WO2024229784A1 - 一种锂离子电池材料的评估方法及其应用 - Google Patents

一种锂离子电池材料的评估方法及其应用 Download PDF

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WO2024229784A1
WO2024229784A1 PCT/CN2023/093418 CN2023093418W WO2024229784A1 WO 2024229784 A1 WO2024229784 A1 WO 2024229784A1 CN 2023093418 W CN2023093418 W CN 2023093418W WO 2024229784 A1 WO2024229784 A1 WO 2024229784A1
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positive electrode
electrode material
evaluation method
tested
temperature storage
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French (fr)
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钟进
杜锐
阮丁山
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 CN202380009539.0A priority Critical patent/CN116848401B/zh
Priority to PCT/CN2023/093418 priority patent/WO2024229784A1/zh
Publication of WO2024229784A1 publication Critical patent/WO2024229784A1/zh
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    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure belongs to the field of lithium-ion batteries, for example, a method for evaluating lithium-ion battery materials and applications thereof.
  • lithium-ion batteries have been successful due to their high energy density, long cycle life, and good rate performance, and are widely used in portable consumer electronics, electric vehicles, energy storage, etc.
  • the electrode material interface of lithium-ion batteries reacts more complexly with the electrolyte, which not only causes performance loss at high temperatures, but may also cause safety issues, such as the generation of gas that causes battery swelling, which can easily cause hidden dangers.
  • the high-temperature storage performance of positive electrode materials and lithium batteries containing them is often evaluated by preparing soft-pack full batteries, and the electrical performance changes and swelling rates of the full battery are tested after different periods of time or before and after storage at different temperatures. The reliability and safety are measured by comparing the degree of change in electrical performance indicators and the degree of battery swelling.
  • CN108267693B discloses a rapid evaluation method for the high-temperature storage performance of lithium battery positive electrode materials, which uses lithium-ion button half-cells to perform high-temperature floating charge on positive electrode materials, and can infer the difference in high-temperature storage performance between different positive electrode materials based on the floating charge capacity test data.
  • this rapid evaluation method can only infer the difference in high-temperature storage performance between different positive electrode materials, and cannot intuitively characterize the performance changes of positive electrode materials during high-temperature storage.
  • CN110658473B discloses a method for quickly evaluating the high-temperature storage performance of a lithium battery positive electrode material, which simulates the environmental state of the positive electrode material in the high-temperature storage of the whole battery, and obtains the delithiation state by chemical delithiation.
  • the positive electrode material is subjected to an equivalent high-temperature storage test for the de-lithiated positive electrode material, and the capacity retention rate is evaluated by the first discharge capacity ratio.
  • This method obtains the de-lithiated positive electrode material by strengthening the oxidant. During the reaction with the oxidant, the interface becomes complicated, and the amount of de-lithiated cannot be guaranteed.
  • the button cell is prepared again, and its discharge capacity is not stable, which reduces the reliability of the evaluation.
  • the present disclosure provides an evaluation method for lithium-ion battery materials and its application.
  • the evaluation method first prepares the positive electrode material to be tested as a de-lithiated positive electrode material, then places it in an electrolyte for heating and stirring, and uses the filtrate obtained after solid-liquid separation to perform an ICP test to obtain the main element dissolution data.
  • the obtained powder is subjected to an EIS test to obtain the interface charge transfer impedance R CT value, and finally the high-temperature storage performance of the soft-pack battery containing the positive electrode material to be tested is comprehensively evaluated based on the two obtained data.
  • the evaluation method can simulate the actual high-temperature reaction process of the positive electrode material and the electrolyte to obtain a fully charged positive electrode material and obtain its main element dissolution data and R CT value, so as to quickly infer and evaluate the high-temperature storage performance of the positive electrode material.
  • the evaluation method is simple to operate, low in cost, and conducive to improving the evaluation efficiency.
  • the present invention adopts the following technical solutions:
  • an embodiment of the present disclosure provides a method for evaluating lithium-ion battery materials, the method comprising the following steps:
  • step (2) placing the delithiation positive electrode material described in step (1) in an electrolyte, heating and stirring, and performing solid-liquid separation to obtain a filtrate and a powder;
  • step (3) The filtrate obtained in step (2) is subjected to an ICP (Inductively Coupled Plasma) test to obtain the main element dissolution data; at the same time, the powder in step (2) is used as a positive electrode material to prepare a button half-cell, and an EIS (Electrochemical Impedance Spectroscopy) test is performed to obtain the interface charge transfer impedance R CT value;
  • ICP Inductively Coupled Plasma
  • EIS Electrochemical Impedance Spectroscopy
  • the evaluation method described in the embodiment of the present disclosure prepares the positive electrode material as a delithiated positive electrode material, which can simulate the actual high-temperature reaction process of the positive electrode material and the electrolyte, and makes the positive electrode material fully charged (delithiated), and then performs a test to obtain the main element dissolution data and R CT value at this time, so as to quickly infer and evaluate the high-temperature storage performance of the positive electrode material.
  • the evaluation method is simple to operate, low in cost, and is conducive to improving evaluation efficiency.
  • the electrolyte includes 9-15wt% lithium salt, 77-88wt% non-aqueous organic solvent and 3-8wt% additives;
  • the lithium salt includes at least one of lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6) or a new lithium salt lithium bis(fluorosulfonyl)imide (LiFSI);
  • the non-aqueous organic solvent includes at least one of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or ethyl methyl carbonate (EMC);
  • the additive includes at least one of a film-forming additive, a high/low temperature additive, an overcharge protection additive, a flame retardant additive, and a rate-type additive, for example, vinylene carbonate (VC) and/or fluoroethylene carbonate (FEC) can be selected.
  • VC vinylene carbonate
  • FEC fluoro
  • the positive electrode material to be tested in step (1) includes any one of lithium cobalt oxide, lithium iron phosphate or a ternary positive electrode material, or a combination of at least two of them.
  • Typical but non-limiting examples of the combination include a combination of lithium cobalt oxide and lithium iron phosphate, a combination of lithium cobalt oxide and a ternary positive electrode material, or a combination of lithium iron phosphate and a ternary positive electrode material.
  • the method for preparing the delithiated positive electrode material in step (1) includes:
  • An oxidant is added to the positive electrode material to be tested to carry out a delithiation reaction to obtain the delithiation positive electrode material.
  • the oxidant includes any one of hypobromous acid, metaperiodic acid, hypochlorous acid, chlorous acid, permanganic acid, perbromic acid or hydrogen peroxide, or a combination of at least two of them.
  • Typical but non-limiting examples of the combination include a combination of hypobromous acid and metaperiodic acid, a combination of metaperiodic acid and hypochlorous acid, a combination of chlorous acid and permanganic acid, a combination of permanganic acid and perbromic acid, and a combination of chlorous acid and hydrogen peroxide.
  • the amount of the oxidant is 4 to 8 mL per gram of the positive electrode material to be tested, for example 4 mL, 4.5 mL, 5 mL, 5.5 mL, 6 mL, 6.5 mL, 7 mL, 7.5 mL or 8 mL, and the concentration of the oxidant is 1.4 to 8 mol/L, for example 1.4 mol/L, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L, 5 mol/L, 5.5 mol/L, 6 mol/L, 6.5 mol/L, 7 mol/L, 7.5 mol/L or 8 mol/L, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the delithiation reaction is carried out under stirring.
  • the delithiation reaction time is 18 to 22 hours, such as 18 hours, 19 hours, 20 hours, 21 hours or 22 hours, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the solid-liquid ratio of the delithiation positive electrode material to the electrolyte in step (2) is 1g:(1.5 ⁇ 2.5)g, for example, 1g:1.5g, 1g:1.6g, 1g:1.7g, 1g:1.8g, 1g:1.9g, 1g:2g, 1g:2.1g, 1g:2.2g, 1g:2.3g, 1g:2.4g or 1g:2.5g, etc., but is not limited to the listed values, and other values not listed within the above numerical range are equally applicable.
  • the amount of the electrolyte is 20 to 200 mL, for example, 20 mL, 50 mL, 80 mL, 110 mL, 140 mL, 170 mL or 200 mL, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the heating and stirring in step (3) is carried out in a vacuum or a dehumidified environment.
  • the heating and stirring described in the embodiments of the present disclosure need to be carried out in a vacuum or dehumidified environment to prevent the electrolyte from absorbing moisture. After obtaining the filtrate, it should also be sealed and stored to prevent water absorption.
  • the heating and stirring in step (3) is carried out in a hydrothermal kettle with a polytetrafluoroethylene liner.
  • the temperature of the heating and stirring in step (3) is 40-80°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the heating and stirring time in step (3) is 2 to 4 hours, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h or 4h, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the stirring rate of the heating stirring in step (3) is 80 to 200 r/min, for example, 80 r/min, 100 r/min, 120 r/min, 140 r/min, 160 r/min, 180 r/min or 200 r/min, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • step (4) of the evaluation method further includes:
  • the main element dissolution data and the standard R CT value are associated with the high temperature storage performance of the soft-pack battery containing the positive electrode material to be tested, and a database is established to simulate the linear relationship between the main element dissolution data and the high temperature storage performance and/or simulate the linear relationship between the R CT value and the high temperature storage performance; the high temperature storage performance of the soft-pack battery containing the positive electrode material to be tested is inferred based on the linear relationship.
  • the database includes at least 10 different main element dissolution data of the positive electrode materials to be tested, standard R CT values, and data on high temperature storage performance of soft-pack batteries containing the positive electrode materials to be tested.
  • the evaluation method includes the following steps:
  • the positive electrode material to be tested includes any one of lithium cobalt oxide, lithium iron phosphate or a ternary positive electrode material or a combination of at least two;
  • the oxidant includes any one of hypobromous acid, metaperiodic acid, hypochlorous acid, chlorous acid, permanganic acid, perbromic acid or hydrogen peroxide or a combination of at least two;
  • the delithiation positive electrode material and the electrolyte in step (1) are placed in a polytetrafluoroethylene liner in a hydrothermal kettle at a solid-liquid ratio of 1 g:(1.5-2.5) g and mixed evenly, so that the amount of electrolyte is 20-200 mL, and then the hydrothermal kettle is placed in an oven preheated to 40-80° C., the stirring rate is set to 80-200 r/min, and the heating and stirring are carried out for 2-4 hours. After the reaction is completed, the filtrate is filtered to obtain a powder, and the obtained powder is washed and dried for use;
  • step (3) performing an ICP test on the filtrate obtained in step (2) to obtain the dissolution data of the main elements; at the same time, using the powder obtained in step (2) as a positive electrode material to prepare a button-type half-cell, performing an EIS test, and obtaining the interface charge transfer impedance R CT value;
  • an embodiment of the present disclosure provides an application of the evaluation method according to the first aspect in the field of lithium-ion battery manufacturing.
  • the present invention has at least the following beneficial effects:
  • the evaluation method can simulate the actual high-temperature reaction process of the positive electrode material and the electrolyte to obtain a fully charged positive electrode material and obtain its main element dissolution data and R CT value, thereby quickly inferring and evaluating the high-temperature storage performance of the positive electrode material.
  • the evaluation method is simple to operate, low in cost, and is conducive to improving evaluation efficiency.
  • the electrolyte used in the following embodiments and comparative examples is the lithium ion battery electrolyte provided by CN115117445A, and the electrolyte comprises a lithium salt, a non-aqueous organic solvent and an additive; specifically, in an argon atmosphere glove box with a water content of ⁇ 10 ppm, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and fluoroethylene carbonate are mixed according to a mass percentage of 20 wt%, 30 wt%, 40 wt% and 10 wt% to obtain a mixed organic solvent, and then the fully dried lithium salt is dissolved in the mixed organic solvent, the lithium salt is a mixture of lithium hexafluorophosphate and lithium difluorobisoxalate phosphate, and the concentration of the lithium salt in the electrolyte is 1mol/L, wherein the molar ratio of lithium hexafluorophosphate to lithium difluorobisoxalate phosphate is 95
  • This embodiment provides a method for evaluating lithium-ion battery materials, which is used to evaluate the high-temperature storage performance of lithium cobalt oxide positive electrode materials.
  • the method comprises the following steps:
  • delithiated lithium cobalt oxide materials Four groups of different lithium cobalt oxide materials were selected and labeled as lithium cobalt oxide-1, lithium cobalt oxide-2, lithium cobalt oxide-3, and lithium cobalt oxide-4, and four parallel samples were prepared for each group of lithium cobalt oxides; the delithiation process was carried out in a glove box filled with argon gas, 5 g of the above lithium cobalt oxide materials were placed in a beaker, 30 mL of a 6.6 mol/L hydrogen peroxide H2O2 solution was added, a magnetic stirrer was placed and the speed was set to 45 r /min, and the mixture was stirred for 20 h to obtain delithiated lithium cobalt oxide; the obtained solution was quickly filtered and deionized water was used to remove residual impurities, and the obtained delithiated lithium cobalt oxide material was dried in a vacuum oven for 8 h;
  • Electrolyte powder reaction The four different delithiated lithium cobalt oxide materials prepared in step (1) are mixed with the electrolyte respectively. To prevent the electrolyte from absorbing moisture, the delithiated lithium cobalt oxide materials and the electrolyte are placed in a hydrothermal kettle in a dehumidification room. 5 g of the delithiated lithium cobalt oxide material is added with 10 g of the electrolyte. After sealing, the mixture is placed in an oven preheated to 70° C. The stirring setting is turned on so that the stirring speed in the hydrothermal kettle is 120 r/min. After the reaction is completed, the solution is quickly filtered to obtain a filtrate and a powder. The powder is repeatedly washed with ethanol to remove electrolyte impurities and then dried in a vacuum oven for 8 h.
  • positive electrode material lithium cobalt oxide
  • NMP positive electrode material and conductive carbon black
  • the electrode slurry is evenly coated on aluminum foil to make a pole piece, which is then dried in an oven at 120°C to make a positive electrode piece for standby use; the positive electrode piece is assembled with a separator, a lithium sheet, an electrolyte, etc. into a button-type half-cell.
  • the button-type half-cell is subjected to an EIS test, the frequency range of the EIS test is 0.05 to 106 Hz, and the EIS test is completed within 1.5 hours;
  • step (3) The results obtained in step (3) are shown in Table 2.
  • the data on the amount of cobalt element dissolved and the R CT value in Table 2 are the average values of 4 parallel samples in each group of lithium cobalt oxide.
  • lithium cobalt oxide-1, lithium cobalt oxide-2, lithium cobalt oxide-3, and lithium cobalt oxide-4 before delithiation were prepared as soft-pack full batteries, and high-temperature storage tests were performed at 60°C to obtain storage performance data (capacity retention rate), which are recorded together in Table 1;
  • This embodiment provides a method for evaluating lithium-ion battery materials, which is used to evaluate the high-temperature storage performance of ternary positive electrode materials.
  • the method comprises the following steps:
  • Electrolyte powder reaction The delithiation ternary positive electrode material prepared in step (1) is mixed with the electrolyte respectively. To prevent the electrolyte from absorbing water, it is placed in a hydrothermal kettle in a dehumidification room. Among them, 5g of positive electrode material powder is taken, and 11g of electrolyte is added. After sealing, it is placed in an oven preheated to 65°C, and the stirring setting is turned on. The stirring speed is 180r/min. After the reaction is completed, the solution is quickly filtered to obtain a filtrate and a powder. The powder is repeatedly washed with ethanol to remove electrolyte impurities, and then dried in a vacuum oven for 12h;
  • the prepared positive electrode slurry is evenly coated on aluminum foil to make a pole piece, and dried in an oven at 120°C to make a positive electrode sheet for standby use; the positive electrode sheet is assembled with a diaphragm, a lithium sheet, an electrolyte, etc. into a button-type half-cell.
  • the button-type half-cell is subjected to EIS testing, the frequency range of the EIS test is 0.05 to 106 Hz, and the EIS test is completed within 1.5 hours;
  • step (3) The results obtained in step (3) are shown in Table 4.
  • the manganese element dissolution data and R CT value in Table 4 are the average values of 4 parallel samples in each group of ternary positive electrode materials.
  • ternary-1, ternary-2, ternary-3, and cobalt ternary-4 before delithiation were prepared as soft-pack full batteries, and high-temperature storage tests were performed at 60°C to obtain storage performance data (capacity retention rate), which are recorded together in Table 2;
  • This comparative example provides a method for evaluating lithium-ion battery materials.
  • step (3) only the delithiated lithium cobalt oxide material is mixed with the electrolyte, and heated and allowed to stand without stirring.
  • Other conditions are exactly the same as those in Example 1.
  • This comparative example provides a method for evaluating lithium-ion battery materials.
  • step (3) only the delithiated ternary positive electrode material is mixed with the electrolyte respectively, and heated and allowed to stand without stirring.
  • Other conditions are exactly the same as those in Example 2.

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Abstract

一种锂离子电池材料的评估方法及其应用，评估方法先将待测试正极材料制备为脱锂态正极材料，再置于电解液中加热搅拌，用固液分离后得到的滤液进行ICP测试，获得主元素溶出数据，同时，将得到粉料进行EIS测试，获得界面电荷转移阻抗RCT值，最后根据所得的两种数据综合评估含有待测试正极材料的软包电池的高温存储性能。评估方法能够模拟正极材料与电解液实际高温的反应过程，以得到满电态的正极材料并获取其主元素溶出数据和RCT值，从而快速推测评估该正极材料的高温存储性能。

Description

一种锂离子电池材料的评估方法及其应用 技术领域
本公开属于锂离子电池领域，例如一种锂离子电池材料的评估方法及其应用。
背景技术
目前，锂离子电池因其能量密度高、循环寿命长、倍率性能好等优点获得成功，广泛应用于便携式消费电子、电动汽车、储能等领域。但是在高温状态下，锂离子电池的电极材料界面与电解液反应更加复杂，不仅会造成高温下的性能损失，还可能会引起安全问题，例如产生气体进而导致电池鼓胀，容易造成隐患。
因此，对锂离子电池正极材料进行高温性能的相关测试是非常必要的。目前往往通过制备软包全电池来评价正极材料及含有其的锂电池的高温存储性能，通过测试全电池满电状态下经过不等时间，或者不同温度存储前后电性能变化和鼓胀率。通过对比电性能指标变化程度和电池的鼓胀程度来衡量其可靠性和安全性。
CN108267693B公开了一种锂电池正极材料高温存储性能的快速评价方法，使用锂离子扣式半电池对正极材料进行高温浮充充电，并根据浮充容量测试数据便可以推测不同正极材料之间高温存储性能的差异。但该快速评价方法只能推测不同正极材料之间的高温存储性能的差异，并不能直观表征出高温存储期间正极材料的性能变化。
CN110658473B公开了一种锂电池正极材料高温存储性能的快速评价方法，模拟正极材料在全电池高温存储的环境状态，通过化学法脱锂制备得到脱锂态 正极材料，并针对脱锂态正极材料进行等效高温存储测试，通过首次放电容量比评估容量保持率。该方法通过加强氧化剂得到脱锂态正极材料，在与氧化剂反应过程中，界面情况变得复杂，且脱锂量无法保证，再次制备成扣式电池，其放电容量并不稳定，降低了评估可靠性。
从以上可以看出，尚需要开发一种新的快速判断锂离子电池正极材料高温存储性能的评估方法，以提升测试效率，同时降低评估成本。
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。
本公开提供一种锂离子电池材料的评估方法及其应用，所述评估方法先将待测试正极材料制备为脱锂态正极材料，再置于电解液中加热搅拌，用固液分离后得到的滤液进行ICP测试，获得主元素溶出数据，同时，将得到粉料进行EIS测试，获得界面电荷转移阻抗RCT值，最后根据所得的两种数据综合评估含有所述待测正极材料的软包电池的高温存储性能。所述评估方法能够模拟正极材料与电解液实际高温的反应过程，以得到满电态的正极材料并获取其主元素溶出数据和RCT值，从而快速推测评估该正极材料的高温存储性能，所述评估方法操作简单，成本较低，有利于提升评估效率。
为达此目的，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锂离子电池材料的评估方法，所述评估方法包括如下步骤：
(1)将待测试正极材料制备为脱锂态正极材料；
(2)将步骤(1)所述脱锂态正极材料置于电解液中加热搅拌，经固液分离，得到滤液与粉料；
(3)将步骤(2)所得滤液进行ICP(电感耦合等离子体，Inductively Coupled Plasma)测试，获得主元素溶出数据；同时，将步骤(2)所述粉料作为正极材料制备为扣式半电池，进行EIS(电化学阻抗谱，Electrochemical Impedance Spectroscopy)测试，获得界面电荷转移阻抗RCT值；
(4)步骤(3)所得主元素溶出数据及RCT值越大，则待测正极材料的高温存储性能越差。
本公开实施例所述评估方法将正极材料制备为脱锂态正极材料能够模拟正极材料与电解液实际高温的反应过程，并使正极材料为满电状态(脱锂态)，然后进行测试获取此时的主元素溶出数据和RCT值，从而快速推测评估该正极材料的高温存储性能，所述评估方法操作简单，成本较低，有利于提升评估效率。
本公开实施例对所用的电解液不作具体的限制，本领域的技术人员可以根据使用的待测试正极材料，相应地选择与之适配的电解液即可。
示例性地，按总质量为100wt％计算，所述电解液包括9～15wt％锂盐、77～88wt％的非水有机溶剂和3～8wt％的添加剂；所述锂盐包括四氟硼酸锂(LiBF4)、六氟磷酸锂(LiPF6)或新型锂盐双氟磺酰亚胺锂(LiFSI)中的至少一种；非水有机溶剂包括碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)或碳酸甲乙酯(EMC)中的至少一种；添加剂包括成膜添加剂、高/低温添加剂、过充保护添加剂、阻燃添加剂、倍率型添加剂中的至少一种，例如可以选择碳酸亚乙烯酯(VC)和/或氟代碳酸乙烯酯(FEC)。
以下作为本公开实施例可选的技术方案，但不作为本公开提供的技术方案的限制，通过以下技术方案，可以更好地达到和实现本公开的技术目的和有益效果。
作为本公开实施例可选的技术方案，步骤(1)所述待测试正极材料包括钴酸锂、磷酸铁锂或三元正极材料中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括钴酸锂与磷酸铁锂的组合、钴酸锂与三元正极材料的组合或磷酸铁锂与三元正极材料的组合。
作为本公开实施例可选的技术方案，步骤(1)所述脱锂态正极材料的制备方法包括：
向所述待测试正极材料中加入氧化剂，进行脱锂反应，得到所述脱锂态正极材料。
作为本公开实施例可选的技术方案，所述氧化剂包括次溴酸、偏高碘酸、次氯酸、亚氯酸、高锰酸、高溴酸或过氧化氢中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括次溴酸与偏高碘酸的组合、偏高碘酸与次氯酸的组合、亚氯酸与高锰酸的组合、高锰酸与高溴酸的组合、亚氯酸与过氧化氢的组合。
在一个实施例中，所述氧化剂的用量为每克待测试正极材料使用4～8mL，例如4mL、4.5mL、5mL、5.5mL、6mL、6.5mL、7mL、7.5mL或8mL等，所述氧化剂的浓度为1.4～8mol/L，例如1.4mol/L、2mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L、6mol/L、6.5mol/L、7mol/L、7.5mol/L或8mol/L等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本公开实施例可选的技术方案，所述脱锂反应在搅拌下进行。
在一个实施例中，所述脱锂反应的时间为18～22h，例如18h、19h、20h、21h或22h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本公开实施例可选的技术方案，步骤(2)所述脱锂态正极材料与所述电解液的固液比为1g:(1.5～2.5)g，例如1g:1.5g、1g:1.6g、1g:1.7g、1g:1.8g、1g:1.9g、1g:2g、1g:2.1g、1g:2.2g、1g:2.3g、1g:2.4g或1g:2.5g等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
在一个实施例中，所述电解液的用量为20～200mL，例如20mL、50mL、80mL、110mL、140mL、170mL或200mL等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本公开实施例可选的技术方案，步骤(3)所述加热搅拌在真空中或除湿环境中进行。
本公开实施例所述加热搅拌需要在真空中或除湿环境中进行，以防止电解液吸入水分，在得到所述滤液也应注意密封保存，以防吸水。
在一个实施例中，步骤(3)所述加热搅拌在有聚四氟乙烯内胆的水热釜中进行。
在一个实施例中，步骤(3)所述加热搅拌的温度为40～80℃，例如40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃或80℃等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
在一个实施例中，步骤(3)所述加热搅拌的时间为2～4h，例如2h、2.2h、2.4h、2.6h、2.8h、3h、3.2h、3.4h、3.6h、3.8h或4h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
在一个实施例中，步骤(3)所述加热搅拌的搅拌速率为80～200r/min，例如80r/min、100r/min、120r/min、140r/min、160r/min、180r/min或200r/min等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本公开实施例可选的技术方案，所述评估方法步骤(4)还包括：
将主元素溶出数据及标准RCT值与含有待测正极材料的软包电池的高温存储性能相关联，建立数据库，模拟所述主元素溶出数据与所述高温存储性能的线性关系和/或模拟所述RCT值与所述高温存储性能的线性关系；根据所述线性关系推算含有所述待测正极材料的软包电池的高温存储性能。
在一个实施例中，所述数据库至少包括10个不同的所述待测正极材料的主元素溶出数据、标准RCT值及含有所述待测正极材料的软包电池的高温存储性能的数据。
作为本公开实施例可选的技术方案，所述评估方法包括如下步骤：
(1)向所述待测试正极材料中加入氧化剂，所述氧化剂的用量为每克待测试正极材料使用4～8mL，所述氧化剂的浓度为1.4～8mol/L，搅拌下进行脱锂反应18～22h，得到所述脱锂态正极材料；所述待测试正极材料包括钴酸锂、磷酸铁锂或三元正极材料中的任意一种或至少两种的组合；所述氧化剂包括次溴酸、偏高碘酸、次氯酸、亚氯酸、高锰酸、高溴酸或过氧化氢中的任意一种或至少两种的组合；
(2)在除湿间中，按照固液比为1g:(1.5～2.5)g将步骤(1)所述脱锂态正极材料与电解液装入水热釜中的聚四氟乙烯内胆中混合均匀，使电解液的用量20～200mL，然后将水热釜放入预先加热到40～80℃下的烘箱中，设置搅拌速率为80～200r/min，进行加热搅拌2～4h，反应结束后抽滤得到滤与粉料，将所得粉料洗涤并烘干后备用；
(3)将步骤(2)所得滤液进行ICP测试，获得主元素溶出数据；同时，将步骤(2)所述粉料作为正极材料制备为扣式半电池，进行EIS测试，获得界面电荷转移阻抗RCT值；
(4)根据步骤(3)所得主元素溶出数据及RCT值评估含有所述待测正极材 料的软包电池的高温存储性能，所得主元素溶出数据及RCT值越大，则待测正极材料的高温存储性能越差；并将主元素溶出数据及标准RCT值与含有待测正极材料的软包电池的高温存储性能相关联，建立至少包括10个样本数据的数据库，模拟所述主元素溶出数据与所述高温存储性能的线性关系和/或模拟所述RCT值与所述高温存储性能的线性关系；根据所述线性关系推算含有所述待测正极材料的软包电池的高温存储性能。
第二方面，本公开实施例提供了一种根据第一方面所述的评估方法在锂离子电池制造领域中的应用。
与相关技术方案相比，本公开至少具有以下有益效果：
所述评估方法能够模拟正极材料与电解液实际高温的反应过程，以得到满电态的正极材料并获取其主元素溶出数据和RCT值，从而快速推测评估该正极材料的高温存储性能，所述评估方法操作简单，成本较低，有利于提升评估效率。
在阅读并理解了详细描述后，可以明白其他方面。
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。
以下实施例及对比例使用的电解液均采用CN115117445A提供的锂离子电池电解液，所述电解液包含锂盐、非水有机溶剂及添加剂；具体地，在含水量<10ppm的氩气气氛手套箱中，将碳酸乙烯酯、碳酸二乙酯、碳酸甲乙酯、氟代碳酸乙烯酯按照质量百分含量20wt％、30wt％、40wt％、10wt％进行混合，得到混合有机溶剂，然后将充分干燥的锂盐溶解于上述混合有机溶剂中，锂盐为六氟磷酸锂和二氟双草酸磷酸锂组成的混合物，锂盐在电解液中的浓度为 1mol/L，其中六氟磷酸锂和二氟双草酸磷酸锂的摩尔比为95:5，添加剂为1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚、碳酸亚乙烯酯和硫酸乙烯酯组成的混合物，1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚、碳酸亚乙烯酯和硫酸乙烯酯的添加量均占电解液总质量的1wt％，加入添加剂搅拌均匀后，获得所述电解液。
实施例1
本实施例提供了一种锂离子电池材料的评估方法，所述评估方法用于钴酸锂正极材料的高温存储性能的评估，所述评估方法包括如下步骤：
(1)脱锂态钴酸锂材料的制备：选择四组不同的钴酸锂材料，分别标记为钴酸锂-1，钴酸锂-2，钴酸锂-3，钴酸锂-4，且每组钴酸锂制备4个平行样；脱锂过程在充满氩气的手套箱中进行，分别取5g上述钴酸锂材料放于烧杯内，加入30mL浓度6.6mol/L的过氧化氢H2O2溶液，放入磁子后在磁力搅拌器上设定转速为45r/min，搅拌20h，得到脱锂态钴酸锂；将所得溶液快速抽滤并使用去离子水去除残留杂质后，把得到的脱锂态钴酸锂材料在真空烘箱中干燥8h；
(2)电解液粉末反应：将步骤(1)制备得到的四种不同的脱锂态钴酸锂材料分别与电解液混合，为防止电解液中吸入水分，在除湿间将脱锂态钴酸锂材料与电解液一同装入水热釜中，其中，脱锂态钴酸锂材料取5g，加入电解液10g，密封好后，放入预先加热到温度70℃的烘箱中，打开搅拌设置，使水热釜内的搅拌速度为120r/min，反应结束后，将溶液快速抽滤，得到滤液与粉料，将所述粉料使用乙醇反复清洗除去电解液杂质后，在真空烘箱中干燥8h；
(3)测试：将步骤(2)所得滤液进行ICP测试，得到极片的主元素钴溶出数据；按照正极材料(钴酸锂):导电碳黑:PVDF＝94％:3％:3％的质量比称取定量物料，将PVDF溶于定量NMP中，加入正极材料与导电碳黑，放入搅拌机中搅拌35min，将上述物料进行均匀混合，制作成均匀的正极浆料。将制作好的正 极浆料均匀涂覆在铝箔上制作成极片，在120℃烘箱中烘干，制作成正极片待用；将正极片与隔膜、锂片、电解液等组装成扣式半电池。将扣式半电池进行EIS测试，EIS测试的频率范围为0.05～106Hz，EIS测试在1.5h内完成；
(4)分析：步骤(3)所得结果如表2所示，表2中的钴元素溶出量数据及RCT值为每组钴酸锂中4个平行样的平均值。同时，为了更直观地表明所述钴酸锂材料的高温存储性能，将脱锂前的钴酸锂-1，钴酸锂-2，钴酸锂-3，钴酸锂-4分别制备为软包全电池，并进行在60℃下进行高温存储测试，得到存储性能数据(容量保持率)，此数据一同记录于表1；
表1
从表1可以看出，不同组别钴酸锂的高温存储性能与钴元素溶出量呈现正相关性，同时，高温存储性能与EIS测试的电荷转移阻抗值也呈现出正相关性，所得钴元素溶出数据及RCT值越大，则待测正极材料的高温存储性能越差。
以上说明本实施例提供的评估方法能有效、快速地对钴酸锂正极材料进行存储性能评估。
实施例2
本实施例提供了一种锂离子电池材料的评估方法，所述评估方法用于三元正极材料的高温存储性能的评估，所述评估方法包括如下步骤：
(1)脱锂态三元正极材料的制备：选择四组不同的三元正极材料，分别标记为三元-1，三元-2，三元-3，三元-4，且每组三元正极材料制备4个平行样；脱锂过程在充满氩气的手套箱中进行，取8g三元材料放于烧杯内，加入50ml浓度2mol/L的次氯酸溶液，放入磁子后在磁力搅拌器上设定转速为55r/min，搅拌24h，得到脱锂态三元正极材料；将所得溶液快速抽滤并使用去离子水去除残留杂质后，把得到的脱锂态三元正极材料在真空烘箱中干燥10h；
(2)电解液粉末反应：将步骤(1)制备得到的脱锂态三元正极材料分别与电解液混合，为防止电解液中吸入水分，在除湿间将其装入水热釜中，其中，正极材料粉末取5g，电解液加11g，密封好后，放入预先加热65℃的烘箱中，打开搅拌设置，搅拌速度180r/min，反应结束后，将溶液快速抽滤，得到滤液与粉料，将所述粉料使用乙醇反复清洗除去电解液杂质后，在真空烘箱中干燥12h；
(3)测试：将步骤(2)所得滤液进行ICP测试，得到极片的主元素锰溶出数据；按照三元正极材料:导电碳黑:PVDF＝94％:3％:3％的质量比称取定量物料，将PVDF溶于定量NMP中，加入正极材料与导电碳黑，放入搅拌机中搅拌35min，将上述物料进行均匀混合，制作成均匀的正极浆料。将制作好的正极浆料均匀涂覆在铝箔上制作成极片，在120℃烘箱中烘干，制作成正极片待用；将正极片与隔膜、锂片、电解液等组装成扣式半电池。将扣式半电池进行EIS测试，EIS测试的频率范围为0.05～106Hz，EIS测试在1.5h内完成；
(4)分析：步骤(3)所得结果如表4所示，表4中的锰元素溶出量数据及RCT值为每组三元正极材料中4个平行样的平均值。同时，为了更直观地表明所述三元正极材料的高温存储性能，将脱锂前的三元-1，三元-2，三元-3，钴三元-4分别制备为软包全电池，并在60℃下进行高温存储测试，得到存储性能数据(容量保持率)，此数据一同记录于表2；
表2
从表2可以看出，不同组别三元正极材料的高温存储性能与锰元素溶出量呈现正相关性，同时，高温存储性能与EIS测试的电荷转移阻抗值也呈现出正相关性，所得锰元素溶出数据及RCT值越大，则待测正极材料的高温存储性能越差。
以上说明本实施例提供的评估方法能有效、快速地对三元正极材料进行存储性能评估。
对比例1
本对比例提供了一种锂离子电池材料的评估方法，所述评估方法在步骤(3)中仅将所述脱锂态钴酸锂材料分别与电解液混合，并加热静置，并不开启搅拌，其他条件与实施例1完全相同。
对比例2
本对比例提供了一种锂离子电池材料的评估方法，所述评估方法在步骤(3)中仅将所述脱锂态三元正极材料分别与电解液混合，并加热静置，并不开启搅拌，其他条件与实施例2完全相同。
对比例1及对比例2步中骤(3)所得数据如表3所示。
表3
从表3可以看出，不同组别钴酸锂正极材料的高温存储性能与钴元素的溶出量、EIS测试电荷转移阻抗值相比于实施例1较小，相似地，不同组别三元正极材料的高温存储性能与锰元素溶出量、EIS测试电荷转移阻抗值相比于实施例2较小；对比例中的各数值之间没有差异性与可靠性，与存储性能相关性不大。这说明步骤(2)中与电解液反应时进行搅拌对劣化模拟存储条件，加速反应至关重要，有利于提高评估方法的准确性，即脱锂是更重要的一步。

Claims (17)

  1. 一种锂离子电池材料的评估方法，所述评估方法包括如下步骤：
    (1)将待测试正极材料制备为脱锂态正极材料；
    (2)将步骤(1)所述脱锂态正极材料置于电解液中加热搅拌，经固液分离，得到滤液与粉料；
    (3)将步骤(2)所得滤液进行ICP测试，获得主元素溶出数据；同时，将步骤(2)所述粉料作为正极材料制备为扣式半电池，进行EIS测试，获得界面电荷转移阻抗RCT值；
    (4)步骤(3)所得主元素溶出数据及RCT值越大，则待测正极材料的高温存储性能越差。
  2. 根据权利要求1所述的评估方法，其中，步骤(1)所述待测试正极材料包括钴酸锂、磷酸铁锂或三元正极材料中的任意一种或至少两种的组合。
  3. 根据权利要求1或2所述的评估方法，其中，步骤(1)所述脱锂态正极材料的制备方法包括：
    向所述待测试正极材料中加入氧化剂，进行脱锂反应，得到所述脱锂态正极材料。
  4. 根据权利要求3所述的评估方法，其中，所述氧化剂包括次溴酸、偏高碘酸、次氯酸、亚氯酸、高锰酸、高溴酸或过氧化氢中的任意一种或至少两种的组合。
  5. 根据权利要求3或4所述的评估方法，其中，所述氧化剂的用量为每克待测试正极材料使用4～8mL；所述氧化剂的浓度为1.4～8mol/L。
  6. 根据权利要求1-5任意一项所述的评估方法，其中，所述脱锂反应在搅拌下进行。
  7. 根据权利要求1-6任意一项所述的评估方法，其中，所述脱锂反应的时 间为18～22h。
  8. 根据权利要求1-7任意一项所述的评估方法，其中，步骤(2)所述脱锂态正极材料与所述电解液的固液比为1g:(1.5～2.5)g。
  9. 根据权利要求1-8任意一项所述的评估方法，其中，步骤(2)所述电解液的用量为20～200mL。
  10. 根据权利要求1-9任意一项所述的评估方法，其中，步骤(3)所述加热搅拌在真空中或除湿环境中进行。
  11. 根据权利要求1-10任意一项所述的评估方法，其中，步骤(3)所述加热搅拌在有聚四氟乙烯内胆的水热釜中进行。
  12. 根据权利要求1-11任意一项所述的评估方法，其中，步骤(3)所述加热搅拌的温度为40～80℃。
  13. 根据权利要求1-12任意一项所述的评估方法，其中，步骤(3)所述加热搅拌的时间为2～4h。
  14. 根据权利要求1-13任意一项所述的评估方法，其中，步骤(3)所述加热搅拌的搅拌速率为80～200r/min。
  15. 根据权利要求1-14任意一项所述的评估方法，其中，所述评估方法步骤(4)还包括：
    将主元素溶出数据及标准RCT值与含有待测正极材料的软包电池的高温存储性能相关联，建立数据库，模拟所述主元素溶出数据与所述高温存储性能的线性关系和/或模拟所述RCT值与所述高温存储性能的线性关系；根据所述线性关系推算含有所述待测正极材料的软包电池的高温存储性能；
    可选地，所述数据库至少包括10个不同的所述待测正极材料的主元素溶出数据、标准RCT值及含有所述待测正极材料的软包电池的高温存储性能的数据。
  16. 根据权利要求1-15任意一项所述的评估方法，其中，所述评估方法包括如下步骤：
    (1)向所述待测试正极材料中加入氧化剂，所述氧化剂的用量为每克待测试正极材料使用4～8mL，所述氧化剂的浓度为1.4～8mol/L，搅拌下进行脱锂反应18～22h，得到所述脱锂态正极材料；所述待测试正极材料包括钴酸锂、磷酸铁锂或三元正极材料中的任意一种或至少两种的组合；所述氧化剂包括次溴酸、偏高碘酸、次氯酸、亚氯酸、高锰酸、高溴酸或过氧化氢中的任意一种或至少两种的组合；
    (2)在除湿间中，按照固液比为1g:(1.5～2.5)g将步骤(1)所述脱锂态正极材料与电解液装入水热釜中的聚四氟乙烯内胆中混合均匀，使电解液的用量20～200mL，然后将水热釜放入预先加热到40～80℃下的烘箱中，设置搅拌速率为80～200r/min，进行加热搅拌2～4h，反应结束后抽滤得到滤与粉料，将所得粉料洗涤并烘干后备用；
    (3)将步骤(2)所得滤液进行ICP测试，获得主元素溶出数据；同时，将步骤(2)所述粉料作为正极材料制备为扣式半电池，进行EIS测试，获得界面电荷转移阻抗RCT值；
    (4)根据步骤(3)所得主元素溶出数据及RCT值评估含有所述待测正极材料的软包电池的高温存储性能，所得主元素溶出数据及RCT值越大，则待测正极材料的高温存储性能越差；并将主元素溶出数据及标准RCT值与含有待测正极材料的软包电池的高温存储性能相关联，建立至少包括10个样本数据的数据库，模拟所述主元素溶出数据与所述高温存储性能的线性关系和/或模拟所述RCT值与所述高温存储性能的线性关系；根据所述线性关系推算含有所述待测正极材料的软包电池的高温存储性能。
  17. 一种根据权利要求1-16任意一项所述的评估方法在锂离子电池制造领域中的应用。
PCT/CN2023/093418 2023-05-11 2023-05-11 一种锂离子电池材料的评估方法及其应用 Ceased WO2024229784A1 (zh)

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