WO2024036698A1 - 锂离子电池的电解液的回收处理方法 - Google Patents

锂离子电池的电解液的回收处理方法 Download PDF

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WO2024036698A1
WO2024036698A1 PCT/CN2022/120625 CN2022120625W WO2024036698A1 WO 2024036698 A1 WO2024036698 A1 WO 2024036698A1 CN 2022120625 W CN2022120625 W CN 2022120625W WO 2024036698 A1 WO2024036698 A1 WO 2024036698A1
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extraction
electrolyte
lithium
molecular sieve
entrainer
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French (fr)
Inventor
李爱霞
张学梅
余海军
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 ES202390169A priority Critical patent/ES3007218B2/es
Priority to US18/288,725 priority patent/US12525662B2/en
Priority to HU2300328A priority patent/HUP2300328A1/hu
Priority to DE112022002886.6T priority patent/DE112022002886T5/de
Priority to GB2313100.6A priority patent/GB2621712B/en
Priority to MA64611A priority patent/MA64611A1/fr
Publication of WO2024036698A1 publication Critical patent/WO2024036698A1/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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to the technical field of battery recycling, and specifically, to a method for recycling electrolyte of lithium-ion batteries.
  • Waste lithium batteries are showing an explosive and cumulative growth trend, and their cumulative effects on health, environment, and safety hazards are multiplying. Recycling and reusing used lithium batteries can improve environmental pollution, safety and other problems caused by the accumulation of used lithium batteries; in particular, the electrolyte of used lithium batteries contains toxic and harmful substances, which are prone to side effects in the natural environment. The reaction causes secondary pollution. Recycling the electrolyte of used lithium batteries can effectively improve the secondary pollution problem.
  • the electrolyte recovery methods for lithium batteries mainly use organic solvent extraction processes and supercritical CO 2 extraction processes.
  • the organic solvent extraction process mainly introduces a solvent with similar dissolving properties to the electrolyte, soaks the broken battery, transfers the electrolyte into the solvent, and then separates the solvent from the electrolyte.
  • the disadvantage of this method is the high cost of the solvent.
  • the extraction product separation process is complex, energy consumption is high, and the extraction product has problems such as solvent residues;
  • the introduction of supercritical CO 2 to extract the battery electrolyte can avoid problems such as solvent residues, but supercritical
  • the polarity of CO 2 is weak, and the mutual solubility effect with the electrolyte needs to be improved.
  • the recovery technology of the electrolyte is difficult, and it is difficult to obtain electrolyte recovery products that can be directly reused.
  • the object of the present invention is to provide a method for recycling electrolyte of lithium-ion batteries, which can obtain an electrolyte recycling product that can be directly reused.
  • the present invention is implemented as follows:
  • the invention provides a method for recycling electrolyte of lithium-ion batteries, which includes:
  • S4 Collect the extraction product through a cryogenic device and use Type lithiated molecular sieve adsorbs water in the extraction product, uses weakly basic anion exchange resin to adsorb HF in the extraction product, uses Type lithiated molecular sieve adsorbs organic acids and alcohols in the extraction product.
  • type lithiated molecular sieve using LiCl ethanol solution Type molecular sieves are prepared by lithiation treatment; and/or,
  • Type molecular sieves are prepared by lithiation treatment.
  • the concentration of the LiCl ethanol solution is 1.8-2.2 mol/L; the number of lithiation treatments is 5-10 times.
  • the entraining agent includes cyclic carbonates.
  • the entraining agent further includes N,N-dimethylformamide.
  • the mass ratio of cyclic carbonates and N,N-dimethylformamide is 3-4:1.
  • extraction includes static extraction and dynamic extraction.
  • the entrainer is added at a flow rate of 8-10% of the CO2 flow rate at the beginning of dynamic extraction.
  • the static extraction time is 18-22 min, and the dynamic extraction time is 35-55 min.
  • the extraction pressure is 21-35MPa and the temperature is 40-55°C.
  • the method for recycling and processing the electrolyte of the lithium-ion battery uses supercritical CO 2 extraction.
  • Type lithiated molecular sieve adsorbs water in the extraction product, uses weakly basic anion exchange resin to adsorb HF in the extraction product, uses Type lithiated molecular sieve adsorbs organic acids and alcohols in the extraction product; in this way, through type lithiated molecular sieves, weakly basic anion exchange resins, and Lithium-type molecular sieves adsorb water, HF, organic acids and alcohols in the extraction product to obtain electrolyte recovery products that can be directly reused.
  • Figure 1 is a graph showing the relationship between the cyclic carbonate entrainer and the electrolyte extraction efficiency of the present invention without adding an entrainer;
  • Figure 2 is a graph showing the relationship between different mass ratios of cyclic carbonates and N,N-dimethylformamide mixed entrainers and electrolyte extraction efficiency in the present invention
  • Figure 3 is a graph showing the relationship between different types of entrainers and their dosage and electrolyte extraction efficiency in the present invention.
  • the invention provides a method for recycling electrolyte of lithium-ion batteries, which can be used to recycle the electrolyte of waste lithium-ion batteries, including:
  • Type lithiated molecular sieve adsorbs water in the extraction product, and uses a weakly basic anion exchange resin (weakly basic anion exchange membrane) to absorb HF in the extraction product.
  • Type lithiated molecular sieve adsorbs organic acids and alcohols in the extraction product.
  • step S1 the used lithium-ion battery needs to be fully discharged before starting the subsequent process.
  • the used lithium-ion battery can be placed in MnSO with a concentration of 0.8mol/L. 4 electrolyte, discharge for 8 hours at a temperature of 80°C and a pH value of 2.78.
  • the lithium battery discharge reaches its optimal level, meeting green and efficient discharge conditions; for lithium-ion batteries for electric vehicles Because the residual capacity is large, it is more suitable to use a charger and discharger to collect the residual power, and then enter the subsequent dismantling or crushing process after detecting that the residual voltage is within a safe range.
  • the disassembly of used lithium-ion batteries is carried out in a -200°C liquid nitrogen environment, which can play a role in safety protection.
  • the present invention adds a specific entrainer, Improve extraction effect and increase extraction efficiency.
  • the entraining agent includes cyclic carbonates, such as ethylene carbonate, propylene carbonate, and butylene carbonate.
  • Cyclic carbonates are commonly used organic solvents for electrolytes. They are relatively polar solvents, so there is no need to worry about residue problems.
  • cyclic carbonates entrainers can also improve the extraction efficiency of LiPF 6 without accelerating the extraction process. Decomposition of LiPF 6 .
  • the entraining agent also includes N,N-dimethylformamide, that is, in other embodiments, the entraining agent is a mixture of cyclic carbonates and N,N-dimethylformamide, the cyclic carbonate
  • the mass ratio of dimethylformamide and N,N-dimethylformamide is 3-4:1, for example: 3:1, 4:1, etc.
  • N,N-dimethylformamide is also a commonly used organic solvent for electrolytes. It is a relatively polar solvent, so there is no need to worry about residual problems. That is, the entraining agents of the present invention are reagents that are easy to separate from the extract; if the entraining agent remains, After using the entrainer, an additional treatment process is required to separate the entrainer after extraction. If the entrainer remains in the extract and is not removed or is difficult to remove, then supercritical fluid extraction will lose the advantages of cleanliness and environmental protection.
  • the inventor determined that the two entrainers, cyclic carbonates and N,N-dimethylformamide, did not destroy the chemical properties of the electrolyte. In this way, the electrolyte recovery method of the present invention will not cause The organic solvent components of the electrolyte decompose or generate new substances, and the components in the electrolyte can be extracted relatively completely.
  • An entrainer mixed with cyclic carbonates and N,N-dimethylformamide is used.
  • the N,N-dimethylformamide entrainer is used to synergistically enhance the extraction efficiency.
  • the mass ratio of the two is 3-4. Extraction efficiency is optimal at :1.
  • the polarity of CO 2 is relatively weak, and higher extraction efficiency can be obtained in pure supercritical CO 2 for lipophilic substances with weak polarity in the lithium ion battery electrolyte; but on the contrary, extremely The extraction efficiency of highly toxic compounds or electrolyte lithium salts is not ideal.
  • the extraction efficiency of polar components can be improved by adjusting the pressure and temperature of supercritical CO2 during the extraction process, the actual operation is restricted by many factors.
  • the use of mixed entrainers of cyclic carbonates and N,N-dimethylformamide can reduce the dissolution pressure of polar solutes, effectively increase the solubility of polar solutes, and significantly improve the extraction efficiency of polar substances. improvement.
  • the present invention utilizes an N,N-dimethylformamide entraining agent that is more polar than a cyclic carbonate entraining agent, and the N,N-dimethylformamide entraining agent has a higher polarity than a cyclic carbonate entraining agent.
  • the lower viscosity of the agent is more conducive to the diffusion of the two entraining agents in the electrolyte adsorbate, increases the contact between the two entraining agents and the electrolyte, and also increases the dissolution of the electrolyte.
  • the pressure is 21-35MPa, such as: 21MPa, 25MPa, 27MPa, 30MPa, 35MPa, etc.
  • the temperature is 40-55°C, such as: 40°C, 45°C, 50°C , 55°C, etc., conduct co-extraction of supercritical CO 2 and entrainer, separate the electrolyte in the electrolyte, and obtain the extraction product.
  • the extraction includes static extraction and dynamic extraction; optionally, the static extraction time is 18-22min, such as: 18min, 20min, 22min, etc., and the dynamic extraction time is 35-55min, 35min, 40min, 45min, 50min, 55min and so on.
  • an entrainer to the supercritical CO 2 extraction instrument in advance.
  • the amount of entrainer can be added according to the corresponding proportion of the extraction tank solvent, such as 10% of the tank solvent.
  • the amount of entrainer in the supercritical CO 2 extraction instrument is maintained at 8-10%, that is, the addition flow rate of the entrainer is 8-10% of the CO 2 flow rate, for example: 8%, 9%, 10 %wait.
  • type lithiated molecular sieve using LiCl ethanol solution Type molecular sieve is produced by lithiation treatment; type lithiated molecular sieve using LiCl ethanol solution Type molecular sieves are prepared by lithiation treatment.
  • the concentration of LiCl ethanol solution is 1.8-2.2mol/L, for example: 1.8mol/L, 2.0mol/L, 2.2mol/L, etc.; the number of lithiation treatments is 5-10 times, for example: 5 times, 6 times, 7 times, 8 times, 9 times, 10 times.
  • type molecular sieve and Type molecular sieve is soaked in LiCl ethanol solution for about 36 hours, vacuum dried, and repeated 5-10 times to obtain type lithiated molecular sieves and Type lithiated molecular sieve.
  • step S2 Add cyclic carbonate entrainer to the supercritical CO2 extraction instrument. Place the pulverized solid in step S1 into a supercritical CO2 extraction instrument under the protection of inert gas.
  • S3 Perform co-extraction of supercritical CO 2 and entrainer at a pressure of 21MPa and a temperature of 40°C, separate the electrolyte in the electrolyte, and obtain the extraction product.
  • the extraction time is static extraction for 20 minutes, and then dynamic extraction 55 minutes.
  • the amount of cyclic carbonate entrainer in the supercritical CO2 extraction instrument is maintained at 8%, and the addition flow rate of the cyclic carbonate entrainer is 8% of the CO2 flow rate.
  • step S4 Collect the extraction product in step S3 through a cryogenic device and use Type lithiated molecular sieve adsorbs water in the extraction product, uses weakly basic anion exchange resin to adsorb HF in the extraction product, uses Lithium-type molecular sieve absorbs organic acids and alcohols in the extraction product to produce reusable electrolyte recovery products.
  • step S2 Add a mixed entrainer of cyclic carbonates and N,N-dimethylformamide to the supercritical CO2 extraction instrument.
  • the mass ratio of cyclic carbonates and N,N-dimethylformamide is 4:1.
  • S3 Perform co-extraction of supercritical CO 2 and entrainer at a pressure of 21MPa and a temperature of 40°C, separate the electrolyte in the electrolyte, and obtain the extraction product.
  • the extraction time is static extraction for 20 minutes, and then dynamic extraction 55 minutes.
  • the amount of the two entrainer mixtures in the supercritical CO2 extraction instrument is maintained at 8%, and the addition flow rate of the two entrainer mixtures is 8% of the CO2 flow rate.
  • step S4 Collect the extraction product in step S3 through a cryogenic device and use Type lithiated molecular sieve adsorbs water in the extraction product, uses weakly basic anion exchange resin to adsorb HF in the extraction product, uses Lithium-type molecular sieve absorbs organic acids and alcohols in the extraction product to produce reusable electrolyte recovery products.
  • step S2 Add a mixed entrainer of cyclic carbonates and N,N-dimethylformamide to the supercritical CO2 extraction instrument.
  • the mass ratio of cyclic carbonates and N,N-dimethylformamide is 4:1.
  • S3 Perform co-extraction of supercritical CO 2 and entrainer at a pressure of 35MPa and a temperature of 55°C, separate the electrolyte in the electrolyte, and obtain the extraction product.
  • the extraction time is static extraction for 20 minutes, and then dynamic extraction 35 minutes.
  • the amount of the two entrainer mixtures in the supercritical CO2 extraction instrument is maintained at 8%, and the addition flow rate of the two entrainer mixtures is 8% of the CO2 flow rate.
  • step S4 Collect the extraction product in step S3 through a cryogenic device and use Type lithiated molecular sieve adsorbs water in the extraction product, uses weakly basic anion exchange resin to adsorb HF in the extraction product, uses Lithium-type molecular sieve absorbs organic acids and alcohols in the extraction product to produce reusable electrolyte recovery products.
  • Comparative Example 1 does not add any entraining agent in step S2, and the remaining processes are as in Example 1.
  • Comparative Example 2 is compared with Example 2.
  • step S2 the mass ratio of cyclic carbonates and N,N-dimethylformamide is 1:1, and the remaining processes are referred to Example 2.
  • Example 3 Comparative Example 3 Compared with Example 2, at the beginning of dynamic extraction, the addition flow rate of the two entrainer mixtures was 4% of the CO 2 flow rate, and the remaining processes were referred to Example 2.
  • Comparative Example 4 is compared with Example 2. At the beginning of dynamic extraction, the addition flow rate of the two entrainer mixtures is 6% of the CO 2 flow rate. The rest of the process is referred to Example 2.
  • Comparative Example 5 uses acetone as the entraining agent in step S2, and the rest of the process is as described in Example 2.
  • step S4 Compared with Example 2 in Comparative Example 6, in step S4, using type molecular sieve and Type molecular sieve adsorbs the extraction product in step S3, and the remaining processes are referred to Example 2.
  • Example 1 A comparative experiment was conducted based on Example 1 and Comparative Example 1. Under the optimized process conditions (pressure is 21MPa, temperature is 40°C, extraction time is static extraction for 20 minutes, and then dynamic extraction for 55 minutes), the amount of entrainer added is 0 ⁇ Under the extraction condition of 8%, the relationship curve between the extraction efficiency of electrolyte and the addition of entrainer and cyclic carbonate entrainer is shown in Figure 1.
  • the electrolyte extraction efficiency of the mixed entrainer of cyclic carbonates and N,N-dimethylformamide of the present invention is much higher than that of using acetone.
  • Example 1 the difference between Example 1 and Example 2 is that: the entraining agent in the Example only includes cyclic carbonates, and the entraining agent in Example 2 is cyclic carbonates and N, N - A mixture of dimethylformamide; according to Figure 1 and Figure 3, it can be seen that the electrolyte extraction efficiency of Example 1 is 88.87%, and the electrolyte extraction efficiency of Example 2 is 96.24% respectively. It can be seen that the cyclic carbonate The synergy between N, N-dimethylformamide and N, N-dimethylformamide significantly improves the electrolyte extraction effect.
  • Example 1 adopts type lithium molecular sieve, Type lithiated molecular sieve and weakly alkaline anion exchange resin remove moisture and HF from the waste lithium-ion battery electrolyte recovery product; among them, the water content can be reduced to less than 20ppm, and the HF content can be reduced to less than 50ppm.
  • the electrolyte recovered in Example 1 was supplemented with ingredients to synthesize a reused electrolyte, and the physical and chemical properties of the reused electrolyte were characterized. The results showed that the HF content and moisture content of the reused electrolyte were , ionic conductivity, lithium ion migration number, electrochemical window, etc. meet relevant index requirements.
  • the electrolyte recovery and treatment method for lithium-ion batteries of the present invention optimizes the parameters of the supercritical CO 2 extraction electrolyte process, and controls the polarity of CO 2 under specific pressure and system temperature to improve electrolysis.
  • Liquid extraction efficiency allows physical properties such as density and polarity of CO2 to be controlled through pressure and temperature, making CO2 more selective for solutes.
  • the present invention also combines static extraction and dynamic extraction.
  • the static extraction is conducive to the full dissolution of the solute, and then the dynamic extraction is performed to reduce the residue of the solute in the matrix and improve the extraction efficiency; while the extraction time is short to reduce volatile components and easily
  • add cyclic carbonate entrainers to improve the extraction efficiency of components which can take into account the extraction rules of most main components and ensure that each component in the extraction product achieves high recovery efficiency.
  • adding a cyclic carbonate entrainer to supercritical CO 2 increases the density of the fluid, resulting in an increase in the solubility of the electrolyte.
  • the synergy between cyclic carbonates and N,N-dimethylformamide can significantly improve the electrolyte extraction effect. , and will not cause the organic solvent components of the electrolyte to decompose or generate new substances, significantly improving the extraction efficiency of the electrolyte.

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Abstract

本发明涉及电池回收再利用技术领域，具体而言，涉及锂离子电池的电解液的回收处理方法，包括：将充分放电后的锂离子电池冷却至电解液凝固点以下，然后拆解、粉碎，得到含有电解液的粉碎固体；在惰性气体的保护下将粉碎固体置于超临界C02萃取仪器内，且超临界C02萃取仪器内添加有夹带剂；萃取；将萃取产物通过低温装置收集，使用4Å型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂吸附萃取产物中的HF,使用5Å型锂化分子筛吸附萃取产物中的有机酸和醇。通过4Å型锂化分子筛、弱碱性阴离子交换树脂以及5Å型锂化分子筛将萃取产物中的水、HF、有机酸和醇吸附，以便于得到可直接再利用的电解液回收产物。

Description

锂离子电池的电解液的回收处理方法 技术领域
本发明涉及电池回收再利用技术领域，具体而言，涉及锂离子电池的电解液的回收处理方法。
背景技术
废旧锂电池正呈现爆发式累积性增长趋势，其健康、环境、安全隐患的累积效应成倍放大。将废旧锂电池回收再利用，可以改善废旧锂电池累积，而带来的环境污染、安全性等问题；特别是，废旧锂电池的电解液内包含有毒有害物质，在自然环境中极易发生副反应，造成二次污染，将废旧锂电池的电解液回收利用，则可以有效地改善二次污染问题。
相关技术提供的锂电池的电解液回收方法主要采用有机溶剂萃取工艺和超临界CO 2萃取工艺。有机溶剂萃取工艺主要通过引入与电解液溶解性能相近的溶剂，对破碎后的电池进行浸泡，将电解液转移到溶剂中，再将溶剂与电解液分离，该方法的不足之处在于溶剂成本高，萃取产物分离工艺复杂，能耗高，萃取产物有溶剂残留等问题；而与有机溶剂萃取工艺相比，引入超临界CO 2对电池电解液进行萃取，可避免溶剂残留等问题，但是超临界CO 2的极性较弱，与电解液之间的互溶效果还有待提高，电解液的回收技术难度大，难以获得能够直接再利用的电解液回收产物。
发明内容
本发明的目的在于提供锂离子电池的电解液的回收处理方法，能够获得可直接再利用的电解液回收产物。
本发明是这样实现的：
本发明提供一种锂离子电池的电解液的回收处理方法，包括：
S1：将充分放电后的废旧锂离子电池冷却至电解液凝固点以下，然后拆解、粉碎，得到含有电解液的粉碎固体；
S2：在惰性气体的保护下将粉碎固体置于超临界CO 2萃取仪器内，且超临界CO 2萃取仪器内添加有夹带剂；
S3：萃取；
S4：将萃取产物通过低温装置收集，使用
Figure PCTCN2022120625-appb-000001
型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂吸附萃取产物中的HF，使用
Figure PCTCN2022120625-appb-000002
型锂化分子筛吸附萃取产物中的有机酸和醇。
在可选的实施方式中，
Figure PCTCN2022120625-appb-000003
型锂化分子筛采用LiCl乙醇溶液对
Figure PCTCN2022120625-appb-000004
型分子筛锂化处理制得；和/或，
Figure PCTCN2022120625-appb-000005
型锂化分子筛采用LiCl乙醇溶液对
Figure PCTCN2022120625-appb-000006
型分子筛锂化处理制得。
在可选的实施方式中，LiCl乙醇溶液的浓度为1.8-2.2mol/L；锂化处理的次数为5-10次。
在可选的实施方式中，夹带剂包括环状碳酸酯类。
在可选的实施方式中，夹带剂还包括N,N-二甲基甲酰胺。
在可选的实施方式中，环状碳酸酯类和N,N-二甲基甲酰胺的质量比为3-4:1。
在可选的实施方式中，萃取包括静态萃取和动态萃取。
在可选的实施方式中，在动态萃取开始时，夹带剂的添加流量为CO 2流量的8-10％。
在可选的实施方式中，静态萃取的时间为18-22min，动态萃取的时间为35-55min。
在可选的实施方式中，萃取的压力为21-35MPa，温度为40-55℃。
本发明具有以下有益效果：
本发明实施例提供的锂离子电池的电解液的回收处理方法，在超临界CO 2萃取后，使用
Figure PCTCN2022120625-appb-000007
型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂吸附萃取产物中的HF，使用
Figure PCTCN2022120625-appb-000008
型锂化分子筛吸附萃取产物中的有机酸和醇；如此，通过
Figure PCTCN2022120625-appb-000009
型锂化分子筛、弱碱性阴离子交换树脂、以及
Figure PCTCN2022120625-appb-000010
型锂化分子筛将萃取产物中的水、HF、有机酸和醇吸附，以便于得到可直接再利用的电解液回收产物。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单的介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本发明中环状碳酸酯类夹带剂和不添加夹带剂与电解液萃取效率关系曲线图；
图2为本发明中环状碳酸酯类和N,N-二甲基甲酰胺混合夹带剂的不同质量比与电解液萃取效率关系曲线图；
图3为本发明中不同种类夹带剂及夹带剂用量与电解液萃取效率关系曲线图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明提供一种锂离子电池的电解液的回收处理方法，可用于回收废 旧锂离子电池的电解液，包括：
S1：将充分放电后的废旧锂离子电池冷却至电解液凝固点以下，然后拆解、粉碎，得到含有电解液的粉碎固体；
S2：在惰性气体的保护下将粉碎固体置于超临界CO 2萃取仪器内，且超临界CO 2萃取仪器内添加有夹带剂；
S3：萃取；
S4：将萃取产物通过低温装置收集，使用
Figure PCTCN2022120625-appb-000011
型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂(弱碱性阴离子交换膜)吸附萃取产物中的HF，使用
Figure PCTCN2022120625-appb-000012
型锂化分子筛吸附萃取产物中的有机酸和醇。
通过
Figure PCTCN2022120625-appb-000013
型锂化分子筛、弱碱性阴离子交换树脂、以及
Figure PCTCN2022120625-appb-000014
型锂化分子筛将萃取产物中的水、HF、有机酸和醇吸附，以便于得到可直接再利用的电解液回收产物。
由于带有残余电量的废旧锂离子电池经过多次的循环，存在内部缺陷的几率增加；在这种状态下，如遇到机械碰撞或特殊温度、湿度及接触不良等情况或环境下可能瞬间放电产生大量电流，引发自燃或爆炸。为了尽量减少这些危害和事故的发生，在步骤S1中，需要使废旧的锂离子电池充分放电后，再开始后续的工艺，例如：可以将废旧锂离子电池放入浓度为0.8mol/L的MnSO 4电解液，在温度为80℃、pH值为2.78条件下，放电8h，当残余电压降低到0.54V时，锂电池放电达到最佳，满足绿色高效的放电条件；对于电动汽车用锂离子电池组，由于残余容量较多，更适宜用充放电机收集残余电量，检测残余电压处于安全范围后再进入后续的拆解或粉碎工艺。
在一些实施方式中，废旧锂离子电池的拆解在-200℃液氮环境下进行，可以起到安全防护的作用。
发明人研究发现，由于工艺条件和设备要求等因素的限制，超临界CO 2流体的溶解度在达到一定上限后，仅仅通过改变工艺条件很难继续改善萃 取效果；故本发明通过加入特定夹带剂，改善萃取效果和提高萃取效率。
在一些实施方式中，夹带剂包括环状碳酸酯类，例如：碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯。环状碳酸酯类为电解液常用有机溶剂，是极性较大的溶剂，不用担心残留问题；而且，环状碳酸酯类夹带剂还对LiPF 6的萃取效率有一定提高作用，且不会加速LiPF 6的分解。
进一步地，夹带剂还包括N,N-二甲基甲酰胺，即在另一些实施方式中，夹带剂为环状碳酸酯类和N,N-二甲基甲酰胺的混合物，环状碳酸酯类和N,N-二甲基甲酰胺的质量比为3-4:1，例如：3:1、4:1等。
N,N-二甲基甲酰胺也是电解液常用有机溶剂，是极性较大的溶剂，不用担心残留问题，即本发明的夹带剂均为容易与萃取物分离的试剂；若是夹带剂残留，则需要在使用夹带剂后在萃取后多一道分离夹带剂的处理工艺，如果夹带剂残留在萃取物中没有去除或不易去除，那么超临界流体萃取就失去了清洁、环保的优点。
发明人通过气相色谱分析，确定环状碳酸酯类和N,N-二甲基甲酰胺两种夹带剂均没有破坏电解液的化学性质，这样一来，本发明的电解液回收方法不会使电解液有机溶剂组分发生分解或生成新的物质，可以将电解液中的组分较为完整的萃取出来。
使用环状碳酸酯类和N,N-二甲基甲酰胺混合的夹带剂，其中，N,N-二甲基甲酰胺夹带剂用于协同增强萃取效率，两者在质量比为3-4:1下萃取效率达到最优。
通过发明人研究发现，CO 2的极性相对较弱，对于锂离子电池电解液中极性较弱的亲脂性物质在纯超临界CO 2中可获得较高的萃取效率；但相反的，极性较强的化合物或者电解液锂盐的萃取效率不够理想。虽然可以通过调节萃取过程中超临界CO 2的压力和温度提高极性组分的萃取效率，但实际操作却受到多种因素的制约。为此，采用环状碳酸酯类和N,N-二甲基甲酰胺混合夹带剂，能够降低极性溶质的溶解压力，有效地提高极性溶质 的溶解度，使极性物质的萃取效率得到显著的提高。
另一方面，本发明利用N,N-二甲基甲酰胺夹带剂的极性大于环状碳酸酯类夹带剂，且N,N-二甲基甲酰胺夹带剂具有比环状碳酸酯类夹带剂更低的黏度，比较利于两种夹带剂在电解液吸附质中的扩散，增加两种夹带剂与电解液的接触，也增加了电解液的溶出。
由此可知，在环状碳酸酯类中加入复配N,N-二甲基甲酰胺夹带剂，在多因素综合作用下，两种夹带剂的协同使用增强萃取效率，且萃取效果远大于使用单一夹带剂。
在一些实施方式中，在步骤S3中，在压力为21-35MPa，例如：21MPa、25MPa、27MPa、30MPa、35MPa等，温度为40-55℃条件下，例如：40℃、45℃、50℃、55℃等，进行超临界CO 2和夹带剂的共同萃取，分离出电解液中的电解质，并获得萃取产物。
进一步地，萃取包括静态萃取和动态萃取；可选地，静态萃取的时间为18-22min，例如：18min、20min、22min等，动态萃取的时间为35-55min，35min、40min、45min、50min、55min等。
静态萃取和动态萃取两种方法结合，先采用静态萃取，待溶质充分溶解后再采用动态萃取，能够减少溶质在样品基体中的残留，提高萃取效率。
可选地，在萃取开始时，提前向超临界CO 2萃取仪器加入夹带剂，夹带剂的用量可以按萃取釜溶剂的相应比例进行添加，如釜溶剂的10％。当动态萃取开始时，超临界CO 2萃取仪器中的夹带剂的量维持在8-10％，即夹带剂的添加流量为CO 2流量的8-10％，例如：8％、9％、10％等。
在一些实施方式中，
Figure PCTCN2022120625-appb-000015
型锂化分子筛采用LiCl乙醇溶液对
Figure PCTCN2022120625-appb-000016
型分子筛锂化处理制得；
Figure PCTCN2022120625-appb-000017
型锂化分子筛采用LiCl乙醇溶液对
Figure PCTCN2022120625-appb-000018
型分子筛锂化处理制得。
进一步地，LiCl乙醇溶液的浓度为1.8-2.2mol/L，例如：1.8mol/L、2.0mol/L、2.2mol/L等；锂化处理的次数为5-10次，例如：5次、6次、7 次、8次、9次、10次。
需要说明的是，将
Figure PCTCN2022120625-appb-000019
型分子筛和
Figure PCTCN2022120625-appb-000020
型分子筛用LiCl乙醇溶液浸泡36h左右后，真空干燥，并重复5-10次，即可获得
Figure PCTCN2022120625-appb-000021
型锂化分子筛和
Figure PCTCN2022120625-appb-000022
型锂化分子筛。
以下结合实施例对本发明作进一步的详细描述。
实施例1
S1：对废旧锂离子电池进行充分放电，然后将废旧锂离子电池冷却至电解液凝固点以下，然后拆解粉碎废旧锂离子电池，获得含有电解液的粉碎固体。
S2：向超临界CO 2萃取仪器中加入环状碳酸酯类夹带剂。在惰性气体的保护下将步骤S1中的粉碎固体置于超临界CO 2萃取仪器。
S3：在压力为21MPa，温度40℃的条件下进行超临界CO 2和夹带剂的共同萃取，分离出所述电解液中的电解质，并获得萃取产物，萃取时间为静态萃取20min，然后动态萃取55min。
其中，当动态萃取开始时，超临界CO 2萃取仪器中的环状碳酸酯类夹带剂的量维持在8％，环状碳酸酯类夹带剂的添加流量为CO 2流量的8％。
S4：将步骤S3中的萃取产物通过低温装置收集，使用
Figure PCTCN2022120625-appb-000023
型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂吸附萃取产物中的HF，使用
Figure PCTCN2022120625-appb-000024
型锂化分子筛吸附萃取产物中的有机酸和醇，制得可再利用电解液回收产物。
实施例2
S1：对废旧锂离子电池进行充分放电，然后将废旧锂离子电池冷却至电解液凝固点以下，然后拆解粉碎废旧锂离子电池，获得含有电解液的粉碎固体。
S2：向超临界CO 2萃取仪器中加入环状碳酸酯类和N,N-二甲基甲酰胺的混合夹带剂，环状碳酸酯类和N,N-二甲基甲酰胺的质量比为4:1。在惰性 气体的保护下将步骤S1中的粉碎固体置于超临界CO 2萃取仪器。
S3：在压力为21MPa，温度40℃的条件下进行超临界CO 2和夹带剂的共同萃取，分离出所述电解液中的电解质，并获得萃取产物，萃取时间为静态萃取20min，然后动态萃取55min。
其中，当动态萃取开始时，超临界CO 2萃取仪器中的两种夹带剂混合物的量维持在8％，两种夹带剂混合物的添加流量为CO 2流量的8％。
S4：将步骤S3中的萃取产物通过低温装置收集，使用
Figure PCTCN2022120625-appb-000025
型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂吸附萃取产物中的HF，使用
Figure PCTCN2022120625-appb-000026
型锂化分子筛吸附萃取产物中的有机酸和醇，制得可再利用电解液回收产物。
实施例3
S1：对废旧锂离子电池进行充分放电，然后将废旧锂离子电池冷却至电解液凝固点以下，然后拆解粉碎废旧锂离子电池，获得含有电解液的粉碎固体。
S2：向超临界CO 2萃取仪器中加入环状碳酸酯类和N,N-二甲基甲酰胺的混合夹带剂，环状碳酸酯类和N,N-二甲基甲酰胺的质量比为4:1。在惰性气体的保护下将步骤S1中的粉碎固体置于超临界CO 2萃取仪器。
S3：在压力为35MPa，温度55℃的条件下进行超临界CO 2和夹带剂的共同萃取，分离出所述电解液中的电解质，并获得萃取产物，萃取时间为静态萃取20min，然后动态萃取35min。
其中，当动态萃取开始时，超临界CO 2萃取仪器中的两种夹带剂混合物的量维持在8％，两种夹带剂混合物的添加流量为CO 2流量的8％。
S4：将步骤S3中的萃取产物通过低温装置收集，使用
Figure PCTCN2022120625-appb-000027
型锂化分子筛吸附萃取产物中的水，使用弱碱性阴离子交换树脂吸附萃取产物中的HF，使用
Figure PCTCN2022120625-appb-000028
型锂化分子筛吸附萃取产物中的有机酸和醇，制得可再利用电解液回收产物。
对比例1
对比例1与实施例1相比，在步骤S2中，没有添加任何的夹带剂，其余工艺均参照实施例1。
对比例2
对比例2与实施例2相比，在步骤S2中，环状碳酸酯类和N,N-二甲基甲酰胺的质量比为1:1，其余工艺均参照实施例2。
对比例3
对比例3与实施例2相比，在动态萃取开始时，两种夹带剂混合物的添加流量为CO 2流量的4％，其余工艺均参照实施例2。
对比例4
对比例4与实施例2相比，在动态萃取开始时，两种夹带剂混合物的添加流量为CO 2流量的6％，其余工艺均参照实施例2。
对比例5
对比例5与实施例2相比，步骤S2中夹带剂选用丙酮，其余工艺均参照实施例2。
对比例6
对比例6与实施例2相比，步骤S4中，利用
Figure PCTCN2022120625-appb-000029
型分子筛和
Figure PCTCN2022120625-appb-000030
型分子筛吸附步骤S3中的萃取产物，其余工艺均参照实施例2。
1、基于实施例1与对比例1进行对比实验，在优化后的工艺条件下(压 力为21MPa，温度40℃，萃取时间为静态萃取20min，然后动态萃取55min)，夹带剂添加量为0～8％的萃取条件下，不添加夹带剂及环状碳酸酯类夹带剂与电解液萃取效率关系曲线如图1所示。
由图1可见，不添加夹带剂与添加环状碳酸酯类夹带剂，两者的萃取效率差距明显，不添加夹带剂(即夹带剂添加量为0％)的电解液萃取效率仅有66.05％。环状碳酸酯类夹带剂的用量0～8％的变化范围内，随着夹带剂的用量的增加，电解液的萃取效率也随之增大。在夹带剂用量达到8％时(实施例1)，使用添加环状碳酸酯类夹带剂的电解液萃取效率为88.87％。
2、基于实施例2与对比例2进行对比实验，在优化后的工艺条件下(压力为21MPa，温度40℃，萃取时间为静态萃取20min，然后动态萃取55min，夹带剂用量8％)，混合夹带剂的不同质量比与电解液萃取效率关系曲线如图2所示。
由图2可见，环状碳酸酯类和N,N-二甲基甲酰胺的质量比，随着N,N-二甲基甲酰胺夹带剂的占比减小，电解液的萃取效率也随之增大。在环状碳酸酯类和N,N-二甲基甲酰胺的质量比达到4:1时(实施例2)，电解液萃取效率分别为96.24％。因此选择4:1的最佳用量。
3、基于实施例2与对比例3、对比例4、对比例5进行对比实验，在优化后的工艺条件下(压力为21MPa，温度40℃，萃取时间为静态萃取20min，然后动态萃取55min，环状碳酸酯类和N,N-二甲基甲酰胺的质量比为4:1)，不同种类夹带剂及夹带剂用量与电解液萃取效率关系曲线如图3所示。
由图3可见，环状碳酸酯类和N,N-二甲基甲酰胺混合夹带剂，随着用量的增大，在8％时(实施例2)为96.24％，电解液的萃取效率也随之增大。随后电解液的萃取效率增速趋于平缓，因此选择8％为夹带剂的最佳用量。
而且，本发明的环状碳酸酯类和N,N-二甲基甲酰胺混合夹带剂，电解液萃取效率远远高于使用丙酮。
4、通过上述实施例的记载可知，实施例1和实施例2的区别在于：实 施例的夹带剂仅包括环状碳酸酯类，实施例2的夹带剂为环状碳酸酯类和N,N-二甲基甲酰胺的混合物；根据图1和图3可知，实施例1的电解液萃取效率为88.87％，实施例2的电解液萃取效率分别为96.24％，由此可见，环状碳酸酯类和N,N-二甲基甲酰胺两者协同对电解液萃取效果有着明显的提升。
5、超临界CO 2回收的电解液中，由于含氟锂盐的分解会导致HF含量较高，HF的去除也是实现电解液再利用的一个重要的环节。由于超临界CO 2萃取过程中水分的影响因素不能完全排除(例如：CO 2、萃取釜和萃取设备管路中的水分)，因此电解液萃取过程中会引入一定量的水分，电解液锂盐的水解过程虽然会消耗一定量的水分，但是水分含量仍会过高。
实施例1采用
Figure PCTCN2022120625-appb-000031
型锂化分子筛、
Figure PCTCN2022120625-appb-000032
型锂化分子筛和弱碱性阴离子交换树脂除去废旧锂离子电池电解液回收产物中的水分和HF；其中，可以使水含量降至20ppm以下，HF含量降低到50ppm以下。按照商品化电解液的配方，给实施例1回收的电解液补充成分合成再利用电解液，并对再利用电解液的物理化学性能进行表征，结果表明，再利用电解液的HF含量、水分含量、离子电导率、锂离子迁移数、电化学窗口等满足相关指标要求。
而对比例6的电解液中HF含量过高会造成电池内部腐蚀，导致电池内阻增大，引起电池比容量和库伦效率衰减等问题。
综上所述，本发明的锂离子电池的电解液的回收处理方法，对超临界CO 2萃取电解液工艺的参数进行优化，在特定压力和体系温度下，控制CO 2的极性以提高电解液萃取效率，使CO 2的密度和极性等物理性质通过压力和温度进行控制，使CO 2对溶质更具选择性。本发明还通过静态萃取和动态萃取相结合，静态萃取时有利于溶质充分溶解，随后进行动态萃取以减少溶质在基体中的残留，提高萃取效率；而萃取时间短以减少易挥发组分和易分解组分的损失，添加环状碳酸酯类夹带剂以提高组分的萃取效率，能够兼顾大多数主要成分的萃取规律，保证在萃取产物中各组分都实现较 高的回收效率。
在本发明特定的体系温度和压力条件下，向超临界CO 2中加入环状碳酸酯类夹带剂，流体密度增加，导致电解液的溶解度增大。另一方面，在特定工艺参数下，结合N,N-二甲基甲酰胺夹带剂，环状碳酸酯类和N,N-二甲基甲酰胺两者协同对电解液萃取效果有着明显的提升，且不会使电解液有机溶剂组分发生分解或生成新的物质，显著提升电解液的萃取效率。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种锂离子电池的电解液的回收处理方法，其特征在于，包括：
    S1：将充分放电后的废旧锂离子电池冷却至电解液凝固点以下，然后拆解、粉碎，得到含有电解液的粉碎固体；
    S2：在惰性气体的保护下将所述粉碎固体置于超临界CO 2萃取仪器内，所述超临界CO 2萃取仪器内添加有夹带剂；
    S3：萃取；
    S4：将萃取产物通过低温装置收集，使用
    Figure PCTCN2022120625-appb-100001
    型锂化分子筛吸附所述萃取产物中的水，使用弱碱性阴离子交换树脂吸附所述萃取产物中的HF，使用
    Figure PCTCN2022120625-appb-100002
    型锂化分子筛吸附所述萃取产物中的有机酸和醇。
  2. 根据权利要求1所述的锂离子电池的电解液的回收处理方法，其特征在于，所述
    Figure PCTCN2022120625-appb-100003
    型锂化分子筛采用LiCl乙醇溶液对
    Figure PCTCN2022120625-appb-100004
    型分子筛锂化处理制得；和/或，
    所述
    Figure PCTCN2022120625-appb-100005
    型锂化分子筛采用LiCl乙醇溶液对
    Figure PCTCN2022120625-appb-100006
    型分子筛锂化处理制得。
  3. 根据权利要求2所述的锂离子电池的电解液的回收处理方法，其特征在于，所述LiCl乙醇溶液的浓度为1.8-2.2mol/L；锂化处理的次数为5-10次。
  4. 根据权利要求1所述的锂离子电池的电解液的回收处理方法，其特征在于，所述夹带剂包括环状碳酸酯类。
  5. 根据权利要求4所述的锂离子电池的电解液的回收处理方法，其特征在于，所述夹带剂还包括N,N-二甲基甲酰胺。
  6. 根据权利要求5所述的锂离子电池的电解液的回收处理方法，其特征在于，所述环状碳酸酯类和所述N,N-二甲基甲酰胺的质量比为3-4:1。
  7. 根据权利要求1-6任一项所述的锂离子电池的电解液的回收处理方法，其特征在于，所述萃取包括静态萃取和动态萃取。
  8. 根据权利要求7所述的锂离子电池的电解液的回收处理方法，其特征在于，在所述动态萃取开始时，所述夹带剂的添加流量为CO 2流量的8-10％。
  9. 根据权利要求7所述的锂离子电池的电解液的回收处理方法，其特征在于，所述静态萃取的时间为18-22min，所述动态萃取的时间为35-55min。
  10. 根据权利要求7所述的锂离子电池的电解液的回收处理方法，其特征在于，所述萃取的压力为21-35MPa，温度为40-55℃。
PCT/CN2022/120625 2022-08-15 2022-09-22 锂离子电池的电解液的回收处理方法 Ceased WO2024036698A1 (zh)

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