WO2020253277A1 - Method for using vacuum microwave drying to prepare ultra dry lithium salt for lithium battery - Google Patents
Method for using vacuum microwave drying to prepare ultra dry lithium salt for lithium battery Download PDFInfo
- Publication number
- WO2020253277A1 WO2020253277A1 PCT/CN2020/079090 CN2020079090W WO2020253277A1 WO 2020253277 A1 WO2020253277 A1 WO 2020253277A1 CN 2020079090 W CN2020079090 W CN 2020079090W WO 2020253277 A1 WO2020253277 A1 WO 2020253277A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- lithium salt
- microwave drying
- ultra
- vacuum
- Prior art date
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
- F26B5/048—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum in combination with heat developed by electro-magnetic means, e.g. microwave energy
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B3/00—Drying solid materials or objects by processes involving the application of heat
- F26B3/32—Drying solid materials or objects by processes involving the application of heat by development of heat within the materials or objects to be dried, e.g. by fermentation or other microbiological action
- F26B3/34—Drying solid materials or objects by processes involving the application of heat by development of heat within the materials or objects to be dried, e.g. by fermentation or other microbiological action by using electrical effects
- F26B3/347—Electromagnetic heating, e.g. induction heating or heating using microwave energy
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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 invention relates to a method for preparing ultra-dry lithium battery lithium salt by vacuum microwave drying.
- lithium-ion batteries have high energy density, high voltage and cycle Long life, no memory effect, good safety performance and other advantages;
- Lithium hexafluorophosphate is currently the main electrolyte for lithium-ion batteries. It can form an appropriate SEI film on the carbon negative electrode and has the advantages of a wide electrochemical stability window; lithium hexafluorophosphate will react with a small amount of water in the electrolyte to produce pentafluoride Phosphorus, phosphorus oxyfluoride and hydrogen fluoride and other harmful substances cause serious harm to lithium-ion batteries;
- Lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide and 4,5-dicyano-2-trifluoromethylimidazole lithium are emerging lithium-ion battery electrolytes. These compounds have good Electrochemical stability and thermal stability, superior conductivity and good compatibility with electrode materials; in the process of preparing these compounds, it is inevitable to use or produce water, carboxylic acids and various organic solvents Etc., the residues of these substances added to the electrolyte will cause great hidden dangers to the safety of lithium-ion batteries;
- lithium hexafluorophosphate As an example, its quality index requires water content ⁇ 20ppm, the best value is less than 10ppm, HF content ⁇ 20ppm, and the best value is less than 5ppm, the content of organic acids, alcohols, aldehydes, ketones, amines, amides and other impurities containing active hydrogen atoms in the molecule is less than 20ppm; the removal of the above substances is generally eluted with a low boiling point solvent, and then heated to vacuum Method of drying.
- Patent US 9079780 and CN 103868330 B describe various methods for concentrating LiFSI to overcome the formation of by-products, drying under a stream of dry inert gas or concentrating the LiFSI solution through a thin film evaporator. This method does not dry completely, and some moisture in the package cannot be effectively taken away.
- Patent CN 109923063 A discloses a method of using an organic solvent to form an azeotrope with water to remove water. This method will be repeated many times, and a large amount of organic solvent will be wasted, which will increase the difficulty of solvent recovery and operation in the later stage.
- Patent CN 103836885 B also uses chemical drying to remove water, but the desiccant used in this method is metal alkyls that easily react with water, but these compounds are expensive, and they are too active and difficult to prepare and store. Moreover, the entire reaction process is difficult to control and is relatively dangerous. Third, most of these compounds are toxic, flammable and explosive, and cause great harm to the human body, so this method is difficult to apply to actual production.
- Microwave drying is a relatively novel drying method. Compared with the traditional vacuum heating and drying method, microwave heating has the advantages of high thermal efficiency, fast heat transfer, and uniform heating of materials. It can overcome the slow heat transfer when heating under traditional vacuum. Uneven heating, unable to provide enough and suitable heat exchange surface and other problems, therefore, microwave drying has been widely used in food thawing, drying, baking, sterilization, sterilization and lignite, titanium concentrate, etc., but microwave is used There are no reports and applications on the drying of lithium batteries, and the present invention breaks through the current limitations of lithium battery drying, and obtains dried lithium salt in a more efficient, energy-saving and environmentally friendly way.
- patent CN 108771156 A mentions that the water content of kidney beans is 7 ⁇ 1% by microwave drying; the patent CN 103234339 B mentions that the moisture content of the titanium concentrate can be reduced to less than 1 wt% by drying the titanium concentrate with a microwave device; Patent CN 108041152 A mentions the use of microwave drying to prepare dried pineapple, and the moisture content of pineapple slices can reach 8-16%.
- microwave drying is applied to lithium batteries, which can reduce the moisture content to less than 20 ppm.
- the present invention provides a method for preparing ultra-dry lithium battery lithium salt by vacuum microwave drying, which can effectively remove the water or solvent added, generated or residual during the preparation process of lithium battery lithium salt, and effectively solve the problem of traditional drying methods in the production process.
- the heat exchange surface is insufficient and the heat exchanger is difficult to design and process. It effectively solves the defects of traditional drying methods such as uneven heating, and can efficiently and energy-savingly prepare ultra-low moisture lithium salts for lithium-ion batteries.
- the present invention provides a method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying.
- the wet product of lithium salt is placed in a vacuum microwave drying device, the device is activated to make the vacuum degree less than 500mmHg, and the microwave heating device is activated. After the microwave operation is over, the evaporable impurities in the lithium salt can be removed to obtain an ultra-dry lithium salt suitable for lithium ion batteries.
- the lithium salt in the lithium salt wet product is lithium hexafluorophosphate (LiPF 6 ), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium bisfluorosulfonimide (LiFSI), and bisoxalic acid boric acid.
- the properties of the wet product of the lithium salt can be a solution, slurry, paste or wet solid with a solid content of more than 30%, but it is not limited to the above mentioned properties;
- the vaporizable impurities in the lithium salt wet product are water and organic solvents such as carboxylic acids, alcohols, ketones, esters, ethers, halogenated hydrocarbons, nitriles, etc., one or more than two Mixture, but not limited to the above solvent types or mixed solvents;
- the vacuum of the device during the drying process is less than 500 mmHg, most preferably 0.1-100.0 mmHg;
- the working temperature of the microwave heating device is -40 to 300°C; the preferred working temperature is 0-150°C, and the most preferred working temperature is 30-60°C;
- the microwave frequency of the microwave heating device is 300MHz-50GHz, preferably 1000-10000MHz, most preferably 2400-2500MHz;
- the microwave working mode can be continuous or intermittent
- the crude product of lithium hexafluorophosphate (LiPF 6 ) (water content ⁇ 5%) was recrystallized in toluene, and the crystals were filtered out. 100g of the crystals were added to the flask and placed in a microwave dryer with a microwave frequency of 2450MHz. Set the maximum working temperature of the microwave dryer to 60°C, start the microwave dryer; after the microwave operation is completed, use high-purity nitrogen to break the air and take samples to determine the moisture and toluene content; test results: water 1.2ppm, toluene 2.3ppm.
- LiDTI 4,5-dicyano-2-trifluoromethylimidazolium
- Lithium bisfluorosulfonimide (LiFSI) crude product (water content ⁇ 5%) was dissolved in ether, the insoluble matter was filtered out, and concentrated into a paste. 20g of the paste was added to the flask and placed in the microwave frequency. In a 2450MHz microwave dryer, vacuumize to 60.0mmHg, set the maximum operating temperature of the microwave dryer to 60°C, and start the microwave dryer; after the microwave operation is completed, use high-purity nitrogen to break the air and sample to determine the moisture and ether content; Test results: water 20.0ppm, ether 0.5ppm.
- Lithium bisfluorosulfonimide (LiFSI) crude product (water content ⁇ 5%) was dissolved in ether, the insoluble matter was filtered out, and concentrated into a paste. 20g of the paste was added to the flask and placed in the microwave frequency.
- a 2450MHz microwave dryer vacuumize to 20.0mmHg under the protection of inert gas, set the maximum working temperature of the microwave dryer to 60°C, and start the microwave dryer; after the microwave operation, use high-purity nitrogen to break the air and sample Determine the content of water and ether; test results: water 20.0ppm, ether 0.5ppm.
Abstract
A method for using vacuum microwave drying to prepare an ultra dry lithium salt for a lithium battery, the method being as follows: placing a lithium salt wet product into a vacuum microwave drying apparatus, initiating the apparatus to cause the vacuum degree to be less than 500 mmHg, and initiating microwaves to heat the apparatus. After microwave operation is completed, evaporable impurities in the lithium salt can be removed, to obtain an ultra dry lithium salt suitable for a lithium ion battery. The lithium salt wet product may be a solution having a solid content of 30% or greater, a slurry, or a solid. Using vacuum microwave drying, a lithium salt can be highly efficiently and evenly heated, effectively removing evaporable impurities in the lithium salt.
Description
本发明涉及一种利用真空微波干燥制备超干锂电池锂盐的方法。The invention relates to a method for preparing ultra-dry lithium battery lithium salt by vacuum microwave drying.
受益于移动设备和新能源汽车等行业的发展，我国乃至全球的动力电池市场迎来爆发式增长，与传统的镍镉、镍氢电池相比，锂离子电池具高能量密度，电压高，循环寿命长，无记忆效应，安全性能好等优点；Benefiting from the development of industries such as mobile devices and new energy vehicles, the power battery market in my country and even the world has ushered in explosive growth. Compared with traditional nickel-cadmium and nickel-hydrogen batteries, lithium-ion batteries have high energy density, high voltage and cycle Long life, no memory effect, good safety performance and other advantages;
六氟磷酸锂是目前主要的锂离子电池电解质，它能在炭负电极上形成适当的SEI膜，具有较宽广的电化学稳定窗口等优点；六氟磷酸锂会电解液中存在微量的水发生反应，产生五氟化磷，三氟氧磷和氟化氢等有害物质，对锂离子电池产生严重的危害；Lithium hexafluorophosphate is currently the main electrolyte for lithium-ion batteries. It can form an appropriate SEI film on the carbon negative electrode and has the advantages of a wide electrochemical stability window; lithium hexafluorophosphate will react with a small amount of water in the electrolyte to produce pentafluoride Phosphorus, phosphorus oxyfluoride and hydrogen fluoride and other harmful substances cause serious harm to lithium-ion batteries;
双三氟甲基磺酰亚胺锂，双氟磺酰亚胺锂和4,5-二氰基-2-三氟甲基咪唑锂等是新兴的锂离子电池电解质，这些化合物都具有良好的电化学稳定性和热稳定性，优越的导电性和与电极材料良好的相容性等特点；在制备这些化合物的过程中，不可避免的需要使用或产生水，羧酸和各种的有机溶剂等，这些物质残留被添加到电解液中会对锂离子电池的安全性造成极大的隐患；Lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide and 4,5-dicyano-2-trifluoromethylimidazole lithium are emerging lithium-ion battery electrolytes. These compounds have good Electrochemical stability and thermal stability, superior conductivity and good compatibility with electrode materials; in the process of preparing these compounds, it is inevitable to use or produce water, carboxylic acids and various organic solvents Etc., the residues of these substances added to the electrolyte will cause great hidden dangers to the safety of lithium-ion batteries;
锂离子电池市场迅猛发展的同时也对其电解质品质要求越来越严格，以六氟磷酸锂为例，其质量指标要求水含量<20ppm，最佳值为小于10ppm，HF含量<20ppm，最佳值为小于5ppm，分子中含 有活泼氢原子的有机酸类，醇类，醛类，酮类，胺类，酰胺类等杂质含量<20ppm；对于上述物质的去除一般是使用低沸点溶剂洗脱，然后加热真空干燥的方法。With the rapid development of the lithium-ion battery market, its electrolyte quality requirements are becoming more and more stringent. Taking lithium hexafluorophosphate as an example, its quality index requires water content <20ppm, the best value is less than 10ppm, HF content <20ppm, and the best value is less than 5ppm, the content of organic acids, alcohols, aldehydes, ketones, amines, amides and other impurities containing active hydrogen atoms in the molecule is less than 20ppm; the removal of the above substances is generally eluted with a low boiling point solvent, and then heated to vacuum Method of drying.
专利US 9079780、CN 103868330 B描述了用于浓缩LiFSI的各种方法，以克服副产物的形成，在干燥的惰性气体流下干燥或通过薄膜蒸发器浓缩LiFSI溶液。该方法干燥不彻底，一些包裹的水分无法被有效带走。Patent US 9079780 and CN 103868330 B describe various methods for concentrating LiFSI to overcome the formation of by-products, drying under a stream of dry inert gas or concentrating the LiFSI solution through a thin film evaporator. This method does not dry completely, and some moisture in the package cannot be effectively taken away.
专利CN 109923063 A公开了一种使用有机溶剂与水形成共沸的方式进行除水。该方式会进行多次重复，会浪费大量的有机溶剂，为后期溶剂的回收和操作增加了困难。Patent CN 109923063 A discloses a method of using an organic solvent to form an azeotrope with water to remove water. This method will be repeated many times, and a large amount of organic solvent will be wasted, which will increase the difficulty of solvent recovery and operation in the later stage.
专利CN 103836885 B也是采用化学干燥除水的方式，但是该方法选用的干燥剂为烷基金属类易与水发生反应的物质，只是这些化合物一是造价较高，二是过于活泼难以制备与储存并且整个反应过程难以控制，比较危险，三是这些化合物大多有毒，易燃易爆，对人体伤害较大，所以该方法很难应用于实际生产。Patent CN 103836885 B also uses chemical drying to remove water, but the desiccant used in this method is metal alkyls that easily react with water, but these compounds are expensive, and they are too active and difficult to prepare and store. Moreover, the entire reaction process is difficult to control and is relatively dangerous. Third, most of these compounds are toxic, flammable and explosive, and cause great harm to the human body, so this method is difficult to apply to actual production.
微波干燥是一门较为新颖的干燥方法，与传统的真空加热干燥的方式相比，微波加热具有热效率高、传热速度快、物料受热均匀等优点，能克服传统真空下加热时热量传递慢，受热不均匀，无法提供足够和合适换热面等问题，因此，微波干燥已广泛应用于食品的解冻、干燥、焙烤、灭菌、杀菌以及用于褐煤、钛精矿等方面，但微波用于锂电方面的干燥未见报道和应用，而本发明突破了目前锂电干燥的局限，用一种更高效、更节能、更环保的方式得到干燥的锂盐。并且， 在专利CN 108771156 A中提到用微波干燥四季豆使之含水量为7±1％；专利CN 103234339 B中提到用微波装置干燥钛精矿可以使之含水量降至1wt％以下；专利CN 108041152 A中提到用微波干燥制备菠萝干，可至菠萝片水分含量为8～16％。而本发明将微波干燥用于锂电池方面，可以使其水分降至20ppm以下。Microwave drying is a relatively novel drying method. Compared with the traditional vacuum heating and drying method, microwave heating has the advantages of high thermal efficiency, fast heat transfer, and uniform heating of materials. It can overcome the slow heat transfer when heating under traditional vacuum. Uneven heating, unable to provide enough and suitable heat exchange surface and other problems, therefore, microwave drying has been widely used in food thawing, drying, baking, sterilization, sterilization and lignite, titanium concentrate, etc., but microwave is used There are no reports and applications on the drying of lithium batteries, and the present invention breaks through the current limitations of lithium battery drying, and obtains dried lithium salt in a more efficient, energy-saving and environmentally friendly way. In addition, the patent CN 108771156 A mentions that the water content of kidney beans is 7±1% by microwave drying; the patent CN 103234339 B mentions that the moisture content of the titanium concentrate can be reduced to less than 1 wt% by drying the titanium concentrate with a microwave device; Patent CN 108041152 A mentions the use of microwave drying to prepare dried pineapple, and the moisture content of pineapple slices can reach 8-16%. In the present invention, microwave drying is applied to lithium batteries, which can reduce the moisture content to less than 20 ppm.
发明内容Summary of the invention
本发明提供一种利用真空微波干燥制备超干锂电池锂盐的方法，可以有效去除锂电池锂盐制备过程中加入，产生或残留的水分或溶剂，有效的解决生产过程中，传统干燥方式存在的换热面不足，换热器难设计加工等问题，有效的解决传统干燥方式加热不均匀等缺陷，能够高效，节能的制备超低水分的用于锂离子电池的锂盐。The present invention provides a method for preparing ultra-dry lithium battery lithium salt by vacuum microwave drying, which can effectively remove the water or solvent added, generated or residual during the preparation process of lithium battery lithium salt, and effectively solve the problem of traditional drying methods in the production process. The heat exchange surface is insufficient and the heat exchanger is difficult to design and process. It effectively solves the defects of traditional drying methods such as uneven heating, and can efficiently and energy-savingly prepare ultra-low moisture lithium salts for lithium-ion batteries.
具体技术方案如下：本发明提供一种利用真空微波干燥制备超干锂电池锂盐的方法，将锂盐湿产品放置于真空微波干燥装置内，启动装置使真空度小于500mmHg，启动微波加热装置，微波工作结束后，即可去除锂盐中的可蒸发杂质，得到适用于锂离子电池的超干锂盐。The specific technical scheme is as follows: The present invention provides a method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying. The wet product of lithium salt is placed in a vacuum microwave drying device, the device is activated to make the vacuum degree less than 500mmHg, and the microwave heating device is activated. After the microwave operation is over, the evaporable impurities in the lithium salt can be removed to obtain an ultra-dry lithium salt suitable for lithium ion batteries.
作为优选方案，锂盐锂盐湿产品中的锂盐为六氟磷酸锂(LiPF
6)，双三氟甲基磺酰亚胺锂(LiTFSI)，双氟磺酰亚胺锂盐(LiFSI)，双草酸硼酸锂(LiBOB)，二氟硼酸草酸锂(LiODFB)，4,5-二氰基-2-三氟甲基咪唑锂(LiDTI)等一种或二种以上的混合物，但不限于上述锂盐及混合物；
As a preferred solution, the lithium salt in the lithium salt wet product is lithium hexafluorophosphate (LiPF 6 ), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium bisfluorosulfonimide (LiFSI), and bisoxalic acid boric acid. Lithium (LiBOB), lithium oxalate difluoroborate (LiODFB), 4,5-dicyano-2-lithium trifluoromethylimidazole (LiDTI), etc. or a mixture of two or more, but not limited to the above-mentioned lithium salts and mixture;
作为优选方案，锂盐锂盐湿产品其性状可为固含量30％以上 的溶液，浆料，膏体或湿性固体，但不限于上述所提性状；As a preferred solution, the properties of the wet product of the lithium salt can be a solution, slurry, paste or wet solid with a solid content of more than 30%, but it is not limited to the above mentioned properties;
作为优选方案，锂盐湿产品中的可蒸发杂质为水和有机溶剂如羧酸类、醇类、酮类、酯类、醚类、卤代烃类、腈类等一种或二种以上的混合物，但不限于上述溶剂种类或混合溶剂；As a preferred solution, the vaporizable impurities in the lithium salt wet product are water and organic solvents such as carboxylic acids, alcohols, ketones, esters, ethers, halogenated hydrocarbons, nitriles, etc., one or more than two Mixture, but not limited to the above solvent types or mixed solvents;
作为优选方案，干燥过程中装置的真空度小于500mmHg，最优选为0.1-100.0mmHg；As a preferred solution, the vacuum of the device during the drying process is less than 500 mmHg, most preferably 0.1-100.0 mmHg;
作为优选方案，微波加热装置的工作温度为-40～300℃；优选的工作温度为0-150℃，最优选的工作温度为30-60℃；As a preferred solution, the working temperature of the microwave heating device is -40 to 300°C; the preferred working temperature is 0-150°C, and the most preferred working temperature is 30-60°C;
作为优选方案，微波加热装置的微波频率为300MHz-50GHz，优选为1000-10000MHz，最优选为2400-2500MHz；As a preferred solution, the microwave frequency of the microwave heating device is 300MHz-50GHz, preferably 1000-10000MHz, most preferably 2400-2500MHz;
作为优选方案，微波工作方式可以是连续式，也可以是间歇式；As a preferred solution, the microwave working mode can be continuous or intermittent;
下面结合具体实施例，对本发明的内容做进一步详细说明：The content of the present invention will be further described in detail below in conjunction with specific embodiments:
实施例1Example 1
六氟磷酸锂(LiPF
6)粗产品(水含量≥5％)在甲苯中重结晶，过滤出晶体，将100g该晶体加入烧瓶并放置于微波频率为2450MHz的微波干燥器中，抽真空至50.0mmHg，设定微波干燥器的最高工作温度为60℃，启动微波干燥器；微波工作结束后，用高纯氮气破空后取样测定水分和甲苯含量；检测结果：水1.2ppm，甲苯2.3ppm。
The crude product of lithium hexafluorophosphate (LiPF 6 ) (water content ≥5%) was recrystallized in toluene, and the crystals were filtered out. 100g of the crystals were added to the flask and placed in a microwave dryer with a microwave frequency of 2450MHz. Set the maximum working temperature of the microwave dryer to 60℃, start the microwave dryer; after the microwave operation is completed, use high-purity nitrogen to break the air and take samples to determine the moisture and toluene content; test results: water 1.2ppm, toluene 2.3ppm.
实施例2Example 2
4,5-二氰基-2-三氟甲基咪唑锂(LiDTI)粗产品(水含量≥5％)溶于乙腈中，过滤后浓缩析出LiDTI晶体，将100g该晶体加入烧瓶 并放置于微波频率为2450MHz的微波干燥器中，抽真空至20.0mmHg，设定微波干燥器的最高工作温度为50℃，启动微波干燥器；微波工作结束后，用高纯氮气破空后取样测定水分和乙腈含量；检测结果：水13.0ppm，乙腈，无检出。The crude product of 4,5-dicyano-2-trifluoromethylimidazolium (LiDTI) (water content ≥5%) was dissolved in acetonitrile, filtered and concentrated to precipitate LiDTI crystals. 100g of the crystals were added to the flask and placed in the microwave In a microwave dryer with a frequency of 2450MHz, vacuumize to 20.0mmHg, set the maximum working temperature of the microwave dryer to 50℃, and start the microwave dryer; after the microwave operation is completed, use high-purity nitrogen to break the air and sample to determine the moisture and acetonitrile Content; test result: water 13.0ppm, acetonitrile, no detection.
实施例3Example 3
双氟磺酰亚胺锂盐(LiFSI)粗产品(水含量≥5％)溶解在乙醚中，过滤掉不溶物，浓缩成膏状物，将20g该膏状物加入烧瓶并放置于微波频率为2450MHz的微波干燥器中，抽真空至60.0mmHg，设定微波干燥器的最高工作温度为60℃，启动微波干燥器；微波工作结束后，用高纯氮气破空后取样测定水分和乙醚含量；检测结果：水20.0ppm，乙醚0.5ppm。Lithium bisfluorosulfonimide (LiFSI) crude product (water content ≥5%) was dissolved in ether, the insoluble matter was filtered out, and concentrated into a paste. 20g of the paste was added to the flask and placed in the microwave frequency. In a 2450MHz microwave dryer, vacuumize to 60.0mmHg, set the maximum operating temperature of the microwave dryer to 60℃, and start the microwave dryer; after the microwave operation is completed, use high-purity nitrogen to break the air and sample to determine the moisture and ether content; Test results: water 20.0ppm, ether 0.5ppm.
实施例4Example 4
双氟磺酰亚胺锂盐(LiFSI)粗产品(水含量≥5％)溶解在乙醚中，过滤掉不溶物，浓缩成膏状物，将20g该膏状物加入烧瓶并放置于微波频率为2450MHz的微波干燥器中，在惰性气体的保护下抽真空至20.0mmHg，设定微波干燥器的最高工作温度为60℃，启动微波干燥器；微波工作结束后，用高纯氮气破空后取样测定水分和乙醚含量；检测结果：水20.0ppm，乙醚0.5ppm。Lithium bisfluorosulfonimide (LiFSI) crude product (water content ≥5%) was dissolved in ether, the insoluble matter was filtered out, and concentrated into a paste. 20g of the paste was added to the flask and placed in the microwave frequency. In a 2450MHz microwave dryer, vacuumize to 20.0mmHg under the protection of inert gas, set the maximum working temperature of the microwave dryer to 60℃, and start the microwave dryer; after the microwave operation, use high-purity nitrogen to break the air and sample Determine the content of water and ether; test results: water 20.0ppm, ether 0.5ppm.
上面的实施例为用来说明本发明的几个具体的实施方式，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。The above examples are used to illustrate several specific embodiments of the present invention, but the present invention is not limited to these specific embodiments. Those skilled in the art should realize that the present invention covers all alternatives, improvements and equivalents that may be included within the scope of the claims.
Claims (8)
- 一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于包括以下步骤：A method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying is characterized in that it comprises the following steps:(1)将锂盐湿产品放置于真空微波干燥装置内(1) Place the wet lithium salt product in a vacuum microwave drying device(2)启动装置使装置内真空度小于500mmHg，然后启动微波加热装置(2) Start the device to make the vacuum in the device less than 500mmHg, then start the microwave heating device(3)微波工作结束后，即可去除锂盐中的可蒸发杂质，得到适用于锂离子电池的超干锂盐。(3) After the microwave operation is over, the evaporable impurities in the lithium salt can be removed to obtain an ultra-dry lithium salt suitable for lithium ion batteries.
- 根据权利要求1所述一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于所述步骤(1)中的锂盐为六氟磷酸锂(LiPF 6)，双三氟甲基磺酰亚胺锂(LiTFSI)，双氟磺酰亚胺锂盐(LiFSI)，双草酸硼酸锂(LiBOB)，二氟硼酸草酸锂(LiODFB)，4,5-二氰基-2-三氟甲基咪唑锂(LiDTI)等一种或二种以上的混合物，但不限于上述锂盐及混合物。 The method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying according to claim 1, wherein the lithium salt in step (1) is lithium hexafluorophosphate (LiPF 6 ), bistrifluoromethanesulfonate Lithium amide (LiTFSI), lithium bisfluorosulfonimide (LiFSI), lithium bisoxalate borate (LiBOB), lithium oxalate difluoroborate (LiODFB), 4,5-dicyano-2-trifluoromethylimidazole Lithium (LiDTI) or a mixture of two or more, but not limited to the above-mentioned lithium salts and mixtures.
- 根据权利要求1所述一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于所述步骤(1)中的锂盐湿产品为固含量30％以上的溶液，浆料，膏体或湿性固体，但不限于上述所提性状。The method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying according to claim 1, characterized in that the wet product of lithium salt in said step (1) is a solution, slurry, paste with a solid content of more than 30% Body or wet solid, but not limited to the above mentioned properties.
- 根据权利要求3所述一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于锂盐湿产品中的可蒸发杂质为水和有机溶剂如羧酸类、醇类、酮类、酯类、醚类、卤代烃类、腈类等一种或二种以上的混合物，但不限于上述溶剂种类或混合溶剂。The method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying according to claim 3, characterized in that the evaporable impurities in the wet product of lithium salt are water and organic solvents such as carboxylic acids, alcohols, ketones, One or a mixture of two or more of esters, ethers, halogenated hydrocarbons, nitriles, etc., but not limited to the above-mentioned solvent types or mixed solvents.
- 根据权利要求1所述一种利用真空微波干燥制备超干锂电池锂盐 的方法，其特征在于所述步骤(2)中的装置真空度小于500mmHg。The method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying according to claim 1, characterized in that the vacuum degree of the device in the step (2) is less than 500 mmHg.
- 根据权利要求1所述一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于所述步骤(2)中的微波加热装置的工作温度为-40～300℃。The method for preparing ultra-dry lithium battery lithium salt by vacuum microwave drying according to claim 1, wherein the working temperature of the microwave heating device in the step (2) is -40-300°C.
- 根据权利要求1所述一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于所述步骤(2)中的微波加热装置的微波频率为300MHz-50GHz。The method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying according to claim 1, wherein the microwave frequency of the microwave heating device in the step (2) is 300 MHz-50 GHz.
- 根据权利要求1所述一种利用真空微波干燥制备超干锂电池锂盐的方法，其特征在于所述步骤(2)中的微波工作方式可以是连续式，也可以是间歇式。The method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying according to claim 1, wherein the microwave working mode in step (2) can be continuous or intermittent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202080002482.8A CN112204329A (en) | 2020-03-13 | 2020-03-13 | Method for preparing lithium salt of ultra-dry lithium battery by vacuum microwave drying |
| PCT/CN2020/079090 WO2020253277A1 (en) | 2020-03-13 | 2020-03-13 | Method for using vacuum microwave drying to prepare ultra dry lithium salt for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/079090 WO2020253277A1 (en) | 2020-03-13 | 2020-03-13 | Method for using vacuum microwave drying to prepare ultra dry lithium salt for lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020253277A1 true WO2020253277A1 (en) | 2020-12-24 |
Family
ID=74033781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2020/079090 WO2020253277A1 (en) | 2020-03-13 | 2020-03-13 | Method for using vacuum microwave drying to prepare ultra dry lithium salt for lithium battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112204329A (en) |
| WO (1) | WO2020253277A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10310425A (en) * | 1997-05-07 | 1998-11-24 | Honjiyou Chem Kk | Production of anhydrous lithium chloride |
| CN104129773A (en) * | 2013-08-15 | 2014-11-05 | 多氟多化工股份有限公司 | Drying method and apparatus for lithium hexafluorophosphate |
| CN204944124U (en) * | 2015-08-07 | 2016-01-06 | 赣州腾远钴业有限公司 | A kind of cobalt acid lithium vacuum microwave drying device |
| CN107204466A (en) * | 2017-03-31 | 2017-09-26 | 宁波中车新能源科技有限公司 | A kind of ultralow temperature battery capacitor and its preparation |
-
2020
- 2020-03-13 WO PCT/CN2020/079090 patent/WO2020253277A1/en active Application Filing
- 2020-03-13 CN CN202080002482.8A patent/CN112204329A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10310425A (en) * | 1997-05-07 | 1998-11-24 | Honjiyou Chem Kk | Production of anhydrous lithium chloride |
| CN104129773A (en) * | 2013-08-15 | 2014-11-05 | 多氟多化工股份有限公司 | Drying method and apparatus for lithium hexafluorophosphate |
| CN204944124U (en) * | 2015-08-07 | 2016-01-06 | 赣州腾远钴业有限公司 | A kind of cobalt acid lithium vacuum microwave drying device |
| CN107204466A (en) * | 2017-03-31 | 2017-09-26 | 宁波中车新能源科技有限公司 | A kind of ultralow temperature battery capacitor and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112204329A (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020134773A1 (en) | Method for recovering and preparing lithium iron phosphate cathode material | |
| CN110835104A (en) | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery | |
| WO2010082261A1 (en) | Method for producing positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery | |
| CN114229816B (en) | Method for recycling and preparing anode material from waste lithium iron phosphate battery | |
| WO2020143364A1 (en) | Method for preparing bcn nanotubes into lithium ion supercapacitor electrode material | |
| CN108598439B (en) | Preparation method of tungsten trioxide/graphene composite anode material | |
| CN114242998A (en) | Method for improving electrochemical performance of lithium-rich manganese-based oxide positive electrode material | |
| CN109888238A (en) | A kind of height ratio capacity, lithium ion battery negative material of high rate capability and preparation method thereof | |
| CN110759379B (en) | Preparation method and application of 0D/2D heterostructure composite negative electrode material | |
| CN112978790B (en) | Preparation method of lithium titanate with electrochemical oscillation effect | |
| WO2020253277A1 (en) | Method for using vacuum microwave drying to prepare ultra dry lithium salt for lithium battery | |
| CN107492648B (en) | Cotton-based carbon fiber/MnO/C material, preparation method and application | |
| CN110713187A (en) | Preparation method of silicon material and application of silicon material in lithium ion battery cathode | |
| CN108448069B (en) | Method for modifying high-nickel lithium ion battery positive electrode material | |
| CN108615870A (en) | The preparation method of low cost and the height ratio capacity porous silica material of energy large-scale production | |
| CN114314537A (en) | Preparation method of lithium phosphide-based composite material and application of lithium phosphide-based composite material as lithium supplement material | |
| CN103715427B (en) | The preparation method of lithium iron phosphate nano single-crystal material | |
| CN111129423A (en) | Lithium ion battery cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery | |
| CN107519666B (en) | Iron ion adsorption column and application thereof | |
| CN115939359B (en) | Silicon-based negative electrode material, preparation method thereof and lithium ion secondary battery | |
| CN114583148B (en) | Preparation method of silicon oxide-based graphite composite anode material for lithium ion battery | |
| CN115406187B (en) | Drying method for battery cell of sodium ion battery | |
| CN113415794B (en) | Water-based zinc battery positive electrode material prepared through phosphating process and preparation method and application thereof | |
| CN109461905B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN115602455A (en) | Pre-sodium treatment method for preparing sodium ion capacitor and sodium ion capacitor prepared by pre-sodium treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20825527 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20825527 Country of ref document: EP Kind code of ref document: A1 |
|
| 32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 17/03/2023) |