffraction patterns of the nitrogen-doped carbon-encapsulated lithium ion sieve electrode materials in example 1 and comparative example 1 according to the present invention.
Fig. 5 is a diagram showing the distribution of elements in the nitrogen-doped carbon encapsulated lithium ion sieve electrode material according to example 1 and comparative example 1 of the present invention, wherein fig. 5a is a diagram showing a scanning electron microscope of the element distribution, fig. 5b is a diagram showing the distribution of each element, fig. 5C is a diagram showing the distribution of C element, fig. 5d is a diagram showing the distribution of N element, fig. 5e is a diagram showing the distribution of O element, and fig. 5f is a diagram showing the distribution of Mn element;
Fig. 6 is an infrared spectrum of a nitrogen-doped carbon-encapsulated lithium ion sieve electrode material in example 1 and comparative example 1, wherein fig. 6a is an infrared spectrum of lithium manganate, polypyrrole-encapsulated lithium manganate, and nitrogen-doped carbon-encapsulated lithium manganate electrode materials, and fig. 6b is a partial enlarged view of an infrared spectrum of polypyrrole-encapsulated lithium manganate and nitrogen-doped carbon-encapsulated lithium manganate electrode materials;
FIG. 7 is a graph showing the lithium ion adsorption capacity of a nitrogen-doped carbon-encapsulated lithium manganate membrane electrode in a single LiCl (0.05mol/L) solution as a function of time in example 1 of the present invention;
fig. 8 is a graph showing the change of ion transport amount in different coexisting mixed solutions of the lithium manganate membrane electrode and the nitrogen-doped carbon-encapsulated lithium manganate membrane electrode in example 1 and comparative example 1 according to the present invention with time, wherein fig. 8a is a graph showing the change of ion electro-adsorption capacity in a Li-Mg mixed solution with time, fig. 8b is a graph showing the change of ion electro-adsorption capacity in a Li-Na mixed solution with time, fig. 8c is a graph showing the change of ion electro-adsorption capacity in a Li-K mixed solution with time, and fig. 8d is a graph showing the change of ion electro-adsorption capacity in a Li-Ca mixed solution with time;
FIG. 9 is a plot of cyclic voltammetry, and current as a function of V for lithium manganate film electrodes and nitrogen-doped carbon-encapsulated lithium manganate film electrodes of example 1 and comparative example 1 in accordance with the present invention 1/2/s1/29a and 9b are respectively a cyclic voltammogram and a current as a function of V of the nitrogen-doped carbon-packaged lithium manganate membrane electrode under the sweep rate of 0.1-0.5mV/s1/2/s1/29c and 9d are graphs of cyclic voltammetry of lithium manganate membrane electrode at sweep rate of 0.1-0.5mV/s and current as a function of V, respectively1/2/s1/2A change map of (c); FIGS. 9e and 9f are graphs showing the change of current with voltage after 30 cyclic voltammetry processes for the lithium manganate membrane electrode and the nitrogen-doped carbon-packaged lithium manganate membrane electrode, respectively;
FIG. 10 is a graph showing the change of charge-discharge capacity with cycle number of a lithium manganate membrane electrode and a nitrogen-doped carbon-encapsulated lithium manganate membrane electrode in example 1 according to the present invention and comparative example 1;
FIG. 11 is a graph showing the variation of the number of cycles of the electro-adsorption capacity of the N-doped carbon-encapsulated lithium manganese oxide membrane electrode in the process of extracting lithium in example 1 of the present invention
Fig. 12 is a graph showing the change of the electro-adsorption capacity of each ion in simulated concentrated seawater of the nitrogen-doped carbon-encapsulated lithium manganese oxide membrane electrode in example 1 of the present invention with time.
Detailed Description
In the following examples and comparative examples of the present invention, the changes of the concentrations of the cations in the recovered solution with time were measured by a TAS-990F atomic absorption spectrophotometer, and the electrode materials and the membrane electrode performance were analyzed and compared by an electrochemical workstation, an environmental scanning electron microscope, an X-ray diffractometer, and an infrared spectrometer.
The following examples and comparative examples of the present invention were carried out based on the apparatus shown in FIG. 1 (b). The left side is a recovery liquid chamber, the right side is a raw material liquid chamber, the two chambers are isolated by a monovalent selective anion exchange membrane (ACS), the left side electrode is a lithium-rich electrode, the right side electrode is a lithium-poor electrode, and the two electrodes are connected with the anode and the cathode of a constant voltage power supply in a decomposition way.
Example 1
Selecting a main material as lithium manganate, using a carbon packaging material as pyrrole, and feeding lithium manganate in an optimal feeding mass ratio: pyrrole is 1: the preparation and performance test of the nitrogen-doped carbon-packaged lithium manganate electrode material under the condition of 0.135 are carried out as an example, and the preparation and performance test comprise the following steps
(1) Preparation of polypyrrole derived nitrogen-doped carbon-packaged lithium manganate powder
Preparing lithium manganate lithium ion sieve powder by a high-temperature solid phase method. Pyrrole monomer is reacted with LiMn by the method described previously2O4And carrying out three-dimensional coating on the surface of the lithium ion sieve to obtain a nitrogenous polymer packaged lithium manganate intermediate. And placing the obtained intermediate in a crucible, and calcining at high temperature in a tubular furnace under the high-temperature condition. The powder obtained is the example: nitrogen-doped carbon-packaged lithium manganate lithium ion derived from polypyrroleAnd (4) screening.
a) Taking 1g of LiMn 2O4Uniformly dispersed in 100mL of mixed solution of ethanol and deionized water. Wherein the volume ratio of ethanol to water is 1:1, and LiMn2O4The mass ratio of the mixed solution to the mixed solution is 1: 100. Subsequently, LiMn was added in a mass ratio2O4: 135 mu L of pyrrole monomer containing 1:0.135 of nitrogen monomer, after 30min of ultrasonic dispersion, violently stirring for 5h at the rotating speed of 1500r/min at the temperature of minus 1 ℃, and fully and uniformly mixing the monomer and an ion sieve;
b) taking the molar ratio as (NH)4)2S2O8Nitrogen-containing monomers 1: 0.4277g of ammonium persulfate 1 dissolved in ethanol in a volume ratio of: the initiator solution was 40mL of a 1:1 mixed solution. Then, all the solution was dropwise added to the vigorously stirred mixed solution (rotation speed 1500r/min) and reacted at-1 ℃ for 5 hours (total of 5 hours of dropwise addition and reaction time); subsequently, the reactor was moved to ambient temperature (25 ℃ C.) and the reaction was continued for 18h with vigorous stirring (1500 r/min). And after the reaction is finished, carrying out vacuum filtration on the mixed suspension to obtain filter residue, repeatedly washing the filter residue by using absolute ethyl alcohol and deionized water until the filtrate is colorless, and continuously washing for 6 times. Drying at 70 deg.C for 12 h.
c) 3g of the solid powder obtained in the step is placed in a crucible and calcined in a tubular furnace at 500 ℃ for 3h, wherein the heating rate is 5 ℃/min. The obtained solid powder is the nitrogen-doped carbon-packaged lithium manganate;
(2) Preparing a nitrogen-doped carbon packaging lithium manganate membrane electrode and constructing a lithium extraction system.
a) Taking 0.4g of prepared nitrogen-doped carbon-packaged lithium manganate powder, mixing the powder with acetylene black and LA132 binder according to the mass ratio of 8:1:1, adding 2mL of a mixed solution (the mixed solution is ethanol and deionized water with the volume ratio of 1: 1) of the three mixtures with the total mass solid-to-liquid ratio of 1:4, stirring at the rotating speed of 200r/min for 30min, and performing ultrasonic treatment for 1min to obtain a mixed slurry. The obtained slurry was uniformly coated on a 2 x 3.5cm carbon cloth in an amount of 6-7mg/cm2. And drying in vacuum at 70 ℃ to obtain the nitrogen-doped carbon-packaged lithium manganate membrane electrode.
b) Packaging the obtained nitrogen-doped carbon with manganic acidConnecting a lithium membrane electrode with a positive electrode, connecting an AgCl electrode with a negative electrode, applying 1V constant voltage in 0.05mol/L KCl solution until the current is reduced to 0.1mA, and obtaining the electrode which is a nitrogen-doped carbon-packaged lithium manganate membrane electrode in a lithium-poor state, namely Li1-xMn2O4@ CN. On the contrary, the unprocessed lithium-rich nitrogen-doped carbon-packaged lithium manganate lithium ion sieve membrane electrode is LiMn2O4@CN。
c) And connecting the lithium-poor state nitrogen-doped carbon-packaged lithium manganate membrane electrode with a negative electrode of a stabilized power supply, and connecting the lithium-rich state nitrogen-doped carbon-packaged lithium manganate membrane electrode with a positive electrode of the stabilized power supply, thus obtaining the rocking chair type lithium extraction system based on the novel nitrogen-doped carbon-packaged lithium manganate. The details of the construction method of the electrode system can be performed by referring to the prior art scheme of the subject group, such as the construction method disclosed in the chinese patent CN 107201452A.
(3) Electrochemical lithium extraction process driven by external electric field
a) The prepared lithium-rich nitrogen-doped carbon-packaged lithium manganate membrane electrode is connected with a positive electrode of a constant-voltage power supply and placed in a recovery solution, and the lithium-poor nitrogen-doped carbon-packaged lithium manganate membrane electrode is connected with a negative electrode of the constant-voltage power supply and placed in a raw material solution. The raw material solution and the recovery solution form a solution system in the electrochemical lithium extraction process, and the solution system is specifically divided into two types: firstly, a system I: the raw material solution and the recovered solution are respectively provided with coexisting ions (Ca)2+、Na+、K+、Mg2+1.00mol/L) of 80mL of LiCl (0.05mol/L) solution and 80mL of KCl (0.05mol/L) solution; system two: the raw material solution and the recovery solution are 80mL of simulated concentrated seawater and 80mL of KCl (0.05mol/L) solution respectively.
b) A constant external electric field of 0.8V was applied. At this time, lithium ions migrate from the positive electrode into the recovery liquid in the recovery liquid chamber; in the raw material liquid chamber, lithium ions are inserted from the recovered liquid into the negative electrode. Stopping reaction when the current is reduced to 0.1mA, taking out the nitrogen-doped carbon packaging membrane electrode, fully washing the membrane electrode by using deionized water, reversing the positions of two nitrogen-doped carbon packaging lithium manganate membrane electrodes, and repeating the steps to realize the enrichment of lithium ions from the raw material liquid phase recovery liquid.
Comparative example 1
Compared with the electrochemical lithium extraction process in example 1, the electrochemical lithium extraction process in the comparative example has the same operation conditions and electrode system structure, and only differs from the electrochemical lithium extraction process in that the membrane electrode used in the comparative example 2 is a lithium manganate membrane electrode formed by a common lithium manganate lithium ion sieve, and no polypyrrole coating and high-temperature calcination processes are performed. While the embodiment 1 is a nitrogen-doped carbon-packaged lithium manganate membrane electrode.
As shown in fig. 3 and fig. 4, the specific spinel-type octahedral crystal structure of lithium manganate crystals before and after calcination is not changed, and a distinct nitrogen-doped carbon encapsulation layer can be observed in fig. 3(a), and the crystal size is reduced. As shown in fig. 5 and fig. 6, the intermediate polypyrrole-encapsulated lithium manganate and nitrogen-doped carbon-encapsulated lithium manganate both have corresponding infrared characteristic peaks (fig. 6), and elements are uniformly distributed on the crystal surface (fig. 6), which indicates that the nitrogen-doped carbon encapsulation layer is successfully prepared and has a uniform and complete structure. As shown in figure 7, the equilibrium time of the nitrogen-doped carbon-packaged lithium manganate membrane electrode in a single LiCl (0.05mol/L) is about 40min, and the electro-adsorption capacity is 34.57 mg/g.
In Li+：Mg2+0.05 mol/L: after a lithium extraction experiment is carried out in 80mL of 1.00mol/L lithium-magnesium mixed solution, the ion content in the recovery solution is detected by a TAS-990F atomic absorption spectrophotometer, and as shown in figure 8, the equilibrium time of example 1 in the same mixed ion solution is about 40min, which is shorter than that of comparative example 2 (more than 40 min). The lithium ion transport amount of the example 1 at the same time is larger than that of the comparative example 2. Of these, example 1 had about twice the amount of lithium transferred at 5min as compared with comparative example 2. Meanwhile, as shown in table 2, the nitrogen-doped carbon-encapsulated lithium manganate ionic sieve membrane electrode material of example 1 is Ca 2+、Na+、 K+、Mg2 +The selection coefficients of the four coexisting ions are further improved.
TABLE 2
In addition, as shown in fig. 9a to d, it can be seen from the CV curve analysis at different sweep rates that the intercalation and deintercalation of lithium ions on the electrode are controlled by the diffusion process. As shown in Table 3, the diffusion coefficients of lithium ions of the nitrogen-doped carbon-packaged lithium manganate ion sieve membrane electrode are greatly improved. Meanwhile, as shown in fig. 9e to 9f, the nitrogen-doped carbon-packaged lithium manganate ion sieve membrane electrode does not have the displacement of the oxidation-reduction peak after 30 CV cycles, which indicates that the polarization phenomenon of the nitrogen-doped carbon-packaged lithium manganate ion sieve membrane electrode is improved.
TABLE 3
In addition, the initial charge-discharge capacity of the nitrogen-doped carbon-packaged lithium manganate ionic sieve membrane electrode material is 23.56% and 24.77% higher than that of a lithium manganate membrane electrode (shown in figure 10). After 50 charge-discharge cycles, the charge-discharge capacity of the nitrogen-doped carbon-packaged lithium manganate ionic sieve membrane electrode is 28.5 percent and 25.6 percent higher than that of the lithium manganate ionic sieve membrane electrode respectively (figure 10). The electro-adsorbed lithium capacity decayed by about 8% over the course of ten actual cycles of operation (fig. 11). In simulated concentrated seawater, the lithium capacity of the nitrogen-doped carbon-packaged lithium manganate ion sieve membrane electrode can still reach 37.14Mg/g (shown in figure 12), and the separation coefficients for Ca, Na and Mg ions are 1381.89, 2110.64 and 228.25 respectively. In conclusion, the nitrogen-doped carbon-packaged lithium manganate membrane electrode based on the strengthening mechanism shown in fig. 2 is successfully prepared and has ideal electrochemical lithium extraction performance.
Comparative example 2
Compared with the electrochemical lithium extraction process in example 1, the electrochemical lithium extraction process in the comparative example has the same operation conditions and electrode structure, and only differs from the nitrogen-doped carbon encapsulated membrane electrode used in comparative example 2 in different proportions. Specifically, in this comparative example: the dosage of pyrrole monomer is 540 mu L; the dosage of the ammonium persulfate initiator is 1.71 g.
In Li+：Mg2+0.05 mol/L: after a lithium extraction experiment is carried out in 80mL of 1.00mol/L lithium-magnesium mixed solution, the ion content in the recovery solution is detected by a TAS-990F atomic absorption spectrophotometer. The results show thatThe equilibrium time of comparative example 2 in the mixed ion solution of (1) was about 20min, the lithium capacity was 4.56mg/g, and the lithium-magnesium separation coefficient was 42.64.
Comparative example 3
Compared with the electrochemical lithium extraction process in example 1, the electrochemical lithium extraction process in the comparative example has the same operation conditions and electrode structure, and only differs from the nitrogen-doped carbon encapsulated membrane electrode used in comparative example 2 in different proportions. Specifically, in this comparative example: the material feeding amount of the pyrrole monomer is 270 mu L; the dosage of the ammonium persulfate initiator is 0.85 g.
In Li+：Mg2+0.05 mol/L: after a lithium extraction experiment is carried out in 80mL of 1.00mol/L lithium-magnesium mixed solution, the ion content in the recovery liquid is detected by a TAS-990F atomic absorption spectrophotometer. The results show that the equilibration time of comparative example 2 is about 20min and the lithium capacity is 9.39mg/g in the same mixed ion solution.
Comparative example 4
Compared with the electrochemical lithium extraction process in example 1, the electrochemical lithium extraction process in the comparative example has the same operation conditions and electrode structure, and only differs from the nitrogen-doped carbon encapsulated membrane electrode used in comparative example 2 in different proportions. Specifically, in this comparative example: the feeding amount of the pyrrole monomer is 180 mu L; the inventory amount of the ammonium persulfate initiator is 0.57 g.
In Li+：Mg2+0.05 mol/L: after a lithium extraction experiment is carried out in 80mL of 1.00mol/L lithium-magnesium mixed solution, the ion content in the recovery solution is detected by a TAS-990F atomic absorption spectrophotometer. The results show that the equilibration time of comparative example 2 was about 35min, the lithium capacity was 20.74mg/g, and the lithium magnesium separation coefficient was 180.55 in the same mixed ion solution.
Comparative example 5
Compared with the electrochemical lithium extraction process in example 1, the electrochemical lithium extraction process in the comparative example has the same operation conditions and electrode structure, and only differs from the nitrogen-doped carbon encapsulated membrane electrode used in comparative example 2 in different proportions. Specifically, in this comparative example: the feeding amount of the pyrrole monomer is 105 mu L; the dosage of the ammonium persulfate initiator is 0.342 g.
In Li+：Mg2+0.05 mol/L: after a lithium extraction experiment is carried out in 80mL of 1.00mol/L lithium-magnesium mixed solution, the ion content in the recovery solution is detected by a TAS-990F atomic absorption spectrophotometer. The results show that the equilibration time of comparative example 2 was about 35min, the lithium capacity was 25.89mg/g, and the lithium magnesium separation factor was 234.32 in the same mixed ion solution.
Through the comparative example 1, it can be clearly found that the novel membrane electrode material provided by the invention is greatly improved in adsorption rate, equilibrium time and lithium-magnesium separation coefficient compared with the traditional membrane electrode material. Further, based on comparative examples 2 to 5, it can be clearly found that, based on the three core parameters of the balance time, the lithium capacity and the lithium-magnesium separation coefficient, the core parameters of the membrane electrode corresponding to different material charges are different, and the performance of the novel membrane electrode material is optimal under the optimal material charge ratio (example 1) provided by the invention.
Obviously, based on the three core parameters of the balance time, the lithium capacity and the lithium-magnesium separation coefficient, the above examples only clearly illustrate the key preparation method and the use method of the nitrogen-doped carbon-encapsulated lithium ion sieve material and the related membrane electrode material of the present invention, and do not strictly limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
The novel nitrogen-doped carbon packaging membrane electrode provided by the invention has the advantages that the lithium extraction speed is greatly improved and the cycle stability is improved in the field of electrochemical lithium extraction. Taking the embodiment as an example, compared with the earlier stage work of the subject group, under the same working condition, the lithium extraction rate is improved by about 49.19%, and the time consumed by single lithium extraction is shortened from 2h to about 40 min; the lithium-magnesium separation coefficient is improved by about 40%; the cycle performance is improved by about 20 percent. Compared with other similar lithium extraction electrode systems at home and abroad, simulated seawater (C) at low gradeLi+170mg/L), has shorter lithium extraction time and higher lithium capacity (90min,37.14mg/g), and is more suitable for the demand of low-grade raw material liquid for lithium extraction in the future market. The relevant parameters are compared as shown in the following table.
Lithium extraction conditions and performance comparisons of the electrode of the invention with other similar electrode systems
[1]C.P.Lawagon,G.M.Nisola,R.A.I.Cuevas,H.Kim,S.-P.Lee,W.-J.Chung,Li1-xNi0.33Co1/3Mn1/3O2/Ag for electrochemical lithium recovery from brine,Chemical Engineering Journal 348(2018)1000-1011.
[2]X.Zhao,G.Li,M.Feng,Y.Wang,Semi-continuous electrochemical extraction of lithium from brine using CF-NMMO/AC asymmetric hybrid capacitors,Electrochimica Acta 331(2020)135285.
[3]Z.Zhao,X.Si,X.Liu,L.He,X.Liang,Li extraction from high Mg/Li ratio brine with LiFePO4/FePO4 as electrode materials,Hydrometallurgy 133(2013)75-83.
[4]M.-Y.Zhao,Z.-Y.Ji,Y.-G.Zhang,Z.-Y.Guo,Y.-Y.Zhao,J.Liu,J.-S.Yuan,Study on lithium extraction from brines based on LiMn2O4/Li1-xMn2O4 by electrochemical method,Electrochimica Acta 252(2017)350-361.
[5]X.Zhao,Y.Jiao,P.Xue,M.Feng,Y.Wang,Z.Sha,Efficient Lithium Extraction from Brine Using a Three-Dimensional Nanostructured Hybrid Inorganic-Gel Framework Electrode,ACS Sustainable Chemistry& Engineering 8(2020)4827-4837.
In the case of the example 2, the following examples are given,
the other steps are the same as the example 1, except that polypyrrole is replaced by poly-2, 5-dimethoxyaniline, and the calcining temperature is replaced by 600 ℃ from 500 ℃;
the nitrogen-doped carbon-packaged lithium manganate membrane electrode obtained based on polyaniline has similar performance to that of the embodiment 1, the adsorption performance is improved, and the balance time is about 1 h.
Example 3
The other steps are the same as the embodiment 1, except that the polypyrrole is replaced by poly 2, 5-dimethoxyaniline, and the calcination temperature is replaced by 600 ℃ from 500 ℃;
the nitrogen-doped carbon-packaged lithium manganate membrane electrode obtained based on poly (2, 5-dimethoxyaniline) has similar performance to that of the membrane electrode obtained in the examples 1 and 2, the adsorption rate is improved, and the equilibrium time is about 1 h.
Example 4
The other steps are the same as the embodiment 1, except that lithium manganate is replaced by lithium titanate;
the properties of the resulting material were close to those of example 1.
The invention is not the best known technology.
Claims (8)
1. A nitrogen-doped carbon packaging lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources is characterized in that the electrode material of the membrane electrode comprises a main material and a nitrogen-doped carbon packaging material; the mass ratio of the lithium ion sieve forming the main material to the nitrogen-doped carbon-packaged nitrogen-containing monomer is 1: 0.1-1: 10;
the lithium ion sieve material is lithium manganate lithium ion sieve, lithium titanate lithium ion sieve, Li (NiCoMn) O2Lithium ion sieves or LiFePO4A lithium ion sieve;
the nitrogen-doped carbon package is as follows: the three-dimensional in-situ nitrogen-doped carbon packaging layer is derived from an in-situ polymerized nitrogen-containing polymer, wherein the nitrogen-containing polymer monomer comprises any one or more of a five-membered ring nitrogen-containing monomer, a six-membered ring nitrogen-containing monomer and a non-cyclic nitrogen-containing monomer;
The encapsulation layer derived from the nitrogen-containing polymer is coated on the crystal surface of the anode material;
the nitrogen-containing polymer monomer is pyrrole, aniline, acrylonitrile, amide, ethylene imine, dopamine and urethane;
the preparation method of the nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of the dissolved lithium resource comprises the following steps:
(1) dispersing a lithium ion sieve material into the mixed solution A, adding a nitrogen-containing monomer, performing ultrasonic dispersion for 0.1-5 h, and then continuously stirring and mixing; then, dropping an initiator ammonium persulfate solution at the temperature of-10 ℃ to 10 ℃ and under the condition of vigorous stirring, wherein the reaction temperature is-10 ℃ to 10 ℃, and the reaction time is 0.1h to 5 h;
wherein the lithium ion sieve material is one of a lithium manganate lithium ion sieve, a lithium titanate lithium ion sieve or a ternary lithium ion sieve; the mixed solution A consists of ethanol and deionized water in a volume ratio of ethanol: deionized water =1: 0.1-1: 10; the feeding of the lithium ion sieve and the nitrogen-containing monomer meets the following conditions: the mass ratio of the lithium ion sieve material to the deionized water is 1: 50-1: 200; the mass ratio of the lithium ion sieve material to the nitrogen-containing monomer is 1: 0.1-1: 10; the molar weight ratio of the initiator ammonium persulfate to the nitrogen-containing monomer is 1: 0.5-1: 2;
The solvent of the initiator ammonium persulfate solution and the mixed solution A have the same components, and the concentration range of the initiator solution is 4.2775 mg/mL-42.775 mg/mL;
the nitrogen-containing monomer is pyrrole, aniline, acrylonitrile, amide, ethylene imine, dopamine or urethane;
(2) then, moving the reactor to 15-30 ℃, continuously reacting for 0.1-18 h under vigorous stirring, carrying out vacuum filtration to obtain solid powder, washing filter residues until filtrate is colorless, and drying in a vacuum drying oven overnight; the obtained solid powder is an electrode material intermediate encapsulated by the nitrogenous polymer; placing the intermediate in a crucible, heating to 200-700 ℃ in a tubular furnace, and calcining for 0.1-10 h; obtaining solid powder, namely the nitrogen-doped carbon packaging lithium ion sieve material;
(3) adding the nitrogen-doped carbon packaging lithium ion sieve material, acetylene black and a binder into the mixed solution B, uniformly mixing, uniformly coating the obtained slurry on the surface of carbon cloth, and drying overnight to obtain a nitrogen-doped carbon packaging lithium ion sieve membrane electrode;
the coating amount of the slurry on the carbon cloth is 5-8 mg/cm;
in the step (3), the nitrogen-doped carbon-encapsulated lithium ion sieve material, the acetylene black and the binder are mixed according to the mass ratio of 1:1: 1-10: 1: 1; the mixed solution B is ethanol and deionized water in a volume ratio of 1: 0.1-1: 10, and the ratio of the total mass of the liquid to the total mass of the solid is 1: 1-5: 1.
2. The nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources as claimed in claim 1, wherein the thickness of the packaging layer derived from the nitrogen-containing polymer is 1-100 nm.
3. The nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources as claimed in claim 1, wherein in the preparation method, the rotation speed of vigorous stirring is 500r/min to 2000 r/min; the stirring time is 0.1 to 10 hours.
4. The nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources as claimed in claim 1, wherein in the preparation method, the dosage ranges are mass ratio of lithium ion sieve material: the nitrogen-containing monomer =1: 0.130-1: 0.140;
the filter residue washing mode is that the filter residue is washed by absolute ethyl alcohol and deionized water repeatedly until the filtrate is colorless, and then the filter residue is washed for 1-10 times; the drying mode is vacuum drying at 1-100 ℃;
the temperature rise rate of the temperature rise stage is 1-10 ℃/min.
5. The nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources as claimed in claim 1, wherein in the preparation method, the mixing manner is magnetic stirring for 0.1-10 h, and then ultrasonic dispersion for 0.1-1 h; the drying mode is vacuum drying at 25-100 ℃;
The binder is LA132, PDFE or PVDF.
6. The use of the nitrogen-doped carbon-encapsulated lithium ion sieve membrane electrode assembly for electrochemical extraction of a dissolved lithium resource of claim 1, characterized by being used as an electrochemical enrichment of a dissolved lithium resource.
7. The application of the nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources as claimed in claim 6, characterized by comprising the following steps:
(1) connecting the obtained nitrogen-doped carbon-packaged lithium ion sieve membrane electrode with a positive electrode, connecting an AgCl electrode with a negative electrode, applying a constant voltage of 0.1-1.0V in a KCl solution of 0.01-1.00 mol/L until the current is reduced to 0.1mA, and at the moment, obtaining the nitrogen-doped carbon-packaged lithium ion sieve membrane electrode in a lithium-poor state;
in addition, connecting the lithium-poor nitrogen-doped carbon-packaged lithium ion sieve membrane electrode with the negative electrode of the stabilized voltage power supply; connecting a nitrogen-doped carbon-packaged lithium manganate lithium ion sieve membrane electrode with the positive electrode of a stabilized voltage power supply to form a rocking chair type lithium extraction system;
(2) connecting the prepared lithium-rich nitrogen-doped carbon-packaged lithium manganate membrane electrode with a constant-voltage power supply anode, placing the lithium-rich nitrogen-doped carbon-packaged lithium manganate membrane electrode with a constant-voltage power supply anode in a recovery solution, and placing the lithium-poor nitrogen-doped carbon-packaged lithium manganate membrane electrode with a constant-voltage power supply cathode in a raw material solution;
Wherein the raw material liquid is a single solution of Li ⁺ or a mixed solution coexisting with other ions, wherein the coexisting ions specifically comprise one or more of the cations Ca ⁺, Na ⁺, K ⁺ and Mg ⁺; the concentration of lithium ions in the raw material liquid is 20-500 mg/L;
the recovery solution is a solution of cations, said cation being one of Li ⁺, Ca ⁺, K ⁺, Na ⁺, Mg ⁺; the concentration range of the cations in the cation solution is 20-2000 mg/L;
(3) applying a constant voltage of 0.1-1.0V until the electrode capacity is saturated.
8. The use of the nitrogen-doped carbon-encapsulated lithium-ion sieve membrane electrode assembly for electrochemical extraction of dissolved lithium resources according to claim 7, characterized by further comprising the steps of: and (4) taking out the electrode which is subjected to the step (3), cleaning, then, reversing the positions of the two electrodes, continuously applying the same constant voltage, and repeating the steps (2) to (3), so that the enrichment of Li ⁺ from the raw material liquid into the recovery liquid can be realized.
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