CN117813408B - A lithium-based montmorillonite-coated LiFePO4 core-shell material and its preparation method and application - Google Patents
A lithium-based montmorillonite-coated LiFePO4 core-shell material and its preparation method and application Download PDFInfo
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Abstract
本公开属于冶金技术领域，涉及一种锂基蒙脱石包覆LiFePO4核壳材料及其制备方法和应用，该锂基蒙脱石包覆LiFePO4核壳材料包括作为核层的LiFePO4和作为壳层的锂基蒙脱石，锂基蒙脱石包覆于LiFePO4的表面。本公开制备的锂基蒙脱石包覆LiFePO4核壳材料，具备较高离子传导能力，能够弥补LiFePO4‑水界面Li+传导电阻大的缺陷，能够促进Li+在水相‑LiFePO4晶粒之间的传导，即浆料整体电阻率降低，工作电压更低，从而进一步可以降低电化学盐湖提锂能耗。本公开制备获得的锂基蒙脱石包覆LiFePO4核壳材料可以广泛应用于盐湖卤水提锂中。
The present disclosure belongs to the field of metallurgical technology, and relates to a lithium-based montmorillonite-coated LiFePO 4 core-shell material and a preparation method and application thereof, wherein the lithium-based montmorillonite-coated LiFePO 4 core-shell material includes LiFePO 4 as a core layer and lithium-based montmorillonite as a shell layer, and the lithium-based montmorillonite is coated on the surface of LiFePO 4. The lithium-based montmorillonite-coated LiFePO 4 core-shell material prepared by the present disclosure has a high ion conductivity, can make up for the defect of large Li + conduction resistance at the LiFePO 4 -water interface, can promote the conduction of Li + between the aqueous phase-LiFePO 4 grains, that is, the overall resistivity of the slurry is reduced, and the working voltage is lower, thereby further reducing the energy consumption of electrochemical salt lake lithium extraction. The lithium-based montmorillonite-coated LiFePO 4 core-shell material prepared by the present disclosure can be widely used in lithium extraction from salt lake brine.
Description
Technical Field
The disclosure relates to the technical field of metallurgy, in particular to a hectorite-coated LiFePO 4 core-shell material, a preparation method and application thereof.
Background
The lithium resource has wide application in the related fields of lithium ion batteries and the like, and along with the rapid development of the lithium ion battery industry, the demand of industrial production for the lithium resource increases more and more rapidly, and even the situation of the supply and the shortage of lithium raw materials has appeared in recent years. How to efficiently and rapidly extract lithium elements from salt lakes has been a scientific problem to be solved. The lithium content in the salt lake is low, the content of other metals such as magnesium is high, and the difficulty of selectively extracting lithium resources from the salt lake is high due to the similar properties of magnesium and lithium. The electrochemical method is used for extracting lithium from salt lake brine, and compared with the traditional methods such as a precipitation method, a calcination leaching method, a carbonization method, a nanofiltration membrane method, a solvent extraction method, an adsorption method and the like, the electrochemical method has the advantages of being cleaner, lower in energy consumption and higher in extraction efficiency.
The electrochemical method for extracting lithium from salt lake brine is based on the principle that a lithium ion sieve can realize oxidation-reduction reaction under different voltages and complete Li + intercalation/deintercalation process. The existing lithium ion sieve base materials include spinel-type LiMn 2O4, layered oxide-type LiMO 2 (M is transition metal ion, namely Ni, co, mn and the like), and polyanion salt LiFePO 4, but the former two are oxides, and usually involve a metal ion dissolution process, so that the service life of the base materials is poor, and LiFePO 4 is most suitable for electrochemical work under the water system condition. LiFePO 4 is used as a lithium ion sieve to perform electrochemical Li + intercalation/deintercalation process, and polarization phenomenon (higher charge-discharge voltage) exists on a Li + intercalation/deintercalation voltage platform due to the problems of electrode-solution interface resistance and electrode resistance.
In view of this, the present disclosure is specifically proposed.
Disclosure of Invention
The invention aims to provide a hectorite coated LiFePO 4 core-shell material, a preparation method and application thereof.
In order to achieve at least one of the above objects of the present disclosure, the following technical solutions may be adopted:
in a first aspect, the present disclosure provides a hectorite-coated LiFePO 4 core-shell material comprising LiFePO 4 as a core layer and a hectorite as a shell layer, the hectorite coating the surface of the LiFePO 4.
In some embodiments of the present disclosure, the mass ratio of LiFePO 4 to the hectorite is 1:0.1% -1%.
In a second aspect, the present disclosure provides a method for preparing a hectorite-coated LiFePO 4 core-shell material, which includes mixing LiFePO 4 and hectorite, adding an alcohol solvent, performing a gel reaction, drying and grinding the obtained gel.
In some embodiments of the present disclosure, the mass ratio of LiFePO 4 to the hectorite is 1:0.1% -1%.
In some embodiments of the present disclosure, the alcohol solvent is added in an amount of 30% -300% of the mass of LiFePO 4.
In some embodiments of the present disclosure, the alcohol solvent comprises any one or a combination of at least two of ethanol, ethylene glycol, polyethylene glycol, propanol, or methanol.
In some embodiments of the present disclosure, the temperature of the gel reaction is 70-100 ℃.
In some embodiments of the present disclosure, the gel is dried at a temperature of 80-120 ℃ for a drying time of 1-18 hours.
In some embodiments of the present disclosure, the method of preparing the hectorite includes mixing and infiltrating montmorillonite with a first lithium solution, followed by filtering and collecting solid powder, and drying.
In some embodiments of the present disclosure, the lithium ion concentration in the first lithium solution is greater than 1g/L.
In some embodiments of the present disclosure, the temperature of the infiltration is 70-100 ℃, and the time of the infiltration is greater than 12 hours.
In some embodiments of the present disclosure, the solid powder is dried at a temperature of 80-120 ℃ for a drying time of 3-12 hours.
In a third aspect, the present disclosure provides an application of the hectorite-coated LiFePO 4 core-shell material according to any one of the foregoing embodiments or the hectorite-coated LiFePO 4 core-shell material obtained by the preparation method of the hectorite-coated LiFePO 4 core-shell material according to any one of the foregoing embodiments in extracting lithium from salt lake brine.
In a fourth aspect, the present disclosure provides a method for extracting lithium from salt lake brine, which comprises taking the hectorite coated LiFePO 4 core-shell material according to any one of the foregoing embodiments or the hectorite coated LiFePO 4 core-shell material prepared by the method for preparing a hectorite coated LiFePO 4 core-shell material according to any one of the foregoing embodiments as a lithium ion sieve, denoted as M-LiFePO 4, and performing delithiation on a portion of the hectorite coated LiFePO 4 core-shell material to prepare a lithium ion-lean sieve, denoted as M-FePO 4;
Adding the M-LiFePO 4 and the M-FePO 4 into an anode chamber and a cathode chamber respectively for electrochemical lithium extraction;
Or alternatively
And respectively coating the M-LiFePO 4 and the M-FePO 4 on an anode plate and a cathode plate to carry out electrochemical lithium extraction.
In some embodiments of the present disclosure, when the M-LiFePO 4 and the M-FePO 4 are added to the anode chamber and the cathode chamber, respectively, for electrochemical lithium extraction, the following operations are included:
mixing the M-LiFePO 4 with a second lithium solution to prepare slurry, placing the slurry in an anode chamber, mixing the M-FePO 4 with brine to prepare slurry, and placing the slurry in a cathode chamber;
And inserting an anode plate into the anode chamber, inserting a cathode plate into the cathode chamber, separating the anode chamber from the cathode chamber by an anion membrane, applying voltage to the anode plate and the cathode plate, carrying out electrochemical lithium extraction, and stopping working when the first cut-off voltage is reached.
In some embodiments of the disclosure, the solid-to-liquid ratio of the mixed slurry of the M-LiFePO 4 and the second lithium solution is 1:1-30, and the solid-to-liquid ratio of the mixed slurry of the M-FePO 4 and the brine is 1:1-30.
In some embodiments of the present disclosure, the anode compartment and the cathode compartment remain agitated during lithium extraction.
In some embodiments of the present disclosure, the stirring speed is 100 to 1000r/min.
In some embodiments of the present disclosure, the second lithium solution has a primary component of LiCl, wherein the lithium concentration is <15g/L.
In some embodiments of the present disclosure, when the M-LiFePO 4 and the M-FePO 4 are respectively coated on the anode plate and the cathode plate to perform electrochemical lithium extraction, the coating thickness of the M-LiFePO 4 is 0.01 to 1cm, and the coating thickness of the M-FePO 4 is 0.01 to 1cm.
In some embodiments of the present disclosure, the anode plate comprises one of a graphite electrode, a platinum metal sheet, or a carbon fiber electrode.
In some embodiments of the present disclosure, the anode plate is a graphite electrode.
In some embodiments of the present disclosure, the cathode plate comprises one of a graphite electrode, a platinum metal sheet, or a carbon fiber electrode.
In some embodiments of the disclosure, the cathode plate is a graphite electrode.
In some embodiments of the disclosure, the method for preparing the M-FePO 4 comprises the steps of mixing the M-LiFePO 4 with lithium-containing liquid to prepare slurry, placing the slurry in an anode chamber, keeping stirring, filling brine into a cathode chamber, respectively inserting an anode plate and a cathode plate into the chamber, electrifying in a constant-current manner until a cut-off voltage is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and obtaining the M-FePO 4.
In some embodiments of the present disclosure, the lithium-containing liquid comprises a lithium solution or brine.
In some embodiments of the present disclosure, the current density at the time of energizing is 10-100 a/m 2.
In some embodiments of the present disclosure, the first cut-off voltage and the second cut-off voltage are both 0.1-0.6 v.
Compared with the prior art, the beneficial effects of the present disclosure include:
according to the lithium-based montmorillonite coated LiFePO 4 core-shell material, the lithium-based montmorillonite is coated on the surface of a LiFePO 4 lithium ion sieve, the obtained product is of a montmorillonite type core-shell structure, and the resistivity of the aqueous slurry prepared by the synthesized core-shell structure material is remarkably reduced. The lithium-based montmorillonite coated LiFePO 4 core-shell material disclosed by the invention is based on the principle that ions between layers in a montmorillonite layered structure are extremely easy to cause the exchange of a matrix, liFePO 4 coated with the lithium-based montmorillonite can generate extremely strong Li + conduction capacity and excellent hydrophilicity, and the ionic conduction resistance of a solid-liquid interface Li + is obviously reduced, so that the lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method has higher ionic conduction capacity (reduced overall resistance), can make up the defect of large LiFePO 4 -water interface Li + conduction resistance, can promote the conduction of Li + between water phase-LiFePO 4 crystal grains, namely, the overall resistivity of slurry is reduced, and the working voltage is lower, so that the lithium extraction energy consumption of an electrochemical salt lake can be further reduced. The lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method can be widely applied to extracting lithium from salt lake brine.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a schematic diagram of an electrochemical lithium extraction device according to the present disclosure;
Fig. 2 is an SEM image of a hectorite-coated LiFePO4 core-shell material provided in example 1 of the present disclosure;
fig. 3 is a graph of voltage-specific capacity of an electrochemical device assembled in example 1 and comparative example 1 of the present disclosure.
Detailed Description
Embodiments of the present disclosure will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The endpoints of the ranges and any values disclosed in this disclosure are not limited to the precise range or value, and such range or value should be understood to encompass values approaching those range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present disclosure provides a hectorite-coated LiFePO 4 core-shell material comprising LiFePO 4 as a core layer and a hectorite as a shell layer, the hectorite being coated on the surface of LiFePO 4. Wherein the mass ratio of LiFePO 4 to hectorite is 1:0.1-1%.
The present disclosure provides a method for preparing a hectorite coated LiFePO 4 core-shell material, comprising the steps of:
S1, preparing hectorite.
And mixing and soaking montmorillonite and the first lithium solution, wherein the soaking temperature is 70-100 ℃, and the soaking time is more than 12 hours. And then filtering and collecting solid powder, and drying for 3-12 hours at the temperature of 80-120 ℃ to obtain the product.
In the disclosure, the concentration of lithium ions in the first lithium solution is greater than 1g/L, otherwise, lithium-based montmorillonite cannot be obtained, the concentration of lithium ions in the first lithium solution can be, for example, any one or any range between 1g/L, 3g/L, 4g/L, 6g/L, 9g/L or 12g/L, in the disclosure, the temperature of the slurry during stirring and infiltration should be kept at 70-100 ℃, for example, any one or any range between 70 ℃, 75 ℃,80 ℃, 85 ℃,90 ℃,95 or 100 ℃, the infiltration temperature in the disclosure is too small to obtain sufficiently lithiated lithium-based montmorillonite, the reaction is not easy to be performed and the lithiation enhancement effect is not significant, the infiltration time should be greater than 12h, the infiltration time is insufficient, and the infiltration time can be, for example, any one or any range between 12h, 14h, 15h, 16h, 18h or 24 h;
In the present disclosure, the drying temperature should be 80 to 120 ℃, for example, may be a range value between any one or any two of 80 ℃,85 ℃,90 ℃,95 ℃,100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, the drying temperature in the present disclosure is too low to be sufficiently dried, the hectorite structure is easily damaged when the temperature is too high, and the drying time should be 3 to 12 hours, for example, may be a range value between any one or any two of 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, the drying time in the present disclosure is too short to be sufficiently dried, and the hectorite structure is easily damaged when the time is too long.
S2, mixing LiFePO 4 and hectorite, adding an alcohol solvent for a gel reaction, drying and grinding the obtained gel.
In the present disclosure, the mass ratio of LiFePO 4 to hectorite is 1:0.1% -1%. In some exemplary but non-limiting embodiments, the mass ratio of LiFePO 4 to hectorite can be, for example, any one or a range of values between 1:0.1%, 1:0.2%, 1:0.3%, 1:0.4%, 1:0.5%, 1:0.6%, 1:0.7%, 1:0.8%, 1:0.9%, or 1:1%, with the addition of alcohol solvent accounting for 30% -300% of the mass of LiFePO 4.
Wherein the alcohol solvent comprises any one or a combination of at least two of ethanol, glycol, polyethylene glycol, propanol or methanol. The reaction temperature of the gel reaction is 70-100 ℃, for example, the reaction temperature can be any one or any range between 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃, the reaction temperature of the gel reaction in the present disclosure is too low to realize the sufficient coating reaction, too high results in uneven coating layer, the drying temperature of the gel is 80-120 ℃, for example, the drying temperature can be any one or any range between 80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, the drying in the present disclosure is not easy to sufficiently dry, the material structure can be damaged if too high, for example, the drying time can be 1-18h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h or any one or any range between two of lithium-coated shells is not easy to damage, and the drying time of the material in the present disclosure is too short, for example, the drying time can be 1-18h, 2h, 3h, 4h, 5h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 16h, 17h or any range between two or any ranges of lithium-coated shells is easy to damage, and the material is not easy to sufficiently dry.
According to the method, the lithium-based montmorillonite is coated on the surface of the LiFePO 4 lithium ion sieve, the obtained product is of a montmorillonite type core-shell structure, and the resistivity of the aqueous slurry prepared from the synthesized core-shell structure material is remarkably reduced.
The lithium-based montmorillonite coated LiFePO 4 core-shell material disclosed by the disclosure is based on the principle that ions between layers in a montmorillonite layered structure are extremely easy to cause the exchange of a matrix, and can generate extremely strong Li + conduction capability and excellent hydrophilicity after being coated with the lithium-based montmorillonite, so that the ion conduction resistance of a solid-liquid interface Li + is obviously reduced, and therefore, the lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the disclosure can promote the conduction of Li + between water phase-LiFePO 4 crystal grains, namely, the overall resistivity of slurry is reduced, the working voltage is lower, and the lithium can be extracted by using salt lake brine with lower energy consumption.
Since Li + is extracted in unit amount (Q is a constant value), the theoretical operating voltage should be as small as possible, where the energy consumption w= UIt =qu= QIR, U denotes the applied voltage (V), I denotes the passing current (a), R is the electrochemical operating system resistance (Ω), t is the operating time (h), and Q is the charge (Ah) required to extract the target amount Li +. When the LiFePO 4 electrode works in aqueous solution, under the given condition of the resistance of LiFePO 4, the method can obviously reduce the ion conduction resistance of the solid-liquid interface Li +, thereby reducing the actual Li + de/intercalation potential and finally realizing the purpose of reducing the total energy consumption.
The lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method can be widely applied to extracting lithium from salt lake brine.
In order to achieve the technical effect, an electrochemical lithium extraction device is firstly built, as shown in fig. 1, and based on the electrochemical lithium extraction device, method verification is carried out, and the method specifically comprises the following steps:
The lithium-based montmorillonite coated LiFePO 4 core-shell material is used as a lithium ion sieve and is marked as M-LiFePO 4, and a part of the lithium-based montmorillonite coated LiFePO 4 core-shell material is subjected to lithium removal to prepare a lean lithium ion sieve and is marked as M-FePO 4.
The method for preparing the M-FePO 4 comprises the steps of mixing M-LiFePO 4 with lithium-containing liquid (lithium solution or brine) to prepare slurry, placing the slurry in an anode chamber, keeping stirring, filling the brine in a cathode chamber, respectively inserting an anode plate and a cathode plate into the chamber, electrifying in a constant-current mode, wherein the current density is 10-100A/M 2 when the current is electrified until the current reaches a cut-off voltage of 0.1-0.6V, taking out the slurry from the anode chamber, filtering and collecting solids, and obtaining the M-FePO 4.
Wherein in some exemplary but non-limiting embodiments, the current density upon energization is a range of values between either or both of 10A/m2、20A/m2、30A/m2、40A/m2、50A/m2、60A/m2、70A/m2、80A/m2、90A/m2 or 100A/m 2, the cutoff voltage may be, for example, a range of values between either or both of 0.1V, 0.2V, 0.3V, 0.4V, 0.5V, or 0.6V.
The method for extracting lithium from salt lake brine comprises the following two operations:
(1) And respectively adding M-LiFePO 4 and M-FePO 4 into the anode chamber and the cathode chamber to carry out electrochemical lithium extraction.
(2) M-LiFePO 4 and M-FePO 4 are respectively coated on the anode plate and the cathode plate for electrochemical lithium extraction.
Wherein, in the scheme (1), the following operations are included:
mixing M-LiFePO 4 with a second lithium solution to prepare slurry, placing the slurry in an anode chamber, mixing M-FePO 4 with brine to prepare slurry, placing the slurry in a cathode chamber, wherein the main component of the second lithium solution is LiCl, and the lithium concentration is less than 15g/L. The solid-to-liquid ratio of the mixed pulping of the M-LiFePO 4 and the second lithium solution is 1:1-30, and the solid-to-liquid ratio of the mixed pulping of the M-FePO 4 and the brine is 1:1-30. Too small a solid-to-liquid ratio may not meet the requirement of adequate material-to-plate contact, and too large a solid-to-liquid ratio may result in too low current efficiency.
The anode plate is inserted into the anode chamber, the cathode plate is inserted into the cathode chamber, the anode chamber and the cathode chamber are separated by an anion membrane, voltage is applied to the anode plate and the cathode plate, electrochemical lithium extraction is carried out, and the operation is stopped when the cut-off voltage (0.1-0.6V) is reached.
The anode and cathode compartments remain agitated during the lithium extraction process. The stirring speed is 100-1000r/min, and can be, for example, any one or any range value between 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min or 1000 r/min.
In the scheme (2):
the coating thickness of M-LiFePO 4 is 0.01-1 cm, and the coating thickness of M-FePO 4 is 0.01-1 cm.
The anode plate and the cathode plate used in either the embodiment (1) or the embodiment (2) may be commonly used, and specifically, the anode plate includes one of a graphite electrode, a platinum metal sheet, or a carbon fiber electrode, and preferably, the anode plate is a graphite electrode. The cathode plate comprises one of a graphite electrode, a platinum metal sheet or a carbon fiber electrode, preferably the cathode plate is a graphite electrode.
The lithium-based montmorillonite coated LiFePO 4 core-shell material provided by the disclosure has higher ion conduction capacity (reduces overall resistance), can make up for the defect of large conduction resistance of LiFePO 4 -water interface Li +, and realizes the effect of obviously reducing the electrochemical lithium extraction working voltage, thereby further reducing the lithium extraction energy consumption of the electrochemical salt lake.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
The concentrations of the main elements in the salt lake brine used in the examples and the comparative examples provided in the present disclosure are all referred to table 1:
TABLE 1 concentration of major elements in salt lake brine
Example 1
S1, preparing hectorite, namely taking commercial montmorillonite as a raw material, soaking the commercial montmorillonite into a solution with the lithium concentration of 3g/L, preserving heat, stirring and soaking for 16 hours at 80 ℃, then filtering and collecting the obtained solid powder, and drying for 6 hours at 100 ℃ to obtain the hectorite;
S2, preparing a lithium-based montmorillonite coated LiFePO 4 core-shell material, namely mixing the lithium-based montmorillonite obtained in the step 1 with commercial LiFePO 4 according to the mass ratio of 0.2%, adding ethanol according to 30% of the mass of LiFePO 4, performing sol-gel reaction at 100 ℃, drying at 80 ℃ for 18 hours after the gel is evaporated to dryness, and grinding uniformly to obtain the lithium-based montmorillonite coated LiFePO 4 core-shell material shown in figure 2 (called M-LiFePO 4 for short);
S3, preparing a lean lithium ion sieve material, namely mixing M-LiFePO 4 prepared in the step S2 with lithium chloride solution with lithium concentration of 1g/L according to a liquid-solid ratio of 2:1, pulping, placing the mixture in an anode chamber, stirring the mixture at a speed of 100r/min, filling brine in a cathode chamber, respectively inserting a graphite electrode and a graphite electrode into the chamber as an anode plate and a cathode plate, electrifying the mixture in a constant-current mode of 20A/M 2 until a cut-off voltage of 0.3V is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and naming the slurry as the lean lithium ion sieve material (M-FePO 4);
And S4, electrochemically extracting lithium, namely mixing M-LiFePO 4 in the step S2 with lithium chloride solution with lithium concentration of 5g/L according to a liquid-solid ratio of 5:1, pulping, placing the mixed pulp in an anode chamber, mixing M-FePO 4 in the step S3 with brine according to a liquid-solid ratio of 5:1, placing the mixed pulp in a cathode chamber, inserting graphite electrodes and graphite electrodes into the chambers to serve as anode plates and cathode plates respectively, stirring the two chambers at 100r/min, separating the two chambers by an anion membrane, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction according to 20A/M 2, stopping working when the cut-off voltage reaches 0.3V, extracting Li + in the brine by M-FePO 4, releasing the Li-rich solution in the anode chamber, and filtering and collecting the solution in the anode chamber.
Example 2
S1, preparing hectorite, namely taking commercial montmorillonite as a raw material, soaking the commercial montmorillonite into a solution with the lithium concentration of 6g/L, preserving heat, stirring and soaking for 14 hours at the temperature of 70 ℃, then filtering and collecting the obtained solid powder, and drying for 12 hours at the temperature of 80 ℃ to obtain the hectorite;
S2, preparing a lithium-based montmorillonite coated LiFePO 4 core-shell material, namely mixing the lithium-based montmorillonite obtained in the step 1 with commercial LiFePO 4 according to the mass ratio of 0.1%, adding polyethylene glycol according to 300% of the mass of LiFePO 4 to carry out sol-gel reaction at 80 ℃, drying the gel at 120 ℃ for 1h after the gel is evaporated to dryness, and grinding uniformly to obtain the lithium-based montmorillonite coated LiFePO 4 core-shell material (M-LiFePO 4 for short);
S3, preparing a lean lithium ion sieve material, namely pulping the M-LiFePO 4 prepared in the step S2 and a lithium chloride solution with the lithium concentration of 2g/L according to a liquid-solid ratio of 6:1, placing the mixture in an anode chamber, stirring the mixture at 1000r/min, filling brine in the cathode chamber, respectively inserting a platinum metal sheet and a platinum metal sheet into the chamber as an anode plate and a cathode plate, electrifying the mixture in a constant-current mode of 10A/M 2 until a cut-off voltage of 0.6V is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and naming the slurry as the lean lithium ion sieve material (M-FePO 4);
And S4, electrochemically extracting lithium, namely mixing M-LiFePO 4 in the step S2 with lithium chloride solution with lithium concentration of 1g/L according to a liquid-solid ratio of 5:1, pulping, placing in an anode chamber, mixing M-FePO 4 in the step S3 with brine according to a liquid-solid ratio of 5:1, placing in a cathode chamber, inserting graphite electrodes and platinum metal sheets into the chambers to serve as anode plates and cathode plates respectively, stirring the two chambers at 400r/min, separating the two chambers by anion membranes, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction according to 10A/M 2, stopping working when a cut-off voltage of 0.6V is reached, extracting Li + in the brine by M-FePO 4, releasing the Li-rich solution in the anode chamber, and filtering and collecting the anode chamber solution to obtain the lithium-rich solution.
Example 3
S1, preparing hectorite, namely taking commercial montmorillonite as a raw material, soaking the commercial montmorillonite into a solution with the lithium concentration of 1g/L, keeping the temperature at 100 ℃, stirring and soaking for 24 hours, then filtering and collecting the obtained solid powder, and drying for 9 hours at 80 ℃ to obtain the hectorite;
S2, preparing a lithium-based montmorillonite coated LiFePO 4 core-shell material, namely mixing the lithium-based montmorillonite obtained in the step 1 with commercial LiFePO 4 according to the mass ratio of 0.6%, adding ethylene glycol according to 200% of the mass of LiFePO 4 to carry out sol-gel reaction at 70 ℃, drying the gel at 100 ℃ for 6 hours after the gel is evaporated to dryness, and grinding uniformly to obtain the lithium-based montmorillonite coated LiFePO 4 core-shell material (M-LiFePO 4 for short);
s3, preparing a lean lithium ion sieve material, namely pulping the M-LiFePO 4 prepared in the step S2 and a lithium chloride solution with the lithium concentration of 6g/L according to a liquid-solid ratio of 10:1, placing the mixture in an anode chamber, stirring the mixture at 200r/min, filling brine in the cathode chamber, respectively inserting a carbon fiber electrode plate and a carbon fiber electrode plate into the chamber as an anode plate and a cathode plate, electrifying the chamber in a constant current mode of 100A/M 2 until the cutoff voltage of 0.1V is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and obtaining the lean lithium ion sieve material (M-FePO 4);
And S4, electrochemically extracting lithium, namely mixing M-LiFePO 4 in the step S2 with lithium chloride solution with the lithium concentration of 3g/L according to a liquid-solid ratio of 20:1, pulping, placing the mixed pulp in an anode chamber, mixing M-FePO 4 in the step S3 with brine according to a liquid-solid ratio of 20:1, placing the mixed pulp in a cathode chamber, inserting a carbon fiber electrode plate and a carbon fiber electrode plate into the chamber, respectively serving as an anode plate and a cathode plate, stirring the two chambers at 600r/min, separating the two chambers by an anion membrane, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction according to 100A/M 2, stopping the operation when the cut-off voltage of 0.1V is reached, extracting Li + in the brine by M-FePO 4, releasing the solution in the anode chamber, and filtering and collecting the anode chamber solution to obtain the lithium-enriched solution.
Example 4
S1, preparing hectorite, namely taking commercial montmorillonite as a raw material, soaking the commercial montmorillonite into a solution with the lithium concentration of 12g/L, preserving heat at 90 ℃, stirring and soaking for 12 hours, then filtering and collecting the obtained solid powder, and drying for 9 hours at 90 ℃ to obtain the hectorite;
S2, preparing a lithium-based montmorillonite coated LiFePO 4 core-shell material, namely mixing the lithium-based montmorillonite obtained in the step 1 with commercial LiFePO 4 according to the mass ratio of 0.6%, adding propanol according to 150% of the mass of LiFePO 4 to perform sol-gel reaction at 100 ℃, drying the gel at 90 ℃ for 9 hours after the gel is evaporated to dryness, and grinding uniformly to obtain the lithium-based montmorillonite coated LiFePO 4 core-shell material (M-LiFePO 4 for short);
s3, preparing a lean lithium ion sieve material, namely pulping the M-LiFePO 4 prepared in the step S2 and a lithium chloride solution with the lithium concentration of 9g/L according to a liquid-solid ratio of 12:1, placing the mixture in an anode chamber, stirring the mixture at 100r/min, filling brine in a cathode chamber, respectively inserting a graphite electrode and a graphite electrode into the chamber as an anode plate and a cathode plate, electrifying the chamber in a 60A/M 2 constant-current mode until a cut-off voltage of 0.4V is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and naming the slurry as the lean lithium ion sieve material (M-FePO 4);
And S4, electrochemically extracting lithium, namely mixing M-LiFePO 4 in the step S2 with lithium chloride solution with the lithium concentration of 10g/L according to the liquid-solid ratio of 10:1, pulping, placing the mixed pulp in an anode chamber, mixing M-FePO 4 in the step S3 with brine according to the liquid-solid ratio of 10:1, placing the mixed pulp in a cathode chamber, inserting graphite electrodes and graphite electrodes into the chambers to serve as anode plates and cathode plates respectively, stirring the two chambers at 900r/min, separating the two chambers by an anion membrane, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction according to 30A/M 2, stopping the operation when the cut-off voltage reaches 0.6V, extracting Li + in the brine by M-FePO 4, releasing the Li-rich solution in the anode chamber, and filtering and collecting the Li-rich solution in the anode chamber.
Example 5
S1, taking commercial montmorillonite as a raw material, soaking the commercial montmorillonite into a solution with the lithium concentration of 4g/L, keeping the temperature at 90 ℃, stirring and soaking for 18 hours, then filtering and collecting the obtained solid powder, and drying for 3 hours at 120 ℃ to obtain the hectorite;
s2, preparing a hectorite coated LiFePO 4 core-shell material, namely mixing the hectorite obtained in the step 1 with commercial LiFePO 4 according to the mass ratio of 1%, adding methanol according to 250% of the mass of LiFePO 4 to carry out sol-gel reaction at 90 ℃, drying the gel at 110 ℃ for 3 hours after the gel is evaporated to dryness, and grinding uniformly to obtain the hectorite coated LiFePO 4 core-shell material (called M-LiFePO 4 for short);
s3, preparing a lean lithium ion sieve material, namely mixing M-LiFePO 4 prepared in the step S2 with lithium chloride solution with the lithium concentration of 12g/L according to a liquid-solid ratio of 16:1, pulping, placing the mixture in an anode chamber, stirring the mixture at 300r/min, filling brine in a cathode chamber, respectively inserting a graphite electrode and a graphite electrode into the chamber as an anode plate and a cathode plate, electrifying the chamber in a constant-current mode of 30A/M 2 until a cut-off voltage of 0.6V is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and naming the slurry as the lean lithium ion sieve material (M-FePO 4);
And S4, electrochemically extracting lithium, namely mixing M-LiFePO 4 in the step S2 with lithium chloride solution with the lithium concentration of 12g/L according to the liquid-solid ratio of 2:1, pulping, placing the mixed pulp in an anode chamber, mixing M-FePO 4 in the step S3 with brine according to the liquid-solid ratio of 2:1, placing the mixed pulp in a cathode chamber, inserting graphite electrodes and graphite electrodes into the chambers to serve as anode plates and cathode plates respectively, stirring the two chambers at 1000r/min, separating the two chambers by an anion membrane, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction according to 100A/M 2, stopping working when the cut-off voltage reaches 0.6V, extracting Li + in the brine by M-FePO 4, releasing the Li-rich solution in the anode chamber, and filtering and collecting the Li-rich solution in the anode chamber.
Example 6
S1, taking commercial montmorillonite as a raw material, soaking the commercial montmorillonite into a solution with the lithium concentration of 9g/L, maintaining the temperature at 100 ℃, stirring and soaking for 15 hours, filtering and collecting the obtained solid powder, and drying for 12 hours at 120 ℃ to obtain the hectorite;
s2, preparing a lithium-based montmorillonite coated LiFePO 4 core-shell material, namely mixing the lithium-based montmorillonite obtained in the step 1 with commercial LiFePO 4 according to the mass ratio of 0.3%, adding ethanol according to 180% of the mass of LiFePO 4 to carry out sol-gel reaction at 85 ℃, drying the gel at 90 ℃ for 12 hours after the gel is evaporated to dryness, and grinding uniformly to obtain the lithium-based montmorillonite coated LiFePO 4 core-shell material (M-LiFePO 4 for short);
S3, preparing a lean lithium ion sieve material, namely pulping the M-LiFePO 4 prepared in the step S2 and a lithium chloride solution with the lithium concentration of 15g/L according to a liquid-solid ratio of 20:1, placing the mixture in an anode chamber, stirring the mixture at 500r/min, filling brine in the cathode chamber, respectively inserting a platinum metal sheet and a platinum metal sheet into the chamber as an anode plate and a cathode plate, electrifying the mixture in a constant-current mode of 50A/M 2 until a cut-off voltage of 0.3V is reached, taking out the slurry from the anode chamber, filtering and collecting solids, and naming the slurry as the lean lithium ion sieve material (M-FePO 4);
And S4, electrochemically extracting lithium, namely mixing M-LiFePO 4 in the step S2 with lithium chloride solution with the lithium concentration of 15g/L according to the liquid-solid ratio of 9:1, pulping, placing in an anode chamber, mixing M-FePO 4 in the step S3 with brine according to the liquid-solid ratio of 9:1, placing in a cathode chamber, inserting platinum metal sheets into the chambers, respectively serving as an anode plate and a cathode plate, stirring the two chambers at 300r/min, separating the two chambers by an anion membrane, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction according to 60A/M 2, stopping working when the cut-off voltage of 0.1V is reached, extracting Li + in the brine by M-FePO 4, releasing the Li-FePO in the anode chamber, and filtering and collecting the anode chamber solution to obtain the lithium-enriched solution.
Example 7
Steps S1-S3 are the same as in example 1.
And S4, electrochemically extracting lithium, namely coating M-LiFePO 4 in the step S2 on an anode plate, wherein the coating thickness is 0.1cm, coating M-FePO 4 in the step S3 on a cathode plate, wherein the coating thickness is 0.1cm, inserting the anode plate coated with M-LiFePO 4 and the cathode plate coated with M-FePO 4 into a cavity, simultaneously introducing a lithium solution into the anode chamber, introducing brine into the cathode chamber, keeping the two cavities to stir at 100r/min, separating the middle part by an anion membrane, switching on an external power supply for the cathode and the anode, performing electrochemical lithium extraction operation according to 20A/M 2, stopping operation when the cut-off voltage reaches 0.3V, extracting Li + in the brine by M-FePO 4, releasing the Li + in the anode chamber, and filtering and collecting the anode chamber solution to obtain the lithium-rich liquid.
Comparative example 1
The difference from example 1 is that the commercial LiFePO 4 material was used directly to make a lithium-ion lean sieve without performing step S1 and step S2, followed by electrochemical lithium extraction.
Comparative example 2
The difference from example 1 is that step S1 does not lithiate the commercial montmorillonite material, directly coats the LiFePO 4 material with the commercial montmorillonite, and then carries out electrochemical lithium extraction.
Comparative example 3
The difference from example 1 is that the infiltration temperature in step S1 is too high and the infiltration is stirred at 120℃for 16h.
Comparative example 4
The difference from example 1 is that the drying temperature in step S1 is too high and it is dried at 150℃for 6h.
Comparative example 5
The difference from example 1 is that the mass ratio of hectorite to LiFePO 4 material used in step S2 is too small, mixing is performed at 0.01%, and then the other steps are performed for electrochemical lithium extraction.
Comparative example 6
The difference from example 1 is that the mass ratio of hectorite to LiFePO 4 material used in step S2 is too large, mixing is performed at 2% and then the other steps are performed for electrochemical lithium extraction.
Comparative example 7
The difference from example 1 is that the ethanol used in step S2 is replaced with pure water, and then other steps are performed to perform electrochemical lithium extraction.
Comparative example 8
The difference from example 1 is that step S1 is not performed, while the hectorite used in step S2 is replaced with a lepidolite mineral.
Comparative example 9
The difference from example 1 is that LiFePO 4 used in step S2 is replaced with LiCoO 2.
Experimental example 1
Slurry conductivity in pulping the lithium ion sieves provided in examples 1 to 7 and comparative examples 1 to 9 above, the method for detecting slurry conductivity included a slurry resistance test system. The test results are shown in Table 2.
TABLE 2 statistical table of slurry conductivities for various examples of lithium ion sieves in pulping
| Example | Slurry conductivity (S/m) |
| Example 1 | 0.92 |
| Example 2 | 0.79 |
| Example 3 | 0.84 |
| Example 4 | 0.75 |
| Example 5 | 0.88 |
| Example 6 | 0.91 |
| Example 7 | 0.78 |
| Comparative example 1 | 0.21 |
| Comparative example 2 | 0.25 |
| Comparative example 3 | 0.27 |
| Comparative example 4 | 0.28 |
| Comparative example 5 | 0.30 |
| Comparative example 6 | 0.31 |
| Comparative example 7 | 0.26 |
| Comparative example 8 | 0.29 |
| Comparative example 9 | 0.62 |
As can be seen from the above table, in comparative example 1, the LiFePO 4 material was directly used for preparing the lithium ion lean sieve, which was not coated, and the slurry conductivity thereof was significantly lower than that of example 1 and other comparative examples, and in comparative example 2, the LiFePO 4 material was directly coated with montmorillonite, at this time, since the montmorillonite was not coated with lithium, the Li + conductivity and hydrophilicity thereof were significantly reduced, and thus the conductivity of the prepared slurry thereof was slightly higher than that of comparative example 1, but still significantly lower than that of example 1. As can be seen from the data of comparative examples 3-6, when the parameters such as the mass ratio of the wet, dry and coating are beyond the scope of the present disclosure, it will result in a significant decrease in the conductivity of the slurry, while as can be seen from the data of comparative example 7, using pure water instead of ethanol, pure water is not easily volatilized under the same conditions, resulting in an excessively large water content in the gel, which is detrimental to the subsequent drying, and thus results in a significantly lower conductivity of comparative example 7 than example 1, which is sufficient to demonstrate that not all solvents can be used to mix LiFePO 4 and hectorite. As can be seen from the data of comparative example 8, when other lithium-containing minerals were selected, their conductivity remained significantly lower than that of example 1, because of the higher ionic conductivity of hectorite. As can be seen from the data of comparative example 9, when other positive electrode materials were selected as cores, the slurry conductivity was poor, mainly due to the high turn-on onset voltage of LiCoO 2, which resulted in a conductivity that was still significantly lower than that of example 1. Moreover, the lithium cobaltate dissolution rate is high, and more than 30% of Co 2+ and Li + may be dissolved out after the power is turned on. Therefore, the conductivity of the slurry prepared by coating the LiFePO 4 core-shell material with the hectorite provided by the embodiment of the disclosure is significantly higher than that of other LiFePO 4 slurries of comparative examples.
Experimental example 2
The lithium ion sieves provided in examples 1 to 7 and comparative examples 1 to 9 were tested for medium charge and discharge voltage and power consumption required for extracting 1kg of lithium when electrochemically extracting lithium, and the test results are shown in fig. 3 and table 3:
TABLE 3 statistics of charge and discharge Medium pressure, specific Capacity and consumption of 1kg lithium
It can be seen from the above table that to achieve the same level of specific capacity (80 mAh/g), the examples all have lower charge-discharge medium voltage relative to the comparative examples, where the examples are hectorite coated optimized and the comparative examples are uncoated or coated with other materials, so that the hectorite coated LiFePO 4 core-shell material has lower energy consumption per mass of lithium extracted.
In summary, according to the hectorite-coated LiFePO 4 core-shell material provided by the disclosure, the hectorite is coated on the surface of a LiFePO 4 lithium ion sieve, the obtained product is of a montmorillonite-type core-shell structure, and the resistivity of the aqueous slurry prepared by the synthesized core-shell structure material is remarkably reduced. The lithium-based montmorillonite coated LiFePO 4 core-shell material disclosed by the invention is based on the principle that ions between layers in a montmorillonite layered structure are extremely easy to cause the exchange of a matrix, liFePO 4 coated with the lithium-based montmorillonite can generate extremely strong Li + conduction capacity and excellent hydrophilicity, and the ionic conduction resistance of a solid-liquid interface Li + is obviously reduced, so that the lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method has higher ionic conduction capacity (reduced overall resistance), can make up the defect of large LiFePO 4 -water interface Li + conduction resistance, can promote the conduction of Li + between water phase-LiFePO 4 crystal grains, namely, the overall resistivity of slurry is reduced, and the working voltage is lower, so that the lithium extraction energy consumption of an electrochemical salt lake can be further reduced. The lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method can be widely applied to extracting lithium from salt lake brine.
The above describes in detail the optional embodiments of the present disclosure, but the present disclosure is not limited thereto. Within the scope of the technical idea of the present disclosure, various simple modifications may be made to the technical solution of the present disclosure, including that each technical feature is combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosure of the present disclosure, which falls within the protection scope of the present disclosure.
Industrial applicability
According to the lithium-based montmorillonite coated LiFePO 4 core-shell material, the lithium-based montmorillonite is coated on the surface of a LiFePO 4 lithium ion sieve, the obtained product is of a montmorillonite type core-shell structure, and the resistivity of the aqueous slurry prepared by the synthesized core-shell structure material is remarkably reduced. The lithium-based montmorillonite coated LiFePO 4 core-shell material disclosed by the invention is based on the principle that ions between layers in a montmorillonite layered structure are extremely easy to cause the exchange of a matrix, liFePO 4 coated with the lithium-based montmorillonite can generate extremely strong Li + conduction capacity and excellent hydrophilicity, and the ionic conduction resistance of a solid-liquid interface Li + is obviously reduced, so that the lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method has higher ionic conduction capacity (reduced overall resistance), can make up the defect of large LiFePO 4 -water interface Li + conduction resistance, can promote the conduction of Li + between water phase-LiFePO 4 crystal grains, namely, the overall resistivity of slurry is reduced, and the working voltage is lower, so that the lithium extraction energy consumption of an electrochemical salt lake can be further reduced. The lithium-based montmorillonite coated LiFePO 4 core-shell material prepared by the method can be widely applied to extracting lithium from salt lake brine.
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