CN113969359B - Preparation method of membrane electrode for extracting lithium from salt lake, membrane electrode, preparation method of membrane capacitance unit and application of membrane capacitance unit - Google Patents
Preparation method of membrane electrode for extracting lithium from salt lake, membrane electrode, preparation method of membrane capacitance unit and application of membrane capacitance unit Download PDFInfo
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Abstract
The invention relates to a membrane electrode preparation method for extracting lithium from salt lake, a membrane electrode, a membrane capacitor unit preparation method and application thereof; including the formation of LiMnO 2 Powder roasting to obtain spinel phase Li 1.6 Mn 1.6 O 4 A precursor (LMO); mixing Li 1.6 Mn 1.6 O 4 Adding the precursor into a buffer solution, and adding dopamine hydrochloride to obtain a dopamine-coated LMO material; calcining the dopamine-coated LMO material to obtain a carbon-coated LMO material; processing the LMO material coated by the carbon layer by hydrochloric acid, adding the LMO material into a buffer solution, and adding dopamine hydrochloride to obtain a dopamine-modified active electrode material; adding the dopamine modified active electrode material and polyvinylidene fluoride into N, N-dimethylacetamide, and stirring to obtain active electrode slurry; and coating the active electrode slurry on a graphite plate, drying the graphite plate coated with the active electrode slurry in a vacuum drying oven, and pressing the graphite plate to obtain the membrane electrode.
Description
Technical Field
The invention relates to the technical field of lithium extraction in salt lakes, in particular to a preparation method of a membrane electrode, a preparation method of a membrane capacitor unit and application of the membrane electrode.
Background
Lithium is the first and lightest metal element of the periodic table and is called "metallic monosodium glutamate". It is widely used in various fields such as glass enamel, aerospace, medicine and nuclear power, and particularly, batteries account for more than half of the lithium resource terminal market. With the rapid growth of lithium ion batteries in electric vehicles and portable electronic products, the market demand for lithium resources is expected to grow at a rate of 20% per year. The united states geological survey bureau (USGS) reports in 2021 that the global lithium resource amount is about 8000 ten thousand tons, the lithium reserve is 2100 ten thousand tons, the lithium resource in salt lake brine accounts for about 60% of the global total reserve, the lithium resource reserve which has been proved in China is 510 ten thousand tons, and the lithium resource in salt lake brine accounts for 71%. Domestic salt lakes containing lithium resources are mainly concentrated in Qinghai-Tibet plateau and Tibet regions, and domestic salt lake brine is mainly in a sulfate type and a chloride type. Infrastructure shortage at the position of the Tibet salt lake brine mining area is inconvenient to traffic and poor in development condition, and meanwhile, the development difficulty of lithium resources in the Tibet area is large due to the fact that the ecosystem of the Tibet area is fragile and the like. The brine in the Qinghai area has rich lithium resources, but the salt lake has low lithium ion concentration and more impurity ions, so the extraction difficulty is high, and the capacity of extracting lithium ions is low.
At present, aiming at the development of lithium resources in salt lakes, a membrane separation technology is considered to be a promising and environment-friendly lithium recovery and substitution method, because the method has the advantages of high energy efficiency and easiness in operation in a continuous process, a nanofiltration membrane can extract monovalent ions based on steric hindrance and the Tangnan effect, but in actual operation, the nanofiltration membrane cannot completely separate lithium, magnesium and Li + For Mg 2+ The separation factor of (2.6) to (10.4) and the membrane fouling phenomenon occurs over a certain period of use, which reduces the separation efficiency. The electrodialysis is to realize Li by utilizing different diffusion speeds of monovalent cation and divalent cation passing through an ion exchange membrane under the action of an electric field + With Mg 2+ The separation and electrodialysis operation process has low energy consumption and good lithium recovery rate for cations with different valence states>95% but in the presence of monovalent ions (Na) + 、K + 、Li + ) Lithium cannot be extracted efficiently. Introducing bipolar membrane into electrodialysis system, and inducing water decomposition into H under electric field + And OH - Is ionized, and Li is added + LiOH is recovered from salt lake brine, but the bipolar membrane can only concentrate and purify the solution and cannot separate monovalent ions. The supported liquid membrane selectively transmits ions through a solvent immersed in the membrane, and the recovery rate is good in recovery performance>95%, but the supported liquid film organic solvent is liable to leak and requires actual desorption using chemistry. The membrane capacitance method selectively separates monovalent ions by using a permselective exchange membrane through electrostatic attraction, uses an ion sieve as an active electrode material, is applied to extracting lithium from salt lake brine, avoids using acid, and has the advantage of environmental protection. The manganese ion sieve is mainly used at presentFor active electrode material, the lithium extraction capacity is improved by improving the process method, lattice doping and other methods, but the adsorption capacity is still small (<20 mg/g) and a low extraction yield of (<15%) of the cells.
The patent (CN 113265538A) discloses a preparation method of a high-conductivity porous electrode for extracting lithium from a salt lake, wherein inorganic nano particles and polar hydrophilic high-molecular organic matter are adopted to carry out blending modification on a binder in the electrode preparation process, so that the hydrophilicity of the binder is improved; and in the preparation process of the electrode slurry, an inorganic pore-forming agent is added, so that the electrode forms holes, and the mass transfer effect of the solution in the electrode is improved. The extraction capacity of the modified lithium manganate electrode used in the technology in a 1.69g/L solution with a high lithium concentration only reaches 20.3mg/g, and is low.
The patent (CN 113278820A) discloses an electrode material for extracting lithium from a salt lake and a preparation method thereof, wherein the lithium manganate electrode material is coated and modified by graphene oxide and lithium metatitanate, poly-dopamine coating modification is further carried out on the surface of the material, and the modified electrode material is used for Li extraction from Li based on an electrochemical de-intercalation method + Extracting lithium from solution with concentration of 710mg/L, and extracting the extracted Li + The concentration is reduced to 110mg/L, the calculated adsorption capacity is only 7.5mg/g, and the adsorption capacity is lower.
The patent (CN 113293289A) discloses a preparation method of a hydrophilic lithium extraction electrode, wherein a nano metal oxide is used for carrying out hydrophilic modification on an electrode powder material to obtain a nano metal oxide modified electrode powder material to prepare the hydrophilic lithium extraction electrode, and the modified lithium manganate electrode is subjected to Li + The extraction capacity of brine with the concentration of 1.89g/L is 17.8mg/g, and the extraction capacity is lower.
Manganese ion sieves researched more at the present stage mainly comprise LiMn 2 O 4 、Li1.33Mn1.6 7 O 4 、Li 1.6 Mn 1.6 O 4 Etc. with LiMn 2 O 4 (50.4 mg/g) and Li 1.33 Mn 1.67 O 4 (39.6 mg/g) ion sieve prepared from Li as a precursor 1.6 Mn 1.6 O 4 Ion sieves prepared for precursors have higher theoretical capacities: (72.9 mg/g). However, in the process of lithium desorption, manganese dissolution loss is easy to occur in the manganese ion sieve, and the conductivity of the material is low.
Therefore, in order to solve the above problems, the present invention urgently needs to provide a membrane electrode preparation method, a membrane electrode, a membrane capacitor unit preparation method and applications thereof for extracting lithium from salt lakes.
Disclosure of Invention
The invention aims to provide a design of a membrane electrode preparation method for extracting lithium from salt lake, which aims to solve the problem that the existing electrode material for extracting lithium from salt lake in the prior art extracts Li + The extraction capacity of (2) is low.
The invention provides a preparation method of a membrane electrode for extracting lithium from a salt lake, which comprises the following preparation steps:
reacting LiOH & H 2 O and Mn 2 O 3 Mixing the powders in proportion, adding water, putting the mixture into a reaction kettle, carrying out hydrothermal reaction, aging, filtering, washing and drying to obtain grayish green LiMnO 2 Powder;
mixing LiMnO 2 The powder is calcined at high temperature to obtain spinel phase Li 1.6 Mn 1.6 O 4 A precursor (LMO);
mixing Li 1.6 Mn 1.6 O 4 Adding a precursor (LMO) into tris buffer solution with the pH value of 8.5, adding dopamine hydrochloride after ultrasonic dispersion, stirring and washing to obtain a dopamine-coated LMO material (PDA @ LMO);
calcining a dopamine-coated LMO material (PDA @ LMO) at a high temperature to obtain a carbon-coated LMO material (C @ LMO);
treating an LMO material (C @ LMO) coated by a carbon layer by using hydrochloric acid, adding the LMO material into a tris buffer solution with the pH value of 8.5, performing ultrasonic dispersion, adding dopamine hydrochloride, stirring, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
adding a dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain active electrode slurry;
coating the active electrode slurry on a graphite plate, drying the graphite plate coated with the active electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the active electrode slurry to obtain a membrane electrode (pD-C @ HMO).
Preferably, liOH. H is added in a molar ratio of Li/Mn of (2-5): 1 2 O and Mn 2 O 3 Mixing the powder; liOH. H 2 O and Mn 2 O 3 The powder is subjected to hydrothermal reaction for 8-12h at the temperature of 150-250 ℃.
Preferably, liMnO is added under an air atmosphere 2 The powder is roasted for 2-6h at 350-450 ℃.
Preferably, li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) to the tris buffer solution is 1 (1-2.5).
Preferably, the PDA @ LMO obtained is calcined in a muffle furnace at 300-400 ℃ for 1-3h under air atmosphere.
Preferably, C @ LMO is treated with 0.5-1mol/L HCl for 12-16h at room temperature;
adding 0.5-1.0g of C @ LMO into 10-100mL of tris buffer solution, performing dispersion ultrasonic treatment for 30-60min, adding 0.02-0.1g of dopamine hydrochloride, stirring for 1-7h at room temperature in an open air, filtering, and washing to obtain the dopamine modified active electrode material (pD-C @ HMO).
Preferably, manganese carbonate (MnCO) 3 ) Placing the mixture in a muffle furnace, roasting the mixture for 3 to 6 hours at the temperature of between 600 and 1000 ℃ to obtain black Mn 2 O 3 And (3) powder.
The invention also provides a membrane electrode obtained based on the membrane electrode preparation method for extracting lithium from the salt lake.
The invention also provides a preparation method of the film capacitor unit, which comprises the following preparation steps:
adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
and assembling the membrane electrode and the activated carbon counter electrode according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain the membrane capacitance unit.
The invention also provides an application of the membrane capacitor unit in lithium extraction in salt lakes.
The invention also provides application of the membrane capacitor unit obtained based on the preparation method of the membrane capacitor unit in lithium extraction in salt lakes.
The invention uses carbon layer to coat, inhibits manganese dissolution loss, improves the conductivity and electrochemical activity of the material, and utilizes simple coating of dopamine on Li 1.6 Mn 1.6 O 4 The solid surface is carbonized to form a nano-scale coating layer with adjustable thickness, so that the manganese dissolution loss is reduced, meanwhile, the hydrophilicity of the material is improved by utilizing the aggregation of dopamine on the surface, the capability of transmitting lithium ions is improved, and the lithium extraction performance of the material is obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD diagram comparing a membrane electrode material pD-C @ HMO of the present invention with a Li1.6Mn1.6O4 standard card; wherein: a-membrane electrode material pD-C @ HMO, b-Li1.6Mn1.6O4 standard card PDF #52-1841;
FIG. 2 is a TEM image of pD-C @ HMO described in the present invention;
FIG. 3 is an HRTEM image of pD-C @ HMO as described in the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The invention provides a preparation method of a membrane electrode for extracting lithium from a salt lake, which comprises the following preparation steps:
s1) reacting LiOH & H 2 O and Mn 2 O 3 Mixing the powders in proportion, adding water, putting the mixture into a reaction kettle, carrying out hydrothermal reaction, aging, filtering, washing and drying to obtain grayish green LiMnO 2 Powder;
s2) mixing LiMnO 2 The powder is calcined at high temperature to obtain spinel phase Li 1.6 Mn 1.6 O 4 A precursor (LMO);
s3) reacting Li 1.6 Mn 1.6 O 4 Adding a precursor (LMO) into tris buffer solution with the pH value of 8.5, adding dopamine hydrochloride after ultrasonic dispersion, stirring and washing to obtain a dopamine-coated LMO material (PDA @ LMO);
s4) calcining the dopamine-coated LMO material (PDA @ LMO) at high temperature to obtain a carbon-coated LMO material (C @ LMO);
s5) treating an LMO material (C @ LMO) coated by the carbon layer by using hydrochloric acid, adding the LMO material into a tris buffer solution with the pH value of 8.5, ultrasonically dispersing, adding dopamine hydrochloride, stirring, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
s6) adding the dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain active electrode slurry;
s7) coating the active electrode slurry on a graphite plate, drying the graphite plate coated with the active electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the active electrode slurry to obtain a membrane electrode (pD-C @ HMO).
Specifically, liOH. H was added at a Li/Mn molar ratio of (2-5): 1 2 O and Mn 2 O 3 Mixing the powder; liOH. H 2 O and Mn 2 O 3 The powder is subjected to hydrothermal reaction for 8-12h at the temperature of 150-250 ℃.
Specifically, liMnO was added under an air atmosphere 2 The powder is roasted for 2-6h at 350-450 ℃.
In particular, li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) to the tris buffer solution is 1 (1-2.5).
Specifically, the obtained PDA @ LMO is calcined for 1-3h at 300-400 ℃ in a muffle furnace under the air atmosphere.
Specifically, treating C @ LMO with 0.5-1mol/L HCl at room temperature for 12-16h;
adding 0.5-1.0g of C @ LMO into 10-100mL of tris buffer solution, performing dispersion ultrasonic treatment for 30-60min, adding 0.02-0.1g of dopamine hydrochloride, stirring for 1-7h at room temperature in an open air, filtering, and washing to obtain the dopamine modified active electrode material (pD-C @ HMO).
Specifically, manganese carbonate (MnCO) 3 ) Placing the mixture in a muffle furnace, roasting the mixture for 3 to 6 hours at the temperature of between 600 and 1000 ℃ to obtain black Mn 2 O 3 And (3) powder.
The invention also provides a membrane electrode obtained based on the membrane electrode preparation method for extracting lithium from the salt lake.
The invention also provides a preparation method of the film capacitor unit, which comprises the following preparation steps:
adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
and assembling the membrane electrode and the activated carbon counter electrode according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain the membrane capacitance unit.
The invention also provides application of the membrane capacitor unit obtained based on the preparation method of the membrane capacitor unit in lithium extraction in salt lakes.
The invention uses carbon layer to coat, inhibits manganese dissolution loss, improves the conductivity and electrochemical activity of the material, and utilizes simple coating of dopamine on Li 1.6 Mn 1.6 O 4 The solid surface is carbonized to form a nano-scale coating layer with adjustable thickness, so that the manganese dissolution loss is reduced, meanwhile, the hydrophilicity of the material is improved by utilizing the aggregation of dopamine on the surface, the capability of transmitting lithium ions is improved, and the lithium extraction performance of the material is obviously improved.
Example one
Preparing a membrane capacitance unit:
101 Manganese carbonate (MnCO) in an air atmosphere 3 ) Placing in a muffle furnace, and roasting at 800 deg.C for 5 hr to obtain black Mn 2 O 3 Powder; reacting LiOH & H 2 O and Mn 2 O 3 The powder is prepared according to the molar ratio of Li/Mn of 5:1, adding deionized water, placing the mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction at the temperature of 210 ℃ for 12 hours, aging, filtering, washing and drying to obtain grayish green LiMnO 2 Powder;
102 In an air atmosphere, liMnO 2 The powder is roasted for 4 hours at the high temperature of 410 ℃ to obtain Li in a spinel phase 1.6 Mn 1.6 O 4 A precursor (LMO);
103 To Li 1.6 Mn 1.6 O 4 Adding a precursor (LMO) into tris buffer solution with pH of 8.5, reacting the tris buffer solution with Li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) is 200;
104 Putting the dopamine-coated LMO material (PDA @ LMO) into a muffle furnace, and calcining for 1h at 330 ℃ in an air atmosphere to obtain the LMO material (C @ LMO) coated by a carbon layer;
105 Processing the LMO material (C @ LMO) coated by the carbon layer by using 0.5mol/L hydrochloric acid, processing for 12h, adding the LMO material (C @ LMO) into tris buffer solution with the pH value of 8.5, ultrasonically dispersing for 30min, adding 0.04g of dopamine hydrochloride, stirring for 1h in an open manner at room temperature, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
106 Dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) are added into N, N-Dimethylacetamide (DMAC) and stirred to obtain active electrode slurry;
107 Active electrode slurry was coated on a graphite plate, the graphite plate coated with the active electrode slurry was dried in a vacuum oven at 50 ℃ for 12 hours, and the graphite plate coated with the active electrode slurry was pressed to obtain a membrane electrode (pD-c @ hmo).
108 Adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
109 Coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
110 The membrane electrode and the activated carbon counter electrode are assembled according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain a membrane capacitance unit.
Applying 1.2V voltage, introducing 303mg/L LiCl solution for extraction, and reversely applying 1.2V voltage after extraction to release Li + ions into deionized water for recovery.
The method adopts a membrane capacitance unit containing a pD-C @ HMO membrane electrode to extract and recover Li ions, the lithium extraction capacity is 30.6mg/g through a conductivity meter test, the solution concentration is 226.6mg/L after the extraction through the conductivity meter test, the extraction rate is 25.2% through calculation, the hydrophilicity is improved after dopamine modification, the ion enrichment degree on the surface of the electrode is increased, the lithium extraction performance is greatly improved, the solution concentration is 65.0mg/L through the conductivity meter test, and the recovery ratio can reach 85.0% through calculation.
The extraction rate was calculated as follows:
the extraction rate is as follows: [1- (C) 2 /C 1 )]×100％(C 1 (mg/L): introducing a solventThe concentration of the solution; c 2 (mg/L): post-extraction solution concentration);
as shown in FIG. 1, the membrane electrode materials pD-C @ HMO and Li 1.6 Mn 1.6 O 4 XRD pattern of standard card comparison; wherein: a-membrane electrode material pD-C @ HMO, b-Li 1.6 Mn 1.6 O 4 The standard card PDF #52-1841 shows the position of the diffraction peak of the membrane electrode material pD-C @ HMO and Li 1.6 Mn 1.6 O 4 The characteristic peaks of the standard card PDF #52-1841 are consistent and sharp, which indicates that Li with good crystallization and stable crystal phase is formed 1.6 Mn 1.6 O 4 Carbon coating and dopamine treatment did not alter Li 1.6 Mn 1.6 O 4 And (5) structure.
As shown in FIG. 2, it is a TEM image of the pD-C @ HMO, from which it can be seen that the membrane electrode material pD-C @ HMO is nanoparticles of 100-200nm, and has uniform size, no agglomeration and pore-shaped surface.
As shown in FIG. 3, which is an HRTEM image of pD-C @ HMO, it can be seen that the lattice spacing of the material is 0.248nm, corresponding to Li 1.6 Mn 1.6 O 4 The (311) crystal face of the silicon substrate is modified to form a shell layer with the outer layer thickness of about 3 nm.
Example two
Preparing a membrane capacitance unit:
201 Manganese carbonate (MnCO) in an air atmosphere 3 ) Placing in a muffle furnace, and roasting at 800 deg.C for 5 hr to obtain black Mn 2 O 3 Powder; reacting LiOH & H 2 O and Mn 2 O 3 The powder is prepared according to the molar ratio of Li/Mn of 2:1, adding deionized water, placing the mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction at the temperature of 210 ℃ for 12 hours, aging, filtering, washing and drying to obtain grayish green LiMnO 2 Powder;
202 Under an air atmosphere, liMnO 2 The powder is roasted for 4 hours at the high temperature of 410 ℃ to obtain Li in a spinel phase 1.6 Mn 1.6 O 4 A precursor (LMO);
203 To Li 1.6 Mn 1.6 O 4 The pH of the precursor (LMO) is set to8.5 of tris buffer solution, tris buffer solution with Li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) is 200, adding dopamine hydrochloride after ultrasonic dispersion for 0.5h, stirring the mixture for 6h at room temperature in an open manner, and washing to obtain a dopamine-coated LMO material (PDA @ LMO);
204 Putting the dopamine-coated LMO material (PDA @ LMO) into a muffle furnace, and calcining for 1h at 330 ℃ in an air atmosphere to obtain the LMO material (C @ LMO) coated by a carbon layer;
205 Processing the LMO material (C @ LMO) coated by the carbon layer by using 0.5mol/L hydrochloric acid, processing for 12h, adding the LMO material (C @ LMO) into tris buffer solution with the pH value of 8.5, ultrasonically dispersing for 30min, adding 0.04g of dopamine hydrochloride, stirring for 1h in an open manner at room temperature, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
206 Dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) are added into N, N-Dimethylacetamide (DMAC) and stirred to obtain active electrode slurry;
207 Active electrode slurry was coated on a graphite plate, the graphite plate coated with the active electrode slurry was dried in a vacuum oven at 50 ℃ for 12 hours, and the graphite plate coated with the active electrode slurry was pressed to obtain a membrane electrode (pD-c @ hmo).
208 Adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
209 Coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
210 The membrane electrode and the activated carbon counter electrode are assembled according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain a membrane capacitance unit.
Applying 1.2V voltage to introduce 303mg/L LiCl solution for extraction, and applying 1.2V voltage to Li in reverse direction after extraction + The ions are released into deionized water for recovery.
The method adopts a membrane capacitance unit containing a pD-C @ HMO membrane electrode to extract and recover Li ions, the lithium extraction capacity tested by a conductivity meter is 24.1mg/g, the solution concentration tested and extracted by the conductivity meter is 242.8mg/L, the extraction rate is 19.8 percent by calculation, the hydrophilicity is improved after dopamine modification, the ion enrichment degree on the surface of the electrode is increased, the lithium ion migration is improved, the lithium extraction performance is greatly improved, the solution concentration tested and recovered by the conductivity meter is 52.4mg/L, and the recovery ratio can reach 87.0 percent by calculation.
The molar ratio of Li to Mn is well controlled, and the extraction and recovery rate of Li ions by the membrane capacitance unit of the prepared pD-C @ HMO membrane electrode can be ensured.
EXAMPLE III
Preparing a membrane capacitance unit:
301 Manganese carbonate (MnCO) in an air atmosphere 3 ) Placing in a muffle furnace, and roasting at 800 deg.C for 5 hr to obtain black Mn 2 O 3 Powder; reacting LiOH & H 2 O and Mn 2 O 3 The powder was mixed in a molar ratio of Li/Mn of 4:1, adding deionized water, placing the mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction for 8 hours at the temperature of 210 ℃, and aging, filtering, washing and drying the mixture to obtain grayish green LiMnO 2 Powder;
302 In an air atmosphere, liMnO 2 The powder is roasted for 2h at the high temperature of 410 ℃ to obtain Li in a spinel phase 1.6 Mn 1.6 O 4 A precursor (LMO);
303 To Li 1.6 Mn 1.6 O 4 Adding the precursor (LMO) into tris buffer solution with pH of 8.5, reacting with Li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) is 100, adding dopamine hydrochloride after ultrasonic dispersion for 0.5h, stirring the mixture for 8h at room temperature in an open manner, and washing to obtain a dopamine-coated LMO material (PDA @ LMO);
304 Putting the dopamine-coated LMO material (PDA @ LMO) into a muffle furnace, and calcining for 1h at 330 ℃ in an air atmosphere to obtain the LMO material (C @ LMO) coated by a carbon layer;
305 Processing the LMO material (C @ LMO) coated by the carbon layer by using 0.5mol/L hydrochloric acid, processing for 12h, adding the LMO material into tris buffer solution with the pH value of 8.5, ultrasonically dispersing for 30min, adding 0.04g of dopamine hydrochloride, stirring for 3h in an open manner at room temperature, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
306 Dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) are added into N, N-Dimethylacetamide (DMAC) and stirred to obtain active electrode slurry;
307 Active electrode slurry was coated on a graphite plate, the graphite plate coated with the active electrode slurry was dried in a vacuum oven at 50 ℃ for 12 hours, and the graphite plate coated with the active electrode slurry was pressed to obtain a membrane electrode (pD-c @ hmo).
308 Adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
309 Coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
310 The membrane electrode and the activated carbon counter electrode are assembled according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain a membrane capacitance unit.
Applying 1.2V voltage, introducing 303mg/L LiCl solution for extraction, and reversely applying 1.2V voltage after extraction to release Li + ions into deionized water for recovery.
The method adopts a membrane capacitance unit containing a pD-C @ HMO membrane electrode to extract and recover Li ions, the lithium extraction capacity is 33.5mg/g through the test of a conductivity meter, the solution concentration is 219.3mg/L after the extraction through the test of the conductivity meter, the extraction rate is 27.6 percent through calculation, the hydrophilicity is improved after the modification of dopamine, the enrichment degree of the ions on the surface of the electrode is increased, the lithium extraction performance is greatly improved, the concentration of the recovered solution is 72.4mg/L through the test of the conductivity meter, and the recovery ratio can reach 86.5 percent through calculation.
Example four
Preparing a film capacitor unit:
401 Manganese carbonate (MnCO) in an air atmosphere 3 ) Placing in a muffle furnace, and roasting at 800 deg.C for 5 hr to obtain black Mn 2 O 3 Powder; reacting LiOH & H 2 O and Mn 2 O 3 The powder is prepared according to the molar ratio of Li/Mn of 3:1, adding deionized water, placing the mixture into a stainless steel reaction kettle, carrying out hydrothermal reaction for 10 hours at the temperature of 210 ℃, and aging, filtering, washing and drying the mixture to obtain grayish green LiMnO 2 A powder;
402 Under an air atmosphere, liMnO 2 Roasting the powder at 410 ℃ for 3h to obtain spinel-phase Li 1.6 Mn 1.6 O 4 A precursor (LMO);
403 To Li 1.6 Mn 1.6 O 4 Adding the precursor (LMO) into tris buffer solution with pH of 8.5, reacting with Li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) is 150;
404 Putting the dopamine-coated LMO material (PDA @ LMO) into a muffle furnace, and calcining for 1h at 330 ℃ in an air atmosphere to obtain the LMO material (C @ LMO) coated by a carbon layer;
405 Processing the LMO material (C @ LMO) coated by the carbon layer by using 0.5mol/L hydrochloric acid, processing for 12h, adding the LMO material into tris buffer solution with the pH value of 8.5, ultrasonically dispersing for 30min, adding 0.08g of dopamine hydrochloride, stirring for 3h in an open manner at room temperature, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
406 Dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) are added into N, N-Dimethylacetamide (DMAC) and stirred to obtain active electrode slurry;
407 Active electrode slurry was coated on a graphite plate, the graphite plate coated with the active electrode slurry was dried in a vacuum oven at 50 ℃ for 12 hours, and the graphite plate coated with the active electrode slurry was pressed to obtain a membrane electrode (pD-c @ hmo).
408 Adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
409 Coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
410 The membrane electrode and the activated carbon counter electrode are assembled according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain a membrane capacitance unit.
Applying 1.2V voltage, introducing 303mg/L LiCl solution for extraction, and reversely applying 1.2V voltage after extraction to release Li + ions into deionized water for recovery.
The method adopts a membrane capacitance unit containing a pD-C @ HMO membrane electrode to extract and recover Li ions, the lithium extraction capacity tested by a conductivity meter is 31.2mg/g, the solution concentration tested and extracted by the conductivity meter is 225.0mg/L, the extraction rate is 25.7 percent by calculation, the hydrophilicity is improved after dopamine modification, the ion enrichment degree on the surface of the electrode is increased, the lithium ion migration is improved, the lithium extraction performance is greatly improved, the concentration of the recovered solution tested and recovered by the conductivity meter is 67.9mg/L, and the recovery ratio can reach 87.1 percent by calculation.
EXAMPLE five
Preparing a membrane capacitance unit:
501 Manganese carbonate (MnCO) in an air atmosphere 3 ) Placing in a muffle furnace, and roasting at 800 deg.C for 5 hr to obtain black Mn 2 O 3 Powder; reacting LiOH & H 2 O and Mn 2 O 3 The powder is prepared according to the molar ratio of Li/Mn of 5:1, adding deionized water, putting the mixture into a stainless steel reaction kettle, performing hydrothermal reaction at 210 ℃ for 8 hours, aging, filtering, washing and drying to obtain grayish green LiMnO 2 Powder;
502 Under an air atmosphere, liMnO 2 The powder is roasted for 6 hours at the high temperature of 410 ℃ to obtain Li in a spinel phase 1.6 Mn 1.6 O 4 A precursor (LMO);
503 Will beLi 1.6 Mn 1.6 O 4 Adding the precursor (LMO) into tris buffer solution with pH of 8.5, reacting with Li 1.6 Mn 1.6 O 4 The mass ratio of the precursor (LMO) is 250;
504 Putting the dopamine-coated LMO material (PDA @ LMO) into a muffle furnace, and calcining for 1h at 330 ℃ in an air atmosphere to obtain the LMO material (C @ LMO) coated by a carbon layer;
505 Processing the LMO material (C @ LMO) coated by the carbon layer by using 0.5mol/L hydrochloric acid, processing for 12h, adding the LMO material into tris buffer solution with the pH value of 8.5, ultrasonically dispersing for 30min, adding 0.08g of dopamine hydrochloride, stirring for 3h in an open manner at room temperature, and filtering to obtain a black dopamine modified active electrode material (pD-C @ HMO);
506 Dopamine modified active electrode material (pD-C @ HMO) and polyvinylidene fluoride (PVDF) are added into N, N-Dimethylacetamide (DMAC) and stirred to obtain active electrode slurry;
507 Active electrode slurry was coated on a graphite plate, the graphite plate coated with the active electrode slurry was dried in a vacuum oven at 50 ℃ for 12 hours, and the graphite plate coated with the active electrode slurry was pressed to obtain a membrane electrode (pD-c @ hmo).
508 Adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
509 Coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
510 The membrane electrode and the activated carbon counter electrode are assembled according to an organic glass plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/an organic glass plate to obtain a membrane capacitance unit.
Applying 1.2V voltage to introduce 303mg/L LiCl solution for extraction, and applying 1.2V voltage to Li in reverse direction after extraction + Ion release to deionizationAnd (5) recovering the son water.
The method adopts a membrane capacitance unit containing a pD-C @ HMO membrane electrode to extract and recover Li ions, the lithium extraction capacity tested by a conductivity meter is 29.1mg/g, the solution concentration tested and extracted by the conductivity meter is 230.2mg/L, the extraction rate is 24.0 percent by calculation, the hydrophilicity is improved after dopamine modification, the enrichment degree of the ions on the surface of the electrode is increased, the lithium extraction performance is greatly improved, the concentration of the recovered solution tested and recovered by the conductivity meter is 62.5mg/L, and the recovery ratio can reach 85.9 percent by calculation.
Example 5 compared with example 1, the addition amount of dopamine hydrochloride has a certain influence on the extraction rate, and comparison shows that the addition of 0.04g of dopamine hydrochloride has the best effect.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a membrane electrode for extracting lithium from a salt lake is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
reacting LiOH & H 2 O and Mn 2 O 3 Mixing the powders in proportion, adding water, putting the mixture into a reaction kettle, carrying out hydrothermal reaction, aging, filtering, washing and drying to obtain grayish green LiMnO 2 Powder;
mixing LiMnO 2 The powder is calcined at high temperature to obtain spinel phase Li 1.6 Mn 1.6 O 4 A precursor;
mixing Li 1.6 Mn 1.6 O 4 Adding the precursor into tris buffer solution with the pH value of 8.5, adding dopamine hydrochloride after ultrasonic dispersion, stirring and washing to obtain dopamine-coated Li 1.6 Mn 1.6 O 4 A precursor material;
dopamine coated Li 1.6 Mn 1.6 O 4 Calcining the precursor material at high temperature to obtain Li coated with a carbon layer 1.6 Mn 1.6 O 4 A precursor material;
treatment of carbon layer-coated Li with hydrochloric acid 1.6 Mn 1.6 O 4 Adding a precursor material into tris buffer solution with the pH value of 8.5, performing ultrasonic dispersion, adding dopamine hydrochloride, stirring, and filtering to obtain a black dopamine-modified active electrode material;
adding the dopamine modified active electrode material and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain active electrode slurry;
coating the active electrode slurry on a graphite plate, drying the graphite plate coated with the active electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the active electrode slurry to obtain the membrane electrode.
2. The method for preparing the membrane electrode for extracting lithium from the salt lake according to claim 1, wherein the method comprises the following steps: liOH. H is added according to the Li/Mn molar ratio of (2-5): 1 2 O and Mn 2 O 3 Mixing the powder; liOH. H 2 O and Mn 2 O 3 The powder is subjected to hydrothermal reaction for 8-12h at the temperature of 150-250 ℃.
3. The method for preparing the membrane electrode for extracting lithium from the salt lake according to claim 1, wherein the method comprises the following steps: in an air atmosphere, liMnO is added 2 The powder is roasted for 2-6h at 350-450 ℃.
4. The method for preparing the membrane electrode for extracting lithium from the salt lake according to claim 1, wherein the method comprises the following steps: li 1.6 Mn 1.6 O 4 The mass ratio of the precursor to the tris buffer solution is 1 (1-2.5).
5. The method for preparing the membrane electrode for extracting lithium from the salt lake according to claim 1, wherein the method comprises the following steps: dopamine coated Li obtained 1.6 Mn 1.6 O 4 And calcining the precursor material in a muffle furnace for 1-3h at 300-400 ℃ in an air atmosphere.
6. The method for preparing the membrane electrode for extracting lithium from the salt lake according to claim 1, wherein the method comprises the following steps: li coated on carbon layer by using HCl 0.5-1mol/L at room temperature 1.6 Mn 1.6 O 4 Processing the precursor material for 12-16h;
li coating with 0.5-1.0g of carbon layer 1.6 Mn 1.6 O 4 Adding the precursor material into 10-100mL of tris buffer solution, performing dispersion ultrasonic treatment for 30-60min, adding 0.02-0.1g of dopamine hydrochloride, stirring for 1-7h in an open manner at room temperature, filtering, and washing to obtain the dopamine modified active electrode material.
7. The method for preparing the membrane electrode for extracting lithium from the salt lake according to claim 1, wherein the method comprises the following steps: mixing manganese carbonate MnCO 3 Placing the mixture in a muffle furnace, roasting the mixture for 3 to 6 hours at the temperature of between 600 and 1000 ℃ to obtain black Mn 2 O 3 And (3) powder.
8. A membrane electrode obtained based on the membrane electrode preparation method for extracting lithium from a salt lake according to any one of claims 1 to 7.
9. A method for preparing a film capacitor unit is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
adding activated carbon and polyvinylidene fluoride (PVDF) into N, N-Dimethylacetamide (DMAC), and stirring to obtain activated carbon counter electrode slurry;
coating the activated carbon counter electrode slurry on a graphite plate, drying the graphite plate coated with the activated carbon counter electrode slurry in a vacuum drying oven at 50-60 ℃ for 12-24h, and pressing the graphite plate coated with the activated carbon counter electrode slurry to obtain an activated carbon counter electrode;
assembling the membrane electrode and the activated carbon counter electrode according to claim 8 according to a plexiglas plate/an activated carbon counter electrode/an anion exchange membrane/a diaphragm/an activated membrane electrode/a plexiglas plate to obtain a membrane capacitive unit.
10. Use of a membrane capacitive unit obtained on the basis of the method for preparing a membrane capacitive unit according to claim 9 for extracting lithium from salt lakes.
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