WO2024254809A1 - 一种电化学脱嵌提锂的方法与应用 - Google Patents

一种电化学脱嵌提锂的方法与应用 Download PDF

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Publication number
WO2024254809A1
WO2024254809A1 PCT/CN2023/100347 CN2023100347W WO2024254809A1 WO 2024254809 A1 WO2024254809 A1 WO 2024254809A1 CN 2023100347 W CN2023100347 W CN 2023100347W WO 2024254809 A1 WO2024254809 A1 WO 2024254809A1
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lithium
extraction
electrode
optionally
electrolytic cell
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English (en)
French (fr)
Inventor
李爱霞
吴芷菁
谢英豪
余海军
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/CN2023/100347 priority Critical patent/WO2024254809A1/zh
Priority to CN202380009731.XA priority patent/CN117043368B/zh
Priority to ARP240101234A priority patent/AR132696A1/es
Publication of WO2024254809A1 publication Critical patent/WO2024254809A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds

Definitions

  • the present invention relates to the technical field of lithium extraction from salt lakes, for example, a method and application of electrochemical lithium extraction by deintercalation.
  • lithium-ion battery has attracted people's attention as an important direction of clean energy plan.
  • lithium resource is known as "energy metal of the 21st century".
  • Salt lake brine stores about 80% of the world's lithium resources, but the lithium concentration in salt lake brine is low, and how to extract lithium is a problem that still needs to be solved.
  • the commonly used methods for extracting lithium from salt lakes include evaporation precipitation, electrodialysis, nanofiltration, ion exchange, electrochemical adsorption, etc.
  • adsorption is a relatively effective method considering the characteristics of salt lake brine, but the preparation of ion adsorbents is difficult, desorption requires acidic conditions, the production process is difficult to be continuous, and the efficiency of lithium extraction is relatively low.
  • the electrochemical method of extracting lithium from salt lakes has attracted widespread attention from researchers due to its energy-saving, environmental protection and simple operation.
  • CN 105600807A discloses a method for electrochemically extracting lithium salt from brine with a high magnesium-to-lithium ratio.
  • a LiMn2O4 working electrode and a titanium mesh counter electrode are respectively connected to the positive and negative electrodes of a power source for charging, so that lithium ions can be extracted from LiMn2O4 to form a lithium ion sieve; the above electrode system is discharged in brine with a high magnesium-to- lithium ratio, so that lithium ions can be selectively embedded in the lithium ion sieve, and the charge-discharge cycle operation realizes the electrochemical extraction of lithium salt.
  • CN 112645362A provides a method for electrochemically extracting lithium from chloride-type lithium-containing brine to directly prepare lithium carbonate.
  • the chloride-type lithium-containing brine is used as an electrolyte, a lithium ion sieve electrode and a chloride ion capture electrode are used. They are used as positive and negative electrodes to form a primary battery.
  • the lithium ions in the brine are embedded in the lithium ion sieve.
  • the lithium salt recovery solution as the electrolyte
  • the lithium ion sieve electrode embedded with lithium ions and the inert electrode are used as the anode and cathode to construct an electrolytic cell.
  • the electrolytic cell is charged, the lithium ions are released into the lithium salt recovery solution.
  • the composition of brine is complex, and the impurities and miscellaneous ions in the brine will enter the electrode, blocking the mass transfer channel and affecting the lithium extraction effect.
  • the present disclosure provides a method and application of electrochemical deintercalation and lithium extraction, which adopts periodic voltage increase. While extracting lithium, a slight water electrolysis reaction occurs on the electrode through the change of voltage, so that micro-nano-level bubbles are generated inside the electrode. Combined with the ultrasonic effect, ultrasonic cavitation can be caused in the brine inside the electrode, disturbing the brine, promoting the flow of the brine, and unblocking the internal mass transfer channel blocked by impurities.
  • the present invention adopts the following technical solutions:
  • the present disclosure provides a method for electrochemical deintercalation and extraction of lithium, the method comprising the following steps:
  • the present invention adopts a periodic increase in voltage. While extracting lithium, a slight electrolysis reaction of water occurs on the electrode through the change of voltage, so that micro-nano bubbles are generated inside the electrode. With the help of ultrasonic action, ultrasonic cavitation can occur in the brine inside the electrode, disturbing the brine and promoting the flow of the brine. Unblock the internal mass transfer channels blocked by impurities.
  • the electrolytic cell for lithium extraction in step (1) comprises a cathode, an anode, an extraction solution and a recovery solution.
  • a monovalent cation membrane is used to separate the anode extraction solution and the cathode recovery solution.
  • the extract is salt lake brine.
  • the recovery liquid includes a KCl aqueous solution and/or a NaCl aqueous solution.
  • the concentration of the recovery liquid is 0.05-0.1 mol/L, for example, it can be 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L, 0.09 mol/L or 0.1 mol/L, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the cathode comprises a lithium-rich electrode
  • the lithium-rich electrode comprises a lithium-extracting active material
  • the preparation method of the lithium-rich electrode includes: mixing a lithium-extracting active material, a conductive agent and a binder to obtain a slurry, coating the obtained slurry on the surface of a current collector, and obtaining the lithium-rich electrode after drying.
  • the lithium-extracting active material includes any one of lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium titanate, or a combination of at least two of them.
  • Typical but non-limiting combinations include a combination of lithium manganate and lithium iron phosphate, a combination of lithium iron phosphate and lithium iron manganese phosphate, a combination of lithium iron manganese phosphate and lithium titanate, a combination of lithium manganate and lithium iron manganese phosphate, and a combination of lithium iron phosphate and lithium titanate.
  • the mass ratio of the lithium-extracting active material, the conductive agent and the binder is 90:5:5 to 70:15:15, for example, it can be 90:5:5, 85:7:8, 80:10:10, 75:12:13 or 70:15:15, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the conductive agent is a conventional conductive agent, and illustratively, may be conductive acetylene black and/or conductive carbon black.
  • the binder is a conventional binder, and illustratively, may be PTFE and/or PVDF.
  • the current collector is a conventional current collector, and illustratively, may be aluminum foil, carbon cloth, titanium mesh or carbon paper.
  • the coating surface density is 5-25 mg/cm 2 , such as 5 mg/cm 2 , 10 mg/cm 2 , 15 mg/cm 2 , 20 mg/cm 2 or 25 mg/cm 2 , but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the drying temperature is 50-70°C, for example, 50°C, 55°C, 60°C, 65°C or 70°C, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the drying time is 8 to 12 hours, for example, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the anode is a lithium-deficient electrode.
  • the lithium-poor electrode refers to an electrode from which some lithium ions have been deintercalated relative to the lithium-rich electrode, and the lithium content in the lithium-poor electrode is lower than that in the lithium-rich electrode.
  • the method for preparing the lithium-poor electrode includes: using the lithium-rich electrode as a cathode and a silver chloride electrode as an anode to construct an electrolytic cell, and applying constant voltage to the electrolytic cell to remove lithium, and the lithium-rich electrode after delithiation is the lithium-poor electrode.
  • the electrolyte in the electrolytic cell includes a KCl aqueous solution and/or a NaCl aqueous solution.
  • the concentration of the electrolyte is 0.05-0.1 mol/L, for example, it can be 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L, 0.09 mol/L or 0.1 mol/L, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the constant voltage power supply voltage is 0.3 to 1.3 V, for example, 0.3 V, 0.5 V, 0.7 V, 1 V or 1.3 V, but is not limited to the listed values. Other values not listed in the value range are also Applicable.
  • the constant voltage is energized to a current of less than 0.3 mA, for example, 0.3 mA, 0.2 mA, 0.1 mA, 0.05 mA or 0.01 mA, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the power-on in step (2) is a constant voltage power-on with a voltage of 0.3 to 1.3 V, for example, 0.3 V, 0.5 V, 0.7 V, 1 V or 1.3 V, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the premise of periodically increasing the voltage in step (2) is that during the process of power-on lithium extraction, the current drops below 0.3 mA, for example, it can be 0.3 mA, 0.2 mA, 0.1 mA, 0.05 mA or 0.01 mA, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the voltage in step (2) is increased to 1.3-1.8V, for example, 1.3V, 1.4V, 1.5V, 1.6V, 1.7V or 1.8V, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the time for increasing the voltage in step (2) is 1 to 5 minutes, for example, 1 minute, 2 minutes, 3 minutes, 4 minutes or 5 minutes, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the frequency of applying ultrasound in step (2) is 20 to 40 Hz, for example, 20 Hz, 25 Hz, 30 Hz, 35 Hz or 40 Hz, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the number of periodicities is ⁇ 1, for example, 1, 3, 5, 10 or 20. However, it is not limited to the listed values, and other values not listed within the numerical range are also applicable.
  • the current no longer changes, that is, the power is stopped.
  • the process further includes exchanging the positions of the cathode and the anode, and repeating the operation steps of step (2).
  • the repeated steps are: applying power to the electrolytic cell to extract lithium, and during the lithium extraction process, periodically increasing the voltage and applying ultrasound to the electrolytic cell.
  • the number of repetitions is ⁇ 1, for example, it can be 1, 3, 5, 10 or 20, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the method further includes collecting the recovery liquid and determining the concentration of lithium ions in the recovery liquid.
  • the method includes:
  • step (2) using the lithium-rich electrode of step (1) as a cathode, the silver chloride electrode as an anode, and the electrolyte comprising a KCl aqueous solution and/or a NaCl aqueous solution with a concentration of 0.05 to 0.1 mol/L, to construct an electrolytic cell, applying a constant voltage of 0.3 to 1.3 V to the electrolytic cell for lithium removal, and the process ends when the current is less than 0.3 mA, and the lithium-rich electrode after the process ends is the obtained lithium-poor electrode;
  • step (3) using the lithium-rich electrode obtained in step (1) as a cathode and the lithium-poor electrode obtained in step (2) as an anode, separating the anode extract and the cathode recovery liquid by a monovalent cation membrane, wherein the extract is salt lake brine and the recovery liquid is a 0.05-0.1 mol/L KCl aqueous solution and/or a NaCl aqueous solution, to construct a lithium extraction electrolytic cell;
  • step (3) (4) applying a constant voltage of 0.3 to 1.3 V to the electrolytic cell for lithium extraction in step (3) to extract lithium.
  • the voltage is increased to 1.3 to 1.8 V and 20 to 40 Hz ultrasound is applied to the electrolytic cell for 1 to 5 min.
  • lithium extraction is continued at a constant voltage of 0.3 to 1.3 V.
  • the above treatment is repeated until the current does not change and the power is stopped;
  • step (4) exchanging the positions of the anode and the cathode, repeating the operation of step (4) for a number of times ⁇ 1, and then collecting the recovered liquid to complete the electrochemical deintercalation and lithium extraction.
  • the present disclosure provides an application of the method according to the first aspect, wherein the method is used for extracting lithium from brine.
  • the present invention adopts the method of increasing voltage periodically. While extracting lithium, a slight water electrolysis reaction occurs on the electrode through the change of voltage, so that bubbles of micro-nano level are generated inside the electrode.
  • the synergistic effect of ultrasound can cause ultrasonic cavitation of the brine inside the electrode, disturb the brine, promote the flow of the brine, and dredge the internal mass transfer channel blocked by impurities.
  • FIG1 is a mechanism diagram of the electrochemical deintercalation and lithium extraction method.
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, the method comprising:
  • step (2) using the lithium-rich electrode of step (1) as a cathode, the silver chloride electrode as an anode, and the electrolyte comprising a KCl aqueous solution with a concentration of 0.08 mol/L, to construct an electrolytic cell, applying a constant voltage of 0.8 V to the electrolytic cell for lithium removal, and the process ends when the current is less than 0.3 mA, and the lithium-rich electrode after the process ends is the obtained lithium-poor electrode;
  • step (3) using the lithium-rich electrode obtained in step (1) as a cathode and the lithium-poor electrode obtained in step (2) as an anode, separating the anode extract and the cathode recovery liquid by a monovalent cation membrane, wherein the extract is salt lake brine and the recovery liquid is a 0.08 mol/L KCl aqueous solution, to construct a lithium extraction electrolytic cell;
  • step (3) (4) applying a constant voltage of 0.8 V to the electrolytic cell used for lithium extraction in step (3) to extract lithium.
  • the voltage is increased to 1.5 V and 30 Hz ultrasound is applied to the electrolytic cell for 2 min.
  • lithium extraction is continued at a constant voltage of 0.8 V.
  • the above treatment is repeated until the current does not change, and the power is stopped;
  • step (4) exchanging the positions of the anode and the cathode, repeating the operation of step (4) three times, and then collecting the recovered liquid to complete the electrochemical deintercalation and lithium extraction.
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, the method comprising:
  • lithium titanate, conductive carbon black and PVDF are mixed in a mass ratio of 90:5:5 to obtain a slurry, the obtained slurry is coated on the surface of the current collector with a coating surface density of 5 mg/cm 2 , and after drying at 70° C. for 8 h, the lithium-rich electrode is obtained;
  • step (2) using the lithium-rich electrode of step (1) as a cathode, the silver chloride electrode as an anode, and the electrolyte comprising a 0.05 mol/L NaCl aqueous solution to construct an electrolytic cell, applying a constant voltage of 0.3 V to the electrolytic cell for lithium removal, and stopping the process when the current is less than 0.3 mA.
  • the lithium-rich electrode after the process is completed is the obtained lithium-poor electrode;
  • step (3) using the lithium-rich electrode obtained in step (1) as a cathode and the lithium-poor electrode obtained in step (2) as an anode, separating the anode extract and the cathode recovery liquid by a monovalent cation membrane, wherein the extract is salt lake brine and the recovery liquid is a 0.05 mol/L NaCl aqueous solution, to construct a lithium extraction electrolytic cell;
  • step (3) (4) applying a constant voltage of 0.3 V to the electrolytic cell used for lithium extraction in step (3) to extract lithium.
  • the voltage is increased to 1.3 V and 20 Hz ultrasound is applied to the electrolytic cell for 15 min.
  • lithium extraction is continued at a constant voltage of 0.3 V.
  • the above treatment is repeated until the current does not change, and the power is stopped;
  • step (4) exchanging the positions of the anode and the cathode, repeating the operation of step (4) once, and then collecting the recovered liquid to complete the electrochemical deintercalation and lithium extraction.
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, the method comprising:
  • step (2) using the lithium-rich electrode of step (1) as a cathode, the silver chloride electrode as an anode, and the electrolyte comprising a 0.1 mol/L KCl aqueous solution to construct an electrolytic cell, applying a constant voltage of 1.5 V to the electrolytic cell for lithium removal, and stopping the process when the current is less than 0.3 mA.
  • the lithium-rich electrode after the process is completed is the obtained lithium-poor electrode;
  • step (3) using the lithium-rich electrode obtained in step (1) as the cathode and the lithium-poor electrode obtained in step (2) as the The anode and the monovalent cation membrane separate the extracting solution of the anode and the recovering solution of the cathode, wherein the extracting solution is salt lake brine and the recovering solution is a 0.1 mol/L KCl aqueous solution, and an electrolytic cell for extracting lithium is constructed;
  • step (3) (4) applying a constant voltage of 1.3 V to the electrolytic cell used for lithium extraction in step (3) to extract lithium.
  • the voltage is increased to 1.8 V and 40 Hz ultrasound is applied to the electrolytic cell for 1 min.
  • lithium extraction is continued at a constant voltage of 1.3 V.
  • the above treatment is repeated until the current does not change, and the power is stopped;
  • step (4) exchanging the positions of the anode and the cathode, repeating the operation of step (4) twice, and then collecting the recovered liquid to complete the electrochemical deintercalation and lithium extraction.
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, which differs from Embodiment 1 in that the voltage is increased to 2V in step (4).
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, which differs from Embodiment 1 in that the voltage is increased to 1.25V in step (4).
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, which differs from Embodiment 1 in that the frequency of applying ultrasound in step (4) is 50 Hz.
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, which differs from Embodiment 1 in that the frequency of applying ultrasound in step (4) is 10 Hz.
  • This embodiment provides a method for electrochemical deintercalation and extraction of lithium, which differs from Embodiment 1 in that the lithium-poor electrode in step (3) is replaced by a silver chloride electrode.
  • This comparative example provides a method for electrochemical deintercalation and extraction of lithium, which differs from Example 1 in that in step (4), when the current is lower than 0.3 mA, the voltage is not changed and only ultrasonic treatment is applied.
  • This comparative example provides a method for electrochemical deintercalation and extraction of lithium, which differs from Example 1 in that in step (4), when the current is lower than 0.3 mA, only the voltage is changed, and no ultrasonic treatment is applied.
  • This comparative example provides a method for electrochemical deintercalation and extraction of lithium, which differs from Example 1 in that in step (4), when the current is lower than 0.3 mA, the voltage is not changed and ultrasonic treatment is not applied.
  • the present disclosure adopts a periodic voltage increase. While extracting lithium, a slight water electrolysis reaction occurs on the electrode through the change in voltage, so that micro-nano-level bubbles are generated inside the electrode. In conjunction with the ultrasonic effect, ultrasonic cavitation can occur in the brine inside the electrode, disturbing the brine, promoting the flow of the brine, and unblocking the internal mass transfer channel blocked by impurities.

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Abstract

本公开涉及一种电化学脱嵌提锂的方法与应用，所述方法包括如下步骤：(1)构建提锂的电解池；(2)向所述电解池通电进行提锂，提锂的过程中，周期性地提高电压并向电解池中施加超声，完成所述电化学脱嵌提锂。采用周期性提高电压，在提锂的同时，通过电压的变化使得极片上发生轻微的电解水反应，使得电极内部产生微纳米级别的气泡，协同超声作用，可以使电极内部卤水均发生超声空化，扰动卤水，促进卤水的流动，并且疏通被杂质相堵塞的内部传质通道。

Description

一种电化学脱嵌提锂的方法与应用 技术领域
本公开属于盐湖提锂技术领域，例如一种电化学脱嵌提锂的方法与应用。
背景技术
随着经济的发展，锂离子电池作为清洁能源计划的重要方向受到人们的关注。锂资源作为一种重要的战略和经济资源，被誉为“21世纪的能源金属”，随着锂离子电池的快速发展，全球锂资源需求量持续上升，锂资源的开发成为全世界的关注重点。盐湖卤水中储存着全球约80％的锂资源，但盐湖卤水中锂浓度较低，如何将锂提取出来是一个仍需解决的难题。
目前，常用的盐湖提锂方法有蒸发沉淀法、电渗析法、纳滤法、离子交换法、电化学吸附法等。其中针对盐湖卤水的特点，吸附法是一个比较有效的方法，但离子吸附剂制备困难，脱附需要酸性条件，生产过程难以连续，提锂效率较为低下。
利用电化学法进行盐湖提锂的方式，由于其具有节能、环保和操作简单的特点，受到研究人员的广泛关注。
CN 105600807A公开了一种从高镁锂比盐水中电化学提取锂盐的方法，在LiCl溶液中，将LiMn2O4工作电极和钛网对电极分别与电源正负极连接充电可将锂离子从LiMn2O4中脱出形成锂离子筛；将上述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。
CN 112645362A提供了一种从氯化物型含锂盐水中电化学提锂直接制备碳酸锂的方法。以氯化物型含锂盐水为电解液，锂离子筛电极和氯离子捕获电极 分别作为正负极构成原电池，原电池放电将盐水中锂离子嵌入锂离子筛中；以锂盐回收溶液为电解液，嵌入锂离子的锂离子筛电极和惰性电极分别作为阳极和阴极构建电解池，电解池充电将锂离子脱出到锂盐回收溶液中。但卤水成分复杂，卤水中的杂质和杂离子会进入电极内部，堵塞传质通道，影响提锂效果。
因此，针对相关技术中卤水中杂质相进入电极内部，从而堵塞传质通道的问题，如何进行改善，是亟需解决的。
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。
鉴于相关技术中存在的问题，本公开提供了一种电化学脱嵌提锂的方法与应用，采用周期性提高电压，在提锂的同时，通过电压的变化使得极片上发生轻微的电解水反应，使得电极内部产生微纳米级别的气泡，协同超声作用，可以使电极内部卤水均发生超声空化，扰动卤水，促进卤水的流动，并且疏通被杂质相堵塞的内部传质通道。
为达此目的，本公开采用以下技术方案：
第一方面，本公开提供了一种电化学脱嵌提锂的方法，所述方法包括如下步骤：
(1)构建提锂的电解池；
(2)向所述电解池通电进行提锂，提锂的过程中，周期性地提高电压并向电解池中施加超声，完成所述电化学脱嵌提锂。
本公开中采用周期性提高电压，在提锂的同时，通过电压的变化使得极片上发生轻微的电解水反应，使得电极内部产生微纳米级别的气泡，协同超声作用，可以使电极内部卤水均发生超声空化，扰动卤水，促进卤水的流动，并且 疏通被杂质相堵塞的内部传质通道。
在一个实施例中，步骤(1)所述提锂的电解池包括阴极、阳极、提取液和回收液。
在一个实施例中，步骤(1)所述电解池中采用单价阳离子膜隔开阳极的提取液和阴极的回收液。
在一个实施例中，所述提取液为盐湖卤水。
在一个实施例中，所述回收液包括KCl水溶液和/或NaCl水溶液。
在一个实施例中，所述回收液的浓度为0.05～0.1mol/L，例如可以是0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L、0.09mol/L或0.1mol/L，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，所述阴极包括富锂态电极，所述富锂态电极中包括提锂活性物质。
在一个实施例中，所述富锂态电极的制备方式包括：混合提锂活性物质、导电剂和粘结剂，得到浆料，所得浆料涂布于集流体表面，经干燥后，得到所述富锂态电极。
在一个实施例中，所述提锂活性物质包括锰酸锂、磷酸铁锂、磷酸锰铁锂或钛酸锂中的任意一种或至少两种的组合，典型但非限制性的组合包括锰酸锂和磷酸铁锂的组合，磷酸铁锂和磷酸锰铁锂的组合，磷酸锰铁锂和钛酸锂的组合，锰酸锂和磷酸锰铁锂的组合，磷酸铁锂和钛酸锂的组合。
在一个实施例中，所述提锂活性物质、导电剂和粘结剂的质量比为90:5:5～70:15:15，例如可以是90:5:5、85:7:8、80:10:10、75:12:13或70:15:15，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
所述导电剂为常规导电剂，示例性的，可以是导电乙炔黑和/或导电炭黑。
所述粘结剂为常规粘结剂，示例性的，可以是PTFE和/或PVDF。
所述集流体为常规集流体，示例性的，可以是铝箔、碳布、钛网或碳纸。
在一个实施例中，所述涂布的面密度为5～25mg/cm2，例如可以是5mg/cm2、10mg/cm2、15mg/cm2、20mg/cm2或25mg/cm2，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，所述干燥的温度为50～70℃，例如可以是50℃、55℃、60℃、65℃或70℃，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，所述干燥的时间为8～12h，例如可以是8h、9h、10h、11h或12h，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，所述阳极为贫锂态电极。
本公开中贫锂态电极指的是相对于富锂态电极，有部分锂离子脱嵌出去后的电极，贫锂态电极中的锂含量低于富锂态电极。
在一个实施例中，所述贫锂态电极的制备方法包括：以所述富锂态电极为阴极，氯化银电极为阳极，构建电解池，向所述电解池恒压通电进行脱锂，所述脱锂后的富锂态电极为所述贫锂态电极。
在一个实施例中，所述电解池中的电解液包括KCl水溶液和/或NaCl水溶液。
在一个实施例中，所述电解液的浓度为0.05～0.1mol/L，例如可以是0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L、0.09mol/L或0.1mol/L，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，所述恒压通电的电压为0.3～1.3V，例如可以是0.3V、0.5V、0.7V、1V或1.3V，但不限于所列举的数值，数值范围内其它未列举的数值同样 适用。
在一个实施例中，所述恒压通电至电流0.3mA以下，例如可以是0.3mA、0.2mA、0.1mA、0.05mA或0.01mA，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，步骤(2)所述通电为恒电压通电，电压为0.3～1.3V，例如可以是0.3V、0.5V、0.7V、1V或1.3V，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，步骤(2)所述周期性提高电压的前提为：通电提锂过程中，电流降至0.3mA以下，例如可以是0.3mA、0.2mA、0.1mA、0.05mA或0.01mA，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，步骤(2)所述提高电压至1.3～1.8V，例如可以是1.3V、1.4V、1.5V、1.6V、1.7V或1.8V，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
提高电压过高，容易引入杂质，提高电压过低，微气泡产生效率过低。
在一个实施例中，步骤(2)所述提高电压的时间为1～5min，例如可以是1min、2min、3min、4min或5min，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，步骤(2)所述施加超声的频率为20～40Hz，例如可以是20Hz、25Hz、30Hz、35Hz或40Hz，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
当施加超声的频率过高，会损害电极，当施加的频率过低，达不到超声空化的效果。
在一个实施例中，所述周期性的次数≥1，例如可以是1、3、5、10或20， 但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，当提高电压并向电解池中施加超声后，电流不再发生变化，即停止通电。
在一个实施例中，结束步骤(2)所述通电进行提锂后，还包括交换阴极和阳极的位置，重复步骤(2)的操作步骤。
在一个实施例中，所述重复的步骤为：向电解池通电进行提锂，提锂的过程中，周期性地提高电压并向电解池中施加超声。
在一个实施例中，所述重复的次数≥1，例如可以是1、3、5、10或20，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
在一个实施例中，完成步骤(2)后，还包括收集回收液，测定所述回收液中锂离子的浓度。
作为本公开第一方面所述方法的一种可选技术方案，所述方法包括：
(1)混合质量比为90:5:5～70:15:15的提锂活性物质、导电剂和粘结剂，得到浆料，所得浆料涂布于集流体表面，涂布的面密度为5～25mg/cm2，经50～70℃干燥8～12h后，得到所述富锂态电极；
(2)以步骤(1)所述富锂态电极为阴极，氯化银电极为阳极，电解液包括浓度为0.05～0.1mol/L的KCl水溶液和/或NaCl水溶液，构建电解池，向所述电解池恒压通电0.3～1.3V进行脱锂，通电至电流0.3mA以下后结束，结束后的富锂态电极为所得贫锂态电极；
(3)以步骤(1)所得富锂态电极为阴极，以步骤(2)所得贫锂态电极为阳极，单价阳离子膜隔开阳极的提取液和阴极的回收液，所述提取液为盐湖卤水，所述回收液为0.05～0.1mol/L的KCl水溶液和/或NaCl水溶液，构建提锂的电解池；
(4)向步骤(3)所述提锂的电解池恒压通电0.3～1.3V进行提锂，提锂的过程中，电流降至0.3mA以下后，提高电压至1.3～1.8V并向电解池中施加20～40Hz的超声，时间为1～5min，所述处理后继续在0.3～1.3V的恒电压下提锂，当电流低至0.3mA时重复上述处理，直至电流不发生变化，停止通电；
(5)交换阳极和阴极的位置，重复步骤(4)的操作，次数≥1，再收集回收液，完成所述电化学脱嵌提锂。
第二方面，本公开提供了一种根据第一方面所述方法的应用，所述方法用于卤水提锂。
由以上技术方案，本公开的有益效果如下：
本公开中采用周期性提高电压，在提锂的同时，通过电压的变化使得极片上发生轻微的电解水反应，使得电极内部产生微纳米级别的气泡，协同超声作用，可以使电极内部卤水均发生超声空化，扰动卤水，促进卤水的流动，并且疏通被杂质相堵塞的内部传质通道。
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是所述电化学脱嵌提锂方法的机理图。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本公开的技术方案。但下述的实例仅仅是本公开的简易例子，并不代表或限制本公开的权利保护范围，本公开的保护范围以权利要求书为准。
实施例1
本实施例提供一种电化学脱嵌提锂的方法，所述方法包括：
(1)混合质量比为80:10:10的锰酸锂、导电乙炔黑和PVDF，得到浆料，所得浆料涂布于集流体表面，涂布的面密度为15mg/cm2，经60℃干燥10h后，得到所述富锂态电极；
(2)以步骤(1)所述富锂态电极为阴极，氯化银电极为阳极，电解液包括浓度为0.08mol/L的KCl水溶液，构建电解池，向所述电解池恒压通电0.8V进行脱锂，通电至电流0.3mA以下后结束，结束后的富锂态电极为所得贫锂态电极；
(3)以步骤(1)所得富锂态电极为阴极，以步骤(2)所得贫锂态电极为阳极，单价阳离子膜隔开阳极的提取液和阴极的回收液，所述提取液为盐湖卤水，所述回收液为0.08mol/L的KCl水溶液，构建提锂的电解池；
(4)向步骤(3)所述提锂的电解池恒压通电0.8V进行提锂，提锂的过程中，电流降至0.3mA以下后，提高电压至1.5V并向电解池中施加30Hz的超声，时间为2min，所述处理后继续在0.8V的恒电压下提锂，当电流低至0.3mA时重复上述处理，直至电流不发生变化，停止通电；
(5)交换阳极和阴极的位置，重复步骤(4)的操作3次，再收集回收液，完成所述电化学脱嵌提锂。
实施例2
本实施例提供一种电化学脱嵌提锂的方法，所述方法包括：
(1)混合质量比为90:5:5的钛酸锂、导电炭黑和PVDF，得到浆料，所得浆料涂布于集流体表面，涂布的面密度为5mg/cm2，经70℃干燥8h后，得到所述富锂态电极；
(2)以步骤(1)所述富锂态电极为阴极，氯化银电极为阳极，电解液包括浓度为0.05mol/L的NaCl水溶液，构建电解池，向所述电解池恒压通电0.3V进行脱锂，通电至电流0.3mA以下后结束，结束后的富锂态电极为所得贫锂态电极；
(3)以步骤(1)所得富锂态电极为阴极，以步骤(2)所得贫锂态电极为阳极，单价阳离子膜隔开阳极的提取液和阴极的回收液，所述提取液为盐湖卤水，所述回收液为0.05mol/L的NaCl水溶液，构建提锂的电解池；
(4)向步骤(3)所述提锂的电解池恒压通电0.3V进行提锂，提锂的过程中，电流降至0.3mA以下后，提高电压至1.3V并向电解池中施加20Hz的超声，时间为15min，所述处理后继续在0.3V的恒电压下提锂，当电流低至0.3mA时重复上述处理，直至电流不发生变化，停止通电；
(5)交换阳极和阴极的位置，重复步骤(4)的操作1次，再收集回收液，完成所述电化学脱嵌提锂。
实施例3
本实施例提供一种电化学脱嵌提锂的方法，所述方法包括：
(1)混合质量比为70:15:15的磷酸锰铁锂、导电乙炔黑和PVDF，得到浆料，所得浆料涂布于集流体表面，涂布的面密度为25mg/cm2，经70℃干燥8h后，得到所述富锂态电极；
(2)以步骤(1)所述富锂态电极为阴极，氯化银电极为阳极，电解液包括浓度为0.1mol/L的KCl水溶液，构建电解池，向所述电解池恒压通电1.5V进行脱锂，通电至电流0.3mA以下后结束，结束后的富锂态电极为所得贫锂态电极；
(3)以步骤(1)所得富锂态电极为阴极，以步骤(2)所得贫锂态电极为 阳极，单价阳离子膜隔开阳极的提取液和阴极的回收液，所述提取液为盐湖卤水，所述回收液为0.1mol/L的KCl水溶液，构建提锂的电解池；
(4)向步骤(3)所述提锂的电解池恒压通电1.3V进行提锂，提锂的过程中，电流降至0.3mA以下后，提高电压至1.8V并向电解池中施加40Hz的超声，时间为1min，所述处理后继续在1.3V的恒电压下提锂，当电流低至0.3mA时重复上述处理，直至电流不发生变化，停止通电；
(5)交换阳极和阴极的位置，重复步骤(4)的操作2次数，再收集回收液，完成所述电化学脱嵌提锂。
实施例4
本实施例提供一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)所述提高电压至2V。
实施例5
本实施例提供一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)所述提高电压至1.25V。
实施例6
本实施例提供一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)所述施加超声的频率为50Hz。
实施例7
本实施例提供一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)所述施加超声的频率为10Hz。
实施例8
本实施例提供了一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(3)所述贫锂态电极替换为氯化银电极。
对比例1
本对比例提供了一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)中当电流低于0.3mA时不改变电压，仅施加超声处理。
对比例2
本对比例提供了一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)中当电流低于0.3mA时仅改变电压，不施加超声处理。
对比例3
本对比例提供了一种电化学脱嵌提锂的方法，与实施例1的区别为：步骤(4)中当电流低于0.3mA时不改变电压，不施加超声处理。
上述方法所得回收液中，利用ICP测试锂离子的浓度，测试结果如表1所示。
表1

结合图1所示的机理，本公开中采用周期性提高电压，在提锂的同时，通过电压的变化使得极片上发生轻微的电解水反应，使得电极内部产生微纳米级别的气泡，协同超声作用，可以使电极内部卤水均发生超声空化，扰动卤水，促进卤水的流动，并且疏通被杂质相堵塞的内部传质通道。

Claims (14)

  1. 一种电化学脱嵌提锂的方法，所述方法包括如下步骤：
    (1)构建提锂的电解池；
    (2)向所述电解池通电进行提锂，提锂的过程中，周期性地提高电压并向电解池中施加超声，完成所述电化学脱嵌提锂。
  2. 根据权利要求1所述的电化学脱嵌提锂的方法，其中，步骤(1)所述提锂的电解池包括阴极、阳极、提取液和回收液；
    可选地，步骤(1)所述电解池中采用单价阳离子膜隔开提取液和回收液；
    可选地，所述阳极置于提取液中，阴极置于回收液中；
    可选地，所述提取液为盐湖卤水；
    可选地，所述回收液包括KCl水溶液和/或NaCl水溶液。
  3. 根据权利要求2所述的电化学脱嵌提锂的方法，其中，所述回收液的浓度为0.05～0.1mol/L。
  4. 根据权利要求2或3所述的电化学脱嵌提锂的方法，其中，所述阴极包括富锂态电极；
    可选地，所述富锂态电极中包括提锂活性物质；
    可选地，所述提锂活性物质包括锰酸锂、磷酸铁锂、磷酸锰铁锂或钛酸锂中的任意一种或至少两种的组合。
  5. 根据权利要求4所述的电化学脱嵌提锂的方法，其中，所述富锂态电极的制备方式包括：混合提锂活性物质、导电剂和粘结剂，得到浆料，所得浆料涂布于集流体表面，经干燥后，得到所述富锂态电极；
    可选地，所述提锂活性物质、导电剂和粘结剂的质量比为90:5:5～70:15:15；
    可选地，所述涂布的面密度为5～25mg/cm2；
    可选地，所述干燥的温度为50～70℃；
    可选地，所述干燥的时间为8～12h。
  6. 根据权利要求2-5任一项所述的电化学脱嵌提锂的方法，其中，所述阳极为贫锂态电极。
  7. 根据权利要求6所述的电化学脱嵌提锂的方法，其中，所述贫锂态电极的制备方法包括：以所述富锂态电极为阴极，氯化银电极为阳极，构建电解池，向所述电解池恒压通电进行脱锂，所述脱锂后的富锂态电极为所述贫锂态电极；
    可选地，所述电解池中的电解液包括KCl水溶液和/或NaCl水溶液；
    可选地，所述电解液的浓度为0.05～0.1mol/L；
    可选地，所述恒压通电的电压为0.3～1.3V；
    可选地，所述恒压通电至电流0.3mA以下。
  8. 根据权利要求1-7任一项所述的电化学脱嵌提锂的方法，其中，步骤(2)所述通电为恒电压通电，电压为0.3～1.3V；
    可选地，步骤(2)所述周期性提高电压的前提为：通电提锂过程中，电流降至0.3mA以下；
    可选地，步骤(2)所述提高电压至1.3～1.8V；
    可选地，步骤(2)所述提高电压的时间为1～5min。
  9. 根据权利要求1-8任一项所述的电化学脱嵌提锂的方法，其中，步骤(2)所述施加超声的频率为20～40Hz；
    可选地，所述周期性的次数≥1；
    可选地，当提高电压并向电解池中施加超声后，电流不再发生变化，即停止通电。
  10. 根据权利要求1-9任一项所述的电化学脱嵌提锂的方法，其中，结束步骤(2)所述通电进行提锂后，还包括交换阴极和阳极的位置，重复步骤(2) 的操作步骤。
  11. 根据权利要求10所述的电化学脱嵌提锂的方法，其中，所述重复的步骤为：向电解池通电进行提锂，提锂的过程中，周期性地提高电压并向电解池中施加超声；
    可选地，所述重复的次数≥1。
  12. 根据权利要求1-11任一项所述的电化学脱嵌提锂的方法，其中，完成步骤(2)后，还包括收集回收液，测定所述回收液中锂离子的浓度。
  13. 根据权利要求1-12任一项所述的电化学脱嵌提锂的方法，其中，所述方法包括：
    (1)混合质量比为90:5:5～70:15:15的提锂活性物质、导电剂和粘结剂，得到浆料，所得浆料涂布于集流体表面，涂布的面密度为5～25mg/cm2，经50～70℃干燥8～12h后，得到富锂态电极；
    (2)以步骤(1)所述富锂态电极为阴极，氯化银电极为阳极，电解液包括浓度为0.05～0.1mol/L的KCl水溶液和/或NaCl水溶液，构建电解池，向所述电解池恒压通电0.3～1.3V进行脱锂，通电至电流0.3mA以下后结束，结束后的富锂态电极作为贫锂态电极；
    (3)以步骤(1)所述富锂态电极为阴极，以步骤(2)所述贫锂态电极为阳极，单价阳离子膜隔开阳极的提取液和阴极的回收液，所述提取液为盐湖卤水，所述回收液为0.05～0.1mol/L的KCl水溶液和/或NaCl水溶液，构建提锂的电解池；
    (4)向步骤(3)所述提锂的电解池恒压通电0.3～1.3V进行提锂，提锂的过程中，电流降至0.3mA以下后，提高电压至1.3～1.8V并向电解池中施加20～40Hz的超声，时间为1～5min，在0.3～1.3V的恒电压下提锂，当电流低至 0.3mA时重复上述处理，直至电流不发生变化，停止通电；
    (5)交换阳极和阴极的位置，重复步骤(4)的操作，次数≥1，再收集回收液，完成所述电化学脱嵌提锂。
  14. 一种根据权利要求1-13任一项所述方法的应用，其中，所述方法用于卤水提锂。
PCT/CN2023/100347 2023-06-15 2023-06-15 一种电化学脱嵌提锂的方法与应用 Ceased WO2024254809A1 (zh)

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