WO2024259628A1 - 一种磁性富锂态电极及其制备方法和应用 - Google Patents

一种磁性富锂态电极及其制备方法和应用 Download PDF

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WO2024259628A1
WO2024259628A1 PCT/CN2023/101678 CN2023101678W WO2024259628A1 WO 2024259628 A1 WO2024259628 A1 WO 2024259628A1 CN 2023101678 W CN2023101678 W CN 2023101678W WO 2024259628 A1 WO2024259628 A1 WO 2024259628A1
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lithium
magnetic
electrode
rich
optionally
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French (fr)
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余海军
李爱霞
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to PCT/CN2023/101678 priority Critical patent/WO2024259628A1/zh
Priority to CN202380009670.7A priority patent/CN117015867A/zh
Priority to ARP240100494A priority patent/AR132005A1/es
Publication of WO2024259628A1 publication Critical patent/WO2024259628A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials

Definitions

  • the present invention belongs to the technical field of lithium extraction from salt lakes, and relates to a magnetic lithium-rich electrode and a preparation method and application thereof.
  • Lithium is an important strategic resource and is widely used in the field of lithium batteries.
  • the rapid development of the new energy field has led to a rapid increase in the market demand for lithium resources.
  • Low-cost and efficient lithium resource development has become an important guarantee for companies to participate in market competition.
  • the proven lithium resources in nature are mainly found in salt lake brine, seawater and ores, of which salt lake lithium resources account for about 70%. Due to the high cost and difficulty of lithium ore mining, and the fact that it has become increasingly scarce and exhausted with continuous mining, extracting lithium from salt lake brine has become a trend in lithium resource development.
  • the principle of electrochemical lithium extraction is to charge the working electrode to release lithium ions to form a lithium ion sieve, discharge it in brine to allow lithium ions to selectively enter the lithium ion sieve, and achieve lithium enrichment through cyclic operation of the charge and discharge process.
  • CN105600807A discloses a method for electrochemically extracting lithium salt from brine with a high magnesium-to-lithium ratio, wherein a sharp Crystalline LiMn 2 O 4 is uniformly coated on a titanium mesh current collector as a working electrode.
  • the titanium mesh is placed in a LiCl solution as a counter electrode.
  • the electrode is charged at a constant voltage to release lithium ions from LiMn 2 O 4 to form a lithium ion sieve.
  • Discharging the electrode system in a high magnesium-to-lithium ratio brine can selectively embed lithium ions into the lithium ion sieve.
  • the charge and discharge cycle operation realizes the electrochemical extraction of lithium salts.
  • the purpose of the present disclosure is to provide a magnetic lithium-rich electrode and a preparation method and application thereof.
  • the present disclosure applies a magnetic field during the electrode preparation process through a magnetic field-assisted method, which can increase the porosity of the electrode and the lithium ion conduction rate, thereby increasing the mass transfer rate inside the electrode and significantly improving the electrochemical lithium extraction efficiency.
  • an embodiment of the present disclosure provides a magnetic lithium-rich electrode, which includes a current collector and an active material layer arranged on the surface of the current collector, wherein the active material layer includes an electrode active material, a magnetic substance, a conductive agent and a binder, and the porosity of the magnetic lithium-rich electrode is 10 to 60%, for example: 10%, 20%, 30%, 40% or 60%, etc.
  • the magnetic lithium-rich electrode described in the embodiment of the present disclosure contains magnetic material.
  • a magnetic field is applied during the preparation of the electrode.
  • the movement direction of the magnetic particles is controlled by changing the direction of the magnetic field, so that the magnetic particles rotate repeatedly under the action of the changing magnetic field, thereby improving the electrode porosity and lithium ion conductivity.
  • the current collector comprises carbon fiber or titanium mesh.
  • the electrode active material includes any one of lithium manganese oxide, lithium iron phosphate, or lithium manganese iron phosphate, or a combination of at least two thereof.
  • the magnetic substance includes ferrosoferric oxide.
  • the particle size of the magnetic material is 10-200 nm, for example, 10 nm, 50 nm, 80 nm, 100 nm or 200 nm.
  • the conductive agent includes acetylene black and/or conductive carbon black.
  • the binder includes polyvinylidene fluoride.
  • the mass ratio of the electrode active material, magnetic substance, conductive agent and binder is 1:(0.01-0.2):(0.1-0.2):(0.1-0.15), for example: 1:0.01:0.1:0.1, 1:0.05:0.12:0.11, 1:0.1:0.15:0.12, 1:0.15:0.18:0.14 or 1:0.2:0.2:0.15, etc.
  • the lithium ion conductivity of the magnetic lithium-rich electrode is 10 -5 to 10 -2 S/cm, for example, 10 -5 S/cm, 2 ⁇ 10 -4 S/cm, 5 ⁇ 10 -3 S/cm, 8 ⁇ 10 -3 S/cm or 10 -2 S/cm.
  • the porosity of the magnetic lithium-rich electrode is 20-50%.
  • the porosity of the magnetic lithium-rich electrode described in the embodiment of the present disclosure is better controlled at 20-50%. If the pores are too large, the mechanical strength of the electrode is poor, which reduces the cycle performance. If the porosity is too small, the mass transfer effect of the brine solution is poor.
  • the present disclosure provides a method for preparing a magnetic lithium-rich electrode as described in the first aspect, the preparation method comprising the following steps:
  • the electrode active material, magnetic substance, conductive agent, binder and solvent are mixed to obtain slurry, a reversing magnetic field is applied to the current collector, and the slurry is coated on the surface of the current collector to obtain a lithium-rich electrode.
  • a small amount of magnetic material is added when preparing the electrode slurry, and a changing magnetic field is applied during the coating process to make the magnetic material move in different directions in the electrode.
  • the movement trajectory can form a pore structure in the electrode, that is, the path for lithium ions to move in the active material layer, thereby improving the lithium ion conductivity.
  • the solvent comprises N-methylpyrrolidone.
  • the viscosity of the slurry is 1-10 Pa ⁇ s, for example: 1 Pa ⁇ s, 2 Pa ⁇ s, 5 Pa ⁇ s, 8Pa ⁇ s or 10Pa ⁇ s, etc.
  • the intensity of the variable magnetic field is 0.5-5T, for example, 0.5T, 1T, 2T, 3T, 4T or 5T.
  • the coating density is 150-200 mg/cm 2 , for example, 150 mg/cm 2 , 160 mg/cm 2 , 170 mg/cm 2 , 180 mg/cm 2 or 200 mg/cm 2 .
  • the coating is followed by drying.
  • the drying temperature is 50-80°C, for example, 50°C, 55°C, 60°C, 70°C or 80°C.
  • the drying time is 4 to 8 hours, for example: 4 hours, 5 hours, 6 hours, 7 hours or 8 hours.
  • the present disclosure provides a method for extracting lithium from a salt lake by electrochemical deintercalation assisted by a magnetic field, the method comprising the following steps:
  • the electrolysis device is separated into an anode chamber and a cathode chamber by an anion exchange membrane, a magnetic lithium-rich electrode is placed in the anode chamber, and a magnetic lithium-poor electrode is placed in the cathode chamber.
  • Salt lake brine is injected into the cathode chamber, and a salt solution is injected into the anode chamber.
  • a magnetic field is applied to the electrodes while power is supplied at a constant voltage. The current is as low as 150 mA to terminate the reaction.
  • adding a magnetic field during the lithium extraction process can promote the flow of brine, increase the contact rate between brine and active substances, and improve the efficiency of lithium extraction.
  • the electrolyte in step (1) includes sodium chloride solution and/or potassium chloride solution.
  • the concentration of the electrolyte is 0.05-0.1 mol/L, for example, 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L or 0.1 mol/L.
  • the voltage of the constant voltage reaction is 0.8 to 1.2 V, for example, 0.8 V, 0.9 V, 1V, 1.1V or 1.2V, etc.
  • the salt solution in step (2) includes sodium chloride solution and/or potassium chloride solution.
  • the concentration of the salt solution is 0.05-0.1 mol/L, for example, 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L or 0.1 mol/L.
  • the constant voltage power supply in step (2) is 0.3-1.2V, for example, 0.3V, 0.5V, 0.8V, 1V or 1.2V.
  • the strength of the magnetic field is 0.1-1 T, for example, 0.1 T, 0.2 T, 0.5 T, 0.8 T or 1 T.
  • the present disclosure has the following beneficial effects:
  • the present invention adds a small amount of magnetic material when preparing electrode slurry, and applies a changing magnetic field during the coating process to make the magnetic material move in different directions in the electrode.
  • the movement trajectory can form a pore structure in the electrode, that is, a path for lithium ions to move in the active material layer, thereby improving lithium ion conductivity.
  • the present invention applies a magnetic field with controllable size and direction to the electrode, which can adjust the motion state of the magnetic substance in the electrode.
  • the motion of the magnetic substance in the mass transfer channel can disturb the brine, promote the flow of the brine, accelerate the contact between the brine and the active substance, and improve the efficiency of lithium extraction.
  • the electrode prepared in the present invention has a good mass transfer effect on brine. After lithium extraction, the lithium concentration in the lithium-rich anode liquid can reach more than 3.04 g/L, and has excellent electrochemical salt lake lithium extraction performance.
  • FIG1 is a schematic diagram of the structure of the magnetic lithium-rich electrode according to Example 1 of the present disclosure, wherein 1-electrode activity 1-Magnetic material, 2-Magnetic substance, 3-Magnetic lines of force.
  • Figure 2 is a schematic diagram of a device for extracting lithium from salt lakes by means of magnetic field-assisted electrochemical deintercalation according to Example 1 of the present disclosure, wherein 1-coil, 2-iron core, 3-lithium ions, 4-KCl solution, 5-anion exchange membrane, and 6-brine.
  • This embodiment provides a method for extracting lithium from a salt lake by electrochemical deintercalation assisted by a magnetic field, the method comprising the following steps:
  • the slurry was coated on a titanium mesh current collector at a density of 150 mg/cm 2 , and a magnetic field with a strength of 2 T was applied to the current collector at a frequency of 2 times/min, so that the magnetic particles rotated repeatedly under the action of the changing magnetic field, and then dried at 80°C for 4 h to obtain a magnetic lithium-rich electrode with a porosity of 30% and a lithium ion conductivity of 5.83 ⁇ 10 -3 S/cm;
  • the lithium-rich electrode was delithiated at a constant voltage of 1.0 V to obtain a magnetic lithium-poor electrode
  • the electrolysis device is separated into an anode chamber and a cathode chamber by an anion exchange membrane, and a magnetic lithium-rich electrode and a magnetic lithium-poor electrode are placed in the anode chamber and the cathode chamber respectively.
  • Brine is injected into the cathode chamber, and a 0.05KCl solution is injected into the anode chamber.
  • Lithium is extracted at a constant voltage of 0.3V.
  • a 1T reversing magnetic field is applied to the electrode by a magnetic field regulating device.
  • the frequency of the reversing is 3 times/min.
  • the movement state of the magnetic material in the electrode is regulated. When the current is as low as 150mA, the reaction is terminated.
  • FIG1 The schematic diagram of the structure of the magnetic lithium-rich electrode in a magnetic field is shown in FIG1 .
  • a schematic diagram of a device for chemical deintercalation of lithium from salt lakes is shown in FIG2 .
  • the present invention applies a reverse magnetic field during the process of extracting lithium from salt lakes. Due to the presence of magnetic substances in the electrodes, the motion state of the magnetic substances changes under the action of the reverse magnetic field, which can promote the flow of brine, accelerate the contact between brine and active substances, and improve the efficiency of lithium extraction.
  • This embodiment provides a method for extracting lithium from a salt lake by electrochemical deintercalation assisted by a magnetic field, the method comprising the following steps:
  • the slurry was coated on a titanium mesh current collector at a density of 150 mg/cm 2 , and a magnetic field with a strength of 0.5 T was applied to the current collector at a frequency of 2 times/min to make the magnetic particles rotate repeatedly under the action of the changing magnetic field.
  • the mixture was then dried at 50°C for 8 h to obtain a magnetic lithium-rich electrode with a porosity of 20% and a lithium ion conductivity of 4.67 ⁇ 10 -3 S/cm.
  • the lithium-rich electrode was delithiated at a constant voltage of 1.0 V to obtain a magnetic lithium-poor electrode
  • the electrolysis device is separated into an anode chamber and a cathode chamber by an anion exchange membrane, and a magnetic lithium-rich electrode and a magnetic lithium-poor electrode are placed in the anode chamber and the cathode chamber respectively.
  • Brine is injected into the cathode chamber, and a 0.05KCl solution is injected into the anode chamber.
  • Lithium is extracted at a constant voltage of 0.5V.
  • a 0.1T reversing magnetic field is applied to the electrode by a magnetic field adjustment device, and the frequency of reversing is 3 times/min to regulate the motion state of the magnetic material in the electrode.
  • the current is as low as 150mA, the reaction is terminated.
  • This embodiment provides a method for extracting lithium from a salt lake by electrochemical deintercalation assisted by a magnetic field, the method comprising the following steps:
  • the slurry was coated on a titanium mesh current collector at a density of 200 mg/cm 2 , and a magnetic field with a strength of 1 T was applied to the current collector at a frequency of 2 times/min, so that the magnetic particles rotated repeatedly under the action of the changing magnetic field, and then dried at 60°C for 5 h to obtain a magnetic lithium-rich electrode with a porosity of 40% and a lithium ion conductivity of 6.35 ⁇ 10 -3 S/cm;
  • the lithium-rich electrode was delithiated at a constant voltage of 1.0 V to obtain a magnetic lithium-poor electrode
  • the electrolysis device is separated into an anode chamber and a cathode chamber by an anion exchange membrane, and a magnetic lithium-rich electrode and a magnetic lithium-poor electrode are placed in the anode chamber and the cathode chamber respectively.
  • Brine is injected into the cathode chamber, and a 0.05KCl solution is injected into the anode chamber.
  • Lithium is extracted at a constant voltage of 0.5V.
  • a 0.5T reversing magnetic field is applied to the electrode by a magnetic field regulating device, and the frequency of reversing is 3 times/min to regulate the motion state of the magnetic material in the electrode.
  • the current is as low as 150mA, the reaction is terminated.
  • the difference between this embodiment and embodiment 1 is that the magnetic field strength in step (1) is 0.3 T, and a magnetic lithium-rich electrode with a porosity of 10% and a lithium ion conductivity of 2.39 ⁇ 10 -3 S/cm is obtained.
  • Other conditions and parameters are exactly the same as those in embodiment 1.
  • the magnetic field strength in step (1) is 6 T, and a magnetic lithium-rich electrode with a porosity of 60% and a lithium ion conductivity of 6.61 ⁇ 10 -3 S/cm is obtained.
  • Other conditions and parameters are exactly the same as those in embodiment 1.
  • step (1) no magnetic field is applied to the current collector during the coating process, and the other conditions and parameters are exactly the same as those in Example 1.
  • step (3) no magnetic field is applied to the electrodes during the lithium extraction process, and the other conditions and parameters are exactly the same as those in Example 1.
  • a method for extracting lithium from a salt lake by electrochemical deintercalation assisted by a magnetic field comprising the following steps:
  • lithium iron phosphate 100 g was mixed with 10 g of sodium bicarbonate, 20 g of acetylene black and 15 g of PVDF, added to NMP, mixed evenly to obtain an electrode slurry, coated on a titanium mesh current collector at a density of 150 mg/ cm2 , and then dried at 80°C for 4 h to obtain a lithium-rich electrode;
  • the lithium-rich electrode was delithiated at a constant voltage of 1.0 V to obtain a lithium-poor electrode
  • the electrolysis device is separated into an anode chamber and a cathode chamber by an anion exchange membrane, and a lithium-rich electrode and a lithium-poor electrode are placed in the anode chamber and the cathode chamber respectively.
  • Brine is injected into the cathode chamber and a 0.05KCl solution is injected into the anode chamber.
  • Lithium is extracted at a constant voltage of 0.3 V. When the current drops to 150 mA, the reaction is terminated.
  • the lithium concentration of the lithium-rich solution prepared by the method for extracting lithium from salt lakes by magnetic field-assisted electrochemical deintercalation can reach above 3.04 g/L.
  • Example 1 By comparing Example 1 with Examples 4-5, it can be seen that in the lithium extraction process described in the present disclosure, the magnetic field strength applied to the current collector when preparing the lithium-rich electrode will affect the subsequent lithium extraction effect.
  • the first magnetic field strength is controlled at 0.5-5T, and the lithium extraction effect is better. If the strength is too large, the movement range of the magnetic particles is too large and the movement speed is too fast, resulting in excessive pores, poor mechanical strength of the electrode, and reduced cycle performance. If the strength is too small, the magnetic particles cannot rotate, resulting in a small porosity and poor mass transfer of the brine solution.
  • Example 1 By comparing Example 1 with Examples 6-7, it can be seen that in the process of lithium extraction described in the present disclosure, the electrode is applied The magnetic field strength will affect the subsequent lithium extraction effect.
  • the second magnetic field strength is controlled at 0.1 ⁇ 1T, and the lithium extraction effect is better. If the strength is too high, the magnetic particles will move out of a certain range, resulting in uneven distribution, which will lead to uneven disturbance of the brine and uneven mass transfer of the solution. If the strength is too low, the magnetic particles will move with a small amplitude and have little disturbance effect on the brine.
  • Example 1 By comparing Example 1 and Comparative Example 1, it can be seen that when preparing the electrode slurry, the present invention adds a small amount of magnetic material, and applies a changing magnetic field during the coating process to make the magnetic material move in different directions in the electrode.
  • the movement trajectory can form a pore structure in the electrode, that is, the path for lithium ions to move in the active material layer, thereby improving the lithium ion conductivity.
  • Example 1 By comparing Example 1 with Comparative Example 2, it can be seen that in the process of lithium extraction, the present disclosure applies a magnetic field with controllable size and direction to the electrode, which can adjust the motion state of the magnetic substance in the electrode.
  • the motion of the magnetic substance in the mass transfer channel can disturb the brine, promote the flow of the brine, accelerate the contact between the brine and the active substance, and improve the efficiency of lithium extraction.
  • Example 1 By comparing Example 1 and Comparative Example 1, it can be seen that the present invention applies a magnetic field during the preparation of the electrode, and controls the movement direction of the magnetic particles by changing the direction of the magnetic field, so that the magnetic particles rotate repeatedly under the action of the changing magnetic field, thereby improving the electrode porosity and the lithium ion conductivity.
  • the addition of a magnetic field during the lithium extraction process can promote the flow of brine, increase the contact rate between brine and active substances, and improve the lithium extraction efficiency.

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Abstract

本公开提供了一种磁性富锂态电极及其制备方法和应用，所述磁性富锂态电极包括集流体和设置于所述集流体表面的活性物质层，所述活性物质层包括电极活性材料、磁性物质、导电剂和粘结剂，所述磁性富锂态电极的孔隙率为10～60％，本公开通过磁场辅助提锂的方法，在电极制备的过程中施加磁场，可以提高电极的孔隙率以及锂离子传导速率，进而提高电极内部传质速率，明显提高电化学提锂效率。

Description

一种磁性富锂态电极及其制备方法和应用 技术领域
本公开属于盐湖提锂技术领域，涉及一种磁性富锂态电极及其制备方法和应用。
背景技术
锂是一种重要的战略资源，广泛用于锂电池领域。新能源领域的快速发展，带动锂资源的市场需求快速增加，低成本、高效地锂资源开发成为各企业参与市场竞争的重要保证。自然界中已探明的锂资源主要存在于盐湖卤水、海水和矿石中，其中盐湖锂资源约占70％。由于锂矿石开采成本高、难度大，且随着不断开采已日益贫乏和枯竭，因此，从盐湖卤水提取锂已成为锂资源开发的趋势。
我国西部盐湖众多，但由于高镁锂比特征导致其开发程度低。目前国内外从卤水中提锂的方法主要有沉淀法、溶剂萃取法、蒸发结晶法、电渗析法、离子交换吸附法等，沉淀法作为一种已经成熟的提锂技术，存在着耗能较大、工艺流程复杂、成本较高的缺点，锂的回收率也不高。萃取法提锂速率快，但是萃取剂溶解于卤水中容易导致环境污染；吸附法存在吸附容量低、吸附剂溶损以及水耗大等问题。近年来，国内外很多研究者对新的提锂工艺进行了广泛的探索和研究，电化学提锂技术具有良好的使用价值和应用前景。
电化学提锂的原理是对工作电极充电将锂离子脱出形成锂离子筛，在盐水中放电使锂离子选择性地进入锂离子筛中，通过充放电过程循环操作实现锂的富集。
CN105600807A公开了一种从高镁锂比盐水中电化学提取锂盐的方法，将尖 晶石型LiMn2O4均匀涂覆在钛网集流体上作为工作电极，钛网作为对电极置于LiCl溶液中，对电极进行恒压充电，可将锂离子从LiMn2O4中脱出形成锂离子筛，将电极体系在高镁锂比盐水中放电可以选择性地使锂离子嵌入锂离子筛中，充放电循环操作实现电化学提取锂盐，但是由于盐湖卤水中存在大量的杂质元素(如镁、钠等)，导致卤水粘度较大导致该方法存在溶液在电极内部传质缓慢的问题，进一步导致电化学提锂的效率较低。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开的目的在于提供一种磁性富锂态电极及其制备方法和应用，本公开通过磁场辅助的方法，在电极制备的过程中施加磁场，可以提高电极的孔隙率以及锂离子传导速率，进而提高电极内部传质速率，明显提高电化学提锂效率。
为达到此公开目的，本公开采用以下技术方案：
第一方面，本公开实施例提供了一种磁性富锂态电极，所述磁性富锂态电极包括集流体和设置于所述集流体表面的活性物质层，所述活性物质层包括电极活性材料、磁性物质、导电剂和粘结剂，所述磁性富锂态电极的孔隙率为10～60％，例如：10％、20％、30％、40％或60％等。
本公开实施例所述磁性富锂态电极中含有磁性物质，在电极制备的过程中施加磁场，通过改变磁场方向来控制磁性颗粒的运动方向，使磁性颗粒在变向磁场的作用下反复转动，提升电极孔隙率的同时提高锂离子传导性。
在一个实施例中，所述集流体包括碳纤维或钛网。
在一个实施例中，所述电极活性材料包括锰酸锂、磷酸铁锂或磷酸锰铁锂中的任意一种或至少两种的组合。
在一个实施例中，所述磁性物质包括四氧化三铁。
在一个实施例中，所述磁性物质的粒径为10～200nm，例如：10nm、50nm、80nm、100nm或200nm等。
在一个实施例中，所述导电剂包括乙炔黑和/或导电炭黑。
在一个实施例中，所述粘结剂包括聚偏氟乙烯。
在一个实施例中，所述电极活性材料、磁性物质、导电剂和粘结剂的质量比为1:(0.01～0.2):(0.1～0.2):(0.1～0.15)，例如：1:0.01:0.1:0.1、1:0.05:0.12:0.11、1:0.1:0.15:0.12、1:0.15:0.18:0.14或1:0.2:0.2:0.15等。
在一个实施例中，所述磁性富锂态电极的锂离子电导率为10-5～10-2S/cm，例如：10-5S/cm、2×10-4S/cm、5×10-3S/cm、8×10-3S/cm或10-2S/cm等。
在一个实施例中，所述磁性富锂态电极的孔隙率为20～50％。
本公开实施例所述磁性富锂态电极的孔隙率控制在20～50％效果较好，若孔隙过大，电极机械强度差，降低循环性能，若孔隙率过小则卤水溶液的传质作用差。
第二方面，本公开实施例提供了一种如第一方面所述磁性富锂态电极的制备方法，所述制备方法包括以下步骤：
将电极活性材料、磁性物质、导电剂、粘结剂和溶剂混合得到浆料，对集流体施加变向磁场，将所述浆料涂覆在集流体表面，得到富锂态电极。
本公开实施例在制备电极浆料时，加入少量的磁性物质，并在涂布过程中施加变向的磁场，使磁性物质在电极内往不同方向运动，运动轨迹可以形成电极内的孔隙结构，即锂离子在活性物质层内移动的路径，提高锂离子传导性。
在一个实施例中，所述溶剂包括N-甲基吡咯烷酮。
在一个实施例中，所述浆料的粘度为1～10Pa·s，例如：1Pa·s、2Pa·s、5Pa·s、 8Pa·s或10Pa·s等。
在一个实施例中，所述变向磁场的强度为0.5～5T，例如：0.5T、1T、2T、3T、4T或5T等。
在一个实施例中，所述涂覆的密度为150～200mg/cm2，例如：150mg/cm2、160mg/cm2、170mg/cm2、180mg/cm2或200mg/cm2等。
在一个实施例中，所述涂覆后进行烘干。
在一个实施例中，所述烘干的温度为50～80℃，例如：50℃、55℃、60℃、70℃或80℃等。
在一个实施例中，所述烘干的时间为4～8h，例如：4h、5h、6h、7h或8h等。
第三方面，本公开实施例提供了一种磁场辅助电化学脱嵌盐湖提锂的方法，所述方法包括以下步骤：
(1)以第一方面所述的磁性富锂态电极为正极，AgCl电极为负极，注入电解液恒压反应得到磁性贫锂态电极；
(3)用阴离子交换膜将电解装置分隔成阳极室和阴极室，将磁性富锂态电极置于阳极室，磁性贫锂态电极置于阴极室，阴极室注入盐湖卤水，阳极室注入盐溶液，恒压通电的同时对电极施加磁场，电流低至150mA，结束反应。
本公开实施例在提锂过程中加入磁场可以促进卤水流动，提高卤水和活性物质的接触率，提高提锂效率。
在一个实施例中，步骤(1)所述电解液包括氯化钠溶液和/或氯化钾溶液。
在一个实施例中，所述电解液的浓度为0.05～0.1mol/L，例如：0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L或0.1mol/L等。
在一个实施例中，所述恒压反应的电压为0.8～1.2V，例如：0.8V、0.9V、 1V、1.1V或1.2V等。
在一个实施例中，步骤(2)所述盐溶液包括氯化钠溶液和/或氯化钾溶液。
在一个实施例中，所述盐溶液的浓度为0.05～0.1mol/L，例如：0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L或0.1mol/L等。
在一个实施例中，步骤(2)所述恒压通电的电压为0.3～1.2V，例如：0.3V、0.5V、0.8V、1V或1.2V等。
在一个实施例中，所述磁场的强度为0.1～1T，例如：0.1T、0.2T、0.5T、0.8T或1T等。
相对于相关技术，本公开具有以下有益效果：
(1)本公开在制备电极浆料时，加入少量的磁性物质，并在涂布过程中施加变向的磁场，使磁性物质在电极内往不同方向运动，运动轨迹可以形成电极内的孔隙结构，即锂离子在活性物质层内移动的路径，提高锂离子传导性。
(2)本公开在提锂过程中，对电极施加大小、方向可控的磁场，能够调节电极内磁性物质的运动状态。传质通道内磁性物质的运动可以扰动卤水，促进卤水的流动，加快卤水与活性物质的接触，提高提锂效率。
(3)本公开制备的电极对卤水有较好的传质作用，提锂后阳极液富锂液中锂浓度可达3.04g/L以上，具有优异的电化学盐湖提锂性能。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1是本公开实施例1所述磁性富锂态电极的结构示意图，其中，1-电极活 性材料，2-磁性物质，3-磁感线。
图2是本公开实施例1所述磁场辅助电化学脱嵌盐湖提锂的装置示意图。其中，1-线圈，2-铁芯，3-锂离子，4-KCl溶液，5-阴离子交换膜，6-卤水。
具体实施方式
下面通过具体实施方式来进一步说明本公开的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本公开，不应视为对本公开的具体限制。
实施例1
本实施例提供了一种磁场辅助电化学脱嵌盐湖提锂的方法，所述方法包括以下步骤：
(1)将100g磷酸铁锂与10g四氧化三铁(D50＝50nm)、20g乙炔黑和15gPVDF混合，加入到NMP中，形成粘度为10Pa·s的浆料，按150mg/cm2的密度涂覆在钛网集流体上，同时对集流体施加变向、强度为2T的磁场，变向的频率为2次/min，使磁性颗粒在变向磁场的作用下反复转动，然后在80℃下干燥4h得到孔隙率为30％，锂离子电导率为5.83×10-3S/cm的磁性富锂态电极；
(2)以磁性富锂态电极为正极，AgCl电极为负极，0.05mol/L KCl溶液为电解液，在1.0V的恒定电压下对富锂态电极进行脱锂得到磁性贫锂态电极；
(3)用阴离子交换膜将电解装置分隔成阳极室和阴极室，将磁性富锂态电极和磁性贫锂态电极分别置于阳极室和阴极室，往阴极室注入卤水，阳极室注入0.05KCl溶液，在0.3V的恒压电压下进行提锂，同时通过磁场调节装置对电极施加大小为1T的变向磁场，变向的频率为3次/min，调控电极内磁性材料的运动状态，当电流低至150mA时，结束反应。
所述磁性富锂态电极在磁场中的结构示意图如图1所示，所述磁场辅助电 化学脱嵌盐湖提锂的装置示意图如图2所示，由图1-2可以看出，本公开在盐湖提锂的过程中施加变向磁场，由于电极中存在的磁性物质，在变向磁场的作用下磁性物质的运动状态发生变化，可以促进卤水的流动，加快卤水与活性物质的接触，提高提锂效率。
实施例2
本实施例提供了一种磁场辅助电化学脱嵌盐湖提锂的方法，所述方法包括以下步骤：
(1)将100g磷酸铁锂与1g四氧化三铁(D50＝100nm)、10g乙炔黑和10gPVDF混合，加入到NMP中，形成粘度为1Pa·s的浆料，按150mg/cm2的密度涂覆在钛网集流体上，同时对集流体施加变向、强度为0.5T的磁场，变向的频率为2次/min，使磁性颗粒在变向磁场的作用下反复转动，然后在50℃下干燥8h得到孔隙率为20％，锂离子电导率为4.67×10-3S/cm的磁性富锂态电极；
(2)以磁性富锂态电极为正极，AgCl电极为负极，0.05mol/L KCl溶液为电解液，在1.0V的恒定电压下对富锂态电极进行脱锂得到磁性贫锂态电极；
(3)用阴离子交换膜将电解装置分隔成阳极室和阴极室，将磁性富锂态电极和磁性贫锂态电极分别置于阳极室和阴极室，往阴极室注入卤水，阳极室注入0.05KCl溶液，在0.5V的恒压电压下进行提锂，同时通过磁场调节装置对电极施加大小为0.1T的变向磁场，变向的频率为3次/min，调控电极内磁性材料的运动状态。当电流低至150mA时，结束反应。
实施例3
本实施例提供了一种磁场辅助电化学脱嵌盐湖提锂的方法，所述方法包括以下步骤：
(1)将100g磷酸铁锂与15g四氧化三铁(D50＝20nm)、15g乙炔黑和15gPVDF混合，加入到NMP中，形成粘度为5Pa·s的浆料，按200mg/cm2的密度涂覆在钛网集流体上，同时对集流体施加变向、强度为1T的磁场，变向的频率为2次/min，使磁性颗粒在变向磁场的作用下反复转动，然后在60℃下干燥5h得到孔隙率为40％，锂离子电导率为6.35×10-3S/cm的磁性富锂态电极；
(2)以磁性富锂态电极为正极，AgCl电极为负极，0.05mol/L KCl溶液为电解液，在1.0V的恒定电压下对富锂态电极进行脱锂得到磁性贫锂态电极；
(3)用阴离子交换膜将电解装置分隔成阳极室和阴极室，将磁性富锂态电极和磁性贫锂态电极分别置于阳极室和阴极室，往阴极室注入卤水，阳极室注入0.05KCl溶液，在0.5V的恒压电压下进行提锂，同时通过磁场调节装置对电极施加大小为0.5T的变向磁场，变向的频率为3次/min，调控电极内磁性材料的运动状态。当电流低至150mA时，结束反应。
实施例4
本实施例与实施例1区别仅在于，步骤(1)所述磁场强度为0.3T，得到孔隙率为10％，锂离子电导率为2.39×10-3S/cm的磁性富锂态电极，其他条件与参数与实施例1完全相同。
实施例5
本实施例与实施例1区别仅在于，步骤(1)所述磁场强度为6T，得到孔隙率为60％，锂离子电导率为6.61×10-3S/cm的磁性富锂态电极，其他条件与参数与实施例1完全相同。
实施例6
本实施例与实施例1区别仅在于，步骤(3)所述磁场强度为0.05T，其他 条件与参数与实施例1完全相同。
实施例7
本实施例与实施例1区别仅在于，步骤(3)所述磁场强度为1.2T，其他条件与参数与实施例1完全相同。
对比例1
本对比例与实施例1区别仅在于，步骤(1)在涂覆过程中不对集流体施加磁场，其他条件与参数与实施例1完全相同。
对比例2
本对比例与实施例1区别仅在于，步骤(3)在提锂过程中不对电极施加磁场，其他条件与参数与实施例1完全相同。
对比例3
提供了一种磁场辅助电化学脱嵌盐湖提锂的方法，所述方法包括以下步骤：
(1)将100g磷酸铁锂与10g碳酸氢钠、20g乙炔黑和15gPVDF混合，加入到NMP中，混合均匀得到电极浆料，按150mg/cm2的密度涂覆在钛网集流体上，然后在80℃下干燥4h得到富锂态电极；
(2)以富锂态电极为正极，AgCl电极为负极，0.05mol/L KCl溶液为电解液，在1.0V的恒定电压下对富锂态电极进行脱锂得到贫锂态电极；
(3)用阴离子交换膜将电解装置分隔成阳极室和阴极室，将富锂态电极和贫锂态电极分别置于阳极室和阴极室，往阴极室注入卤水，阳极室注入0.05KCl溶液，在0.3V的恒压电压下进行提锂，当电流低至150mA时，结束反应。
性能测试：
对实施例和对比例得到富锂溶液进行锂浓度测试，测试结果如表1所示：
表1
由表1可以看出，由实施例1-3可得，本公开所述磁场辅助电化学脱嵌盐湖提锂的方法制得富锂溶液的锂浓度可达3.04g/L以上。
由实施例1和实施例4-5对比可得，本公开所述提锂的过程中，制备富锂态电极时对集流体施加的磁场强度会影响后续的提锂效果，将第一磁场强度控制在0.5～5T，提锂效果较好，若强度过大，磁性颗粒运动范围太大、运动速度太快，造成孔隙过大，电极机械强度差，降低循环性能，若强度过小，则无法使磁性颗粒转动，导致孔隙率小，卤水溶液的传质作用差。
由实施例1和实施例6-7对比可得，本公开所述提锂的过程中，对电极施加 的磁场强度会影响后续的提锂效果，将第二磁场强度控制在0.1～1T，提锂效果较好，若强度过大，磁性颗粒运动脱离一定范围，造成分布不均匀，从而导致对卤水的扰动不均匀，溶液传质不均匀，若强度过小，则磁性颗粒运动幅度小，对卤水的扰动作用小。
由实施例1和对比例1对比可得，本公开在制备电极浆料时，加入少量的磁性物质，并在涂布过程中施加变向的磁场，使磁性物质在电极内往不同方向运动，运动轨迹可以形成电极内的孔隙结构，即锂离子在活性物质层内移动的路径，提高锂离子传导性。
由实施例1和对比例2对比可得，本公开在提锂过程中，对电极施加大小、方向可控的磁场，能够调节电极内磁性物质的运动状态。传质通道内磁性物质的运动可以扰动卤水，促进卤水的流动，加快卤水与活性物质的接触，提高提锂效率。
由实施例1和对比例1对比可得，本公开在电极制备的过程中施加磁场，通过改变磁场方向来控制磁性颗粒的运动方向，使磁性颗粒在变向磁场的作用下反复转动，提升电极孔隙率的同时提高锂离子传导性，在提锂过程中加入磁场可以促进卤水流动，提高卤水和活性物质的接触率，提高提锂效率。

Claims (14)

  1. 一种磁性富锂态电极，所述磁性富锂态电极包括集流体和设置于所述集流体表面的活性物质层，所述活性物质层包括电极活性材料、磁性物质、导电剂和粘结剂，所述磁性富锂态电极的孔隙率为10～60％。
  2. 如权利要求1所述的磁性富锂态电极，其中，所述集流体包括碳纤维或钛网。
  3. 如权利要求1所述的磁性富锂态电极，其中，所述电极活性材料包括锰酸锂、磷酸铁锂或磷酸锰铁锂中的任意一种或至少两种的组合。
  4. 如权利要求1所述的磁性富锂态电极，其中，所述磁性物质包括四氧化三铁；
    可选地，所述磁性物质的粒径为10～200nm。
  5. 如权利要求1所述的磁性富锂态电极，其中，所述导电剂包括乙炔黑和/或导电炭黑。
  6. 如权利要求1所述的磁性富锂态电极，其中，所述粘结剂包括聚偏氟乙烯。
  7. 如权利要求1-6任一项所述的磁性富锂态电极，其中，所述电极活性材料、磁性物质、导电剂和粘结剂的质量比为1:(0.01～0.2):(0.1～0.2):(0.1～0.15)。
  8. 如权利要求1-7任一项所述的磁性富锂态电极，其中，所述磁性富锂态电极的锂离子电导率为10-5～10-2S/cm；
    可选地，所述磁性富锂态电极的孔隙率为20～50％。
  9. 一种如权利要求1-8任一项所述磁性富锂态电极的制备方法，所述制备方法包括以下步骤：
    将电极活性材料、磁性物质、导电剂、粘结剂和溶剂混合得到浆料，对集流体施加变向磁场，将所述浆料涂覆在集流体表面，得到富锂态电极。
  10. 如权利要求9所述的制备方法，其中，所述溶剂包括N-甲基吡咯烷酮；
    可选地，所述浆料的粘度为1～10Pa·s；
    可选地，所述变向磁场的强度为0.5～5T；
    可选地，所述涂覆的密度为150～200mg/cm2；
    可选地，所述涂覆后进行烘干；
    可选地，所述烘干的温度为50～80℃；
    可选地，所述烘干的时间为4～8h。
  11. 一种磁场辅助电化学脱嵌盐湖提锂的方法，所述方法包括以下步骤：
    (1)以如权利要求1-8任一项所述的磁性富锂态电极为正极，AgCl电极为负极，注入电解液恒压反应得到磁性贫锂态电极；
    (3)用阴离子交换膜将电解装置分隔成阳极室和阴极室，将磁性富锂态电极置于阳极室，磁性贫锂态电极置于阴极室，阴极室注入盐湖卤水，阳极室注入盐溶液，恒压通电的同时对电极施加磁场，电流低至150mA，结束反应。
  12. 如权利要求11所述的方法，其中，步骤(1)所述电解液包括氯化钠溶液和/或氯化钾溶液；
    可选地，所述电解液的浓度为0.05～0.1mol/L；
    可选地，所述恒压反应的电压为0.8～1.2V。
  13. 如权利要求11或12所述的方法，其中，步骤(2)所述盐溶液包括氯化钠溶液和/或氯化钾溶液；
    可选地，所述盐溶液的浓度为0.05～0.1mol/L。
  14. 如权利要求11-13任一项所述的方法，其中，步骤(2)所述恒压通电的电压为0.3～1.2V；
    可选地，所述磁场的强度为0.1～1T。
PCT/CN2023/101678 2023-06-21 2023-06-21 一种磁性富锂态电极及其制备方法和应用 Ceased WO2024259628A1 (zh)

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