WO2023231445A1 - 测定双氟磺酰亚胺碱金属盐纯度的方法 - Google Patents

测定双氟磺酰亚胺碱金属盐纯度的方法 Download PDF

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WO2023231445A1
WO2023231445A1 PCT/CN2023/075332 CN2023075332W WO2023231445A1 WO 2023231445 A1 WO2023231445 A1 WO 2023231445A1 CN 2023075332 W CN2023075332 W CN 2023075332W WO 2023231445 A1 WO2023231445 A1 WO 2023231445A1
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bisfluorosulfonimide
organic amine
alkali metal
salt
metal salt
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PCT/CN2023/075332
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French (fr)
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林锦锋
程思聪
刘志雄
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时代思康新材料有限公司
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Publication of WO2023231445A1 publication Critical patent/WO2023231445A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Definitions

  • the present application relates to the technical field of detection and analysis, and in particular to a method for determining the purity of alkali metal salts of bisfluorosulfonyl imide.
  • Rechargeable and rechargeable batteries have the advantages of small size, high energy density, high safety, small self-discharge, and long life. They are widely used in energy storage, communications, electric vehicles, aerospace and other fields.
  • rechargeable batteries lithium-ion batteries have particularly excellent performance and have been extensively studied in the battery field in order to further improve their performance.
  • Bisfluorosulfonimide alkali metal salt is the main component of the electrolyte of lithium-ion batteries.
  • the purity of bisfluorosulfonimide alkali metal salt has an important impact on the electrolyte. The higher the purity, the better the performance of the lithium-ion battery. ; The lower the purity, the worse the performance of the lithium-ion battery.
  • the current detection accuracy of the purity of bisfluorosulfonimide alkali metal salt is poor and still needs to be improved.
  • the present application provides a method for measuring the purity of bisfluorosulfonimide alkali metal salt, which can improve the detection accuracy of bisfluorosulfonimide alkali metal salt.
  • the embodiment of the present application proposes a method for determining the purity of bisfluorosulfonimide alkali metal salts.
  • the method includes: analyzing a series of bisfluorosulfonimide organic amine salts of different qualities using headspace-gas chromatography.
  • the bisfluorosulfonimide organic ammonium salt according to the embodiment of the present application is mixed with an alkaline solution, the organic amine in the bisfluorosulfonimide organic ammonium salt volatilizes in a gaseous state, and the content of the organic amine is measured by gas chromatography.
  • the content of bisfluorosulfonimide organic ammonium salt is calculated to improve the detection accuracy of the purity of bisfluorosulfonimide alkali metal salt.
  • the molar ratio of the bisfluorosulfonimide alkali metal salt to be measured and the alkaline solution is 1: (1-10).
  • the mass ratio between the bisfluorosulfonimide alkali metal salt and the alkaline solution according to the embodiment of the present application satisfies the above range, and the alkaline solution can fully dissociate the organic amine in the bisfluorosulfonimide organic amine salt. , thereby improving the detection accuracy of the purity of bisfluorosulfonimide alkali metal salt.
  • the molar ratio of the bisfluorosulfonimide alkali metal salt to be measured and the alkaline solution is 1: (2-8).
  • the mass ratio between the bisfluorosulfonimide alkali metal salt and the alkaline solution according to the embodiment of the present application satisfies the above range, which can further improve the detection accuracy of the purity of the bisfluorosulfonimide alkali metal salt.
  • the alkaline solution includes one or more of an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous lithium hydroxide solution, an aqueous calcium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous sodium bicarbonate solution.
  • the alkaline solution of the embodiment of the present application is relatively strong and can fully dissociate the organic amine in the bisfluorosulfonimide organic amine salt, thereby improving detection accuracy.
  • the content of the solute in the alkaline solution is 3% to 10% based on the mass of the alkaline solution.
  • the alkaline solution can inhibit the hydrolysis of the organic amine to a certain extent, and the ionization effect of the organic amine is not obvious, and the activity coefficient is relatively high.
  • Organic amines are easily volatile.
  • the content of the solute in the alkaline solution is 5% to 7% based on the mass of the alkaline solution.
  • the volatilization of the organic amine can be further promoted and the detection accuracy can be improved.
  • the heating time is 20 min to 50 min; optionally, the heating time is 30 min to 40 min.
  • the organic amine is in gas-liquid equilibrium, and the detection accuracy of the organic amine can be further improved.
  • the heating temperature ranges from T0 to T0+100°C, where T0 represents the boiling point of the organic amine.
  • the heating temperature in the embodiment of the present application is controlled within the above range, which allows the organic amine to fully develop into a gaseous state, which is beneficial to improving detection accuracy and basically does not affect other substances.
  • bisfluorosulfonimide organic amine salts include bisfluorosulfonimide triethylamine salt, bisfluorosulfonimide trimethylamine salt, bisfluorosulfonimide tripropylamine salt, and bisfluorosulfonimide One or more of the imide pyridinium salts; optionally, the bisfluorosulfonimide organic amine salt includes bisfluorosulfonimide triethylamine salt.
  • the bisfluorosulfonimide organic amine salt according to the embodiment of the present application is more likely to dissociate into organic amine, thereby improving detection accuracy.
  • the mass content of the alkali metal salt of bisfluorosulfonimide is ⁇ 10%; optionally, the mass content of the alkali metal salt of bisfluorosulfonimide is ⁇ 6%.
  • the alkali metal salt of bisfluorosulfonimide in the embodiment of the present application may decompose to produce acid, resulting in an increase in acidity in the system and a decrease in pH value. , which is not conducive to the volatilization of organic amines, thereby reducing detection accuracy.
  • the mass content of the bisfluorosulfonimide alkali metal salt is within the above range, the detection accuracy is relatively high.
  • Figure 1 is a schematic flow chart for determining the alkali metal salt of bisfluorosulfonimide provided by some embodiments of the present application;
  • Figure 2 is the linear regression equation obtained in Example 1 of the present application.
  • Figure 3 is a chromatogram of the bisfluorosulfonimide organic amine salt among the bisfluorosulfonimide alkali metal salts to be tested in Example 1 of the present application;
  • Figure 4 is a parallel test spectrum of the bisfluorosulfonimide organic amine salt in the alkali metal salt of bisfluorosulfonimide to be tested in Example 1 of the present application;
  • Figure 5 is a chromatogram of the bisfluorosulfonimide organic amine salt among the bisfluorosulfonimide alkali metal salts to be tested in Example 2 of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • a method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) can be added to the method in any order.
  • the method may include steps (a), (b) and (c), and may also include step (a). , (c) and (b), and may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • the fluoride ions in the alkali metal salt of bisfluorosulfonimide have strong electron-withdrawing properties, which weakens the coordination between anions and cations of the alkali metal salt of bisfluorosulfonimide.
  • the alkali metal ions are highly mobile and conductive. It has high resistance, thermal stability and electrochemical stability, and basically does not generate corrosive gases such as hydrofluoric acid. In view of the excellent characteristics of the bisfluorosulfonimide alkali metal salt, when used in the electrolyte of secondary batteries, it can improve the rate performance, cycle life and safety of secondary batteries.
  • the alkali metal ions may be lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, etc.
  • the bisfluorosulfonimide alkali metal salt when applied to the electrolyte of a secondary battery, if the content of the bisfluorosulfonimide organic ammonium salt contained in the bisfluorosulfonimide alkali metal salt is relatively If the value is high, the discoloration may occur due to the unstable performance of the organic amine contained in the bisfluorosulfonimide organic ammonium salt, and the discoloration may occur under the action of electrical energy. Decomposition occurs under conditions, causing safety hazards to secondary batteries. Therefore, the purity of the bisfluorosulfonimide alkali metal salt needs to be tested to ensure the product performance of the bisfluorosulfonimide alkali metal salt.
  • M represents Li, Na, K, Rb or Cs.
  • R represents an organic amine.
  • R represents trimethylamine, triethylamine, tripropylamine or pyridine.
  • the inventor proposed a method for determining the purity of bisfluorosulfonimide alkali metal salt.
  • the method includes:
  • Step S100 is mainly to establish a standard curve.
  • step S100 may include:
  • the alkaline solution reacts with the bisfluorosulfonimide organic amine salt to dissociate the organic amine in the bisfluorosulfonimide organic ammonium salt to facilitate subsequent detection.
  • the bisfluorosulfonimide organic ammonium salt may include bisfluorosulfonimide triethylamine salt, bisfluorosulfonimide trimethylamine salt, bisfluorosulfonimide tripropylamine salt and bisfluorosulfonyl One or more imine pyridinium salts.
  • the type of bisfluorosulfonimide organic ammonium salt selected to establish the standard curve is determined based on the type of bisfluorosulfonimide organic amine salt in the bisfluorosulfonimide alkali metal salt to be tested.
  • the alkaline solution can be one or more of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, calcium hydroxide aqueous solution, sodium carbonate aqueous solution and sodium bicarbonate aqueous solution.
  • This type of alkaline solution is relatively strong in alkalinity and can fully dissociate the organic amines in the bisfluorosulfonimide organic amine salt, thereby improving detection accuracy.
  • the content of the solute in the alkaline solution may be 3% to 10%.
  • the content of the solute in the alkaline solution refers to the ratio of the mass of the solute to the total mass of the solution.
  • the content of the solute in the alkaline solution can be 5% to 7%; exemplarily, the concentration of the alkaline solution can be 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%. Therefore, the embodiments of the present application can adjust the detection limit of the bisfluorosulfonyl imide salt by adjusting the concentration of the alkaline solution.
  • the standard mixed solution is heated to volatilize the organic amine in the standard mixed solution into a gaseous state, so that the content of the gaseous organic amine can be detected.
  • the heating time can be 20min ⁇ 50min, with Organic amines are in gas-liquid equilibrium, which can further improve the detection accuracy of organic amines.
  • the heating time may be 30 min to 40 min; exemplarily, the heating time may be 20 min, 25 min, 30 min, 35 min, 40 min, 45 min or 50 min.
  • Step S200 dissociates the organic amine in the alkali metal salt of bisfluorosulfonimide to be measured, thereby detecting the content of the organic amine salt of bisfluorosulfonimide by measuring the content of the organic amine.
  • the alkaline solution in step S200 can be the same alkaline solution as that in step S110, which will not be described again.
  • the mass content of the alkali metal salt of bisfluorosulfonimide is ⁇ 10%.
  • the mass content of the alkali metal salt of bisfluorosulfonyl imide refers to the mass content of the solution to be tested after dilution to a constant volume. For example, weigh 3 grams of alkali metal salt of bisfluorosulfonyl imide and adjust the volume to 100 ml, which represents The mass content of bisfluorosulfonimide alkali metal salt in the solution to be tested is 3%.
  • the alkali metal salt of bisfluorosulfonimide may decompose to produce acid, which will increase the acidity in the system and decrease the pH value, which is not conducive to the volatilization of organic amines. Thereby reducing the detection accuracy.
  • the mass content of the bisfluorosulfonimide alkali metal salt is ⁇ 6%.
  • the mass content of the bisfluorosulfonimide alkali metal salt may be 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3% or 2%, etc.
  • test method of this application is more suitable for samples with a mass content of bisfluorosulfonimide alkali metal salt less than or equal to 10%.
  • the molar ratio of the alkali metal salt of bisfluorosulfonimide to the alkaline solution is 1: (1-10).
  • the mass ratio of bisfluorosulfonimide alkali metal salt and alkaline solution satisfies the above range.
  • the alkaline solution can fully dissociate the organic amine in the bisfluorosulfonimide organic amine salt, thereby improving the quality of bisfluorosulfonimide. Detection accuracy of the purity of amine alkali metal salts.
  • the molar ratio of the bisfluorosulfonimide alkali metal salt to the alkaline solution is 1: (2-8).
  • the heating temperature should be controlled to be greater than or equal to the boiling point of the organic amine, which can volatilize the organic amine into a gaseous state.
  • the heating temperature can be T0 ⁇ T0+100°C, where T0 represents the boiling point of the organic amine. Controlling the heating temperature within the above range can allow the organic amine to fully develop into a gaseous state, which is beneficial to improving detection accuracy, and will basically not affect other substances, such as the decomposition of the alkali metal salt of bisfluorosulfonyl imide.
  • the heating temperature can be T0 ⁇ T0+50°C.
  • the heating temperature can be T0, T0+5°C, T0+10°C, T0+15°C, T0+20°C, T0+25 °C, T0+30°C, T0+35°C, T0+40°C, T0+45°C, T0+50°C, T0+60°C, T0+70°C, T0+80°C, T0+90°C or T0+90 °C.
  • Heating under constant temperature conditions can stabilize the volatilization of organic amines.
  • the heating time can be adjusted under constant temperature conditions so that the organic amines are fully volatilized and in a state of gas-liquid equilibrium.
  • the heating conditions in step S300 and the heating conditions in step S120 may be the same and will not be described again.
  • S400 uses gas chromatography to detect the chromatographic peak area signal value of gaseous organic amines, and compares the chromatographic peak area signal value with the standard curve to obtain the quality of bisfluorosulfonimide organic ammonium salt.
  • the gaseous organic amine is detected by gas chromatography, and then the mass of the bisfluorosulfonimide organic ammonium salt is calculated to obtain the purity of the bisfluorosulfonimide alkali metal salt to be measured.
  • the bisfluorosulfonimide organic ammonium salt is mixed with an alkaline solution, the organic amine in the bisfluorosulfonimide organic ammonium salt volatilizes in a gaseous manner, and the content of the organic amine is determined by gas chromatography.
  • the content of bisfluorosulfonimide organic ammonium salt is calculated to improve the detection accuracy of the purity of bisfluorosulfonimide alkali metal salt.
  • Chromatographic column SH-624 capillary column (60m ⁇ 0.32mm ⁇ 1.80 ⁇ m); vaporization temperature: 200°C; FID detector temperature: 240°C.
  • Carrier gas N 2 (pressure 80.0 kPa); combustion gas: H 2 (flow rate 40 mL/min) and air (flow rate 400 mL/min); column temperature: programmed temperature rise, starting temperature 50°C, maintaining for 3 minutes, and then increasing to 10°C /min heating rate to 210°C and maintained for 5 minutes.
  • Constant temperature furnace temperature 85°C
  • sample flow path temperature 100°C
  • transmission line temperature 120°C
  • sample bottle thermostat time 30min
  • sample bottle pressurization air pressure 160kPa
  • sample bottle pressurization time 1.00min
  • pressure balance time 0.0min
  • introduction equilibrium time 0.10min
  • injection time 1.00min
  • quantitative tube volume 1ml.
  • Y represents the area
  • X represents the concentration (that is, the mass content of the bisfluorosulfonimide organic ammonium salt).
  • the content of bisfluorosulfonimide organic amine salt in the alkali metal salt of bisfluorosulfonimide to be tested was 25.077 ⁇ g/g, and the alkali metal salt of bisfluorosulfonyl imide to be tested was added with a standard of 10.00 ⁇ g/g.
  • the content of bisfluorosulfonimide organic amine salt was 35.989 ⁇ g/g, and the recovery rate was 109.12%.
  • the chromatogram of Example 1 is shown in Figure 3 .
  • Example 2 Different from Example 1, 4% sodium hydroxide aqueous solution is used to adjust the alkali metal salt of bisfluorosulfonyl imide to the volume.
  • the molar ratio of the alkali metal salt of bisfluorosulfonyl imide to be measured and the aqueous sodium hydroxide solution is about 1 :6.
  • the content of bisfluorosulfonimide organic amine salt in the bisfluorosulfonimide alkali metal salt to be tested was 61.391 ⁇ g/g, and the bisfluorosulfonyl imide alkali metal salt to be tested was spiked with 30.00 ⁇ g/g.
  • the content of bisfluorosulfonimide organic amine salt was 91.419 ⁇ g/g, and the recovery rate was 100.09%.
  • the chromatogram of Example 2 is shown in Figure 5 .

Abstract

一种测定双氟磺酰亚胺碱金属盐纯度的方法，包括：将一系列不同质量的双氟磺酰亚胺有机胺盐采用顶空-气相色谱进行分析检测，并将所得到的色谱峰面积信号值与双氟磺酰亚胺有机胺盐的质量相关联建立标准曲线；将待测双氟磺酰亚胺碱金属盐与碱性溶液混合，以得到含有机胺的混合溶液；于密封条件下加热混合溶液，以使混合溶液中的有机胺挥发为气态有机胺；采用气相色谱法检测气态有机胺的色谱峰面积信号值，并将色谱峰面积信号值与标准曲线进行比对，得到双氟磺酰亚胺有机铵盐的质量。

Description

测定双氟磺酰亚胺碱金属盐纯度的方法
相关申请的交叉引用
本申请要求享有于2022年06月02日提交的名称为“测定双氟磺酰亚胺碱金属盐纯度的方法”的中国专利申请202210623449.8的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请涉及检测分析技术领域，特别是涉及测定双氟磺酰亚胺碱金属盐纯度的方法。
背景技术
可充放电的电池，具有体积小、能量密度高、安全性高、自放电小、寿命长等有点，在储能、通信、电动汽车、航空航天等多个领域广泛应用。可充放电的电池中的锂离子电池的性能尤为优异，在电池领域被广泛研究，以期进一步提高其性能。
双氟磺酰亚胺碱金属盐作为锂离子电池的电解液中的主要组成，双氟磺酰亚胺碱金属盐的纯度对电解液具有重要影响，纯度越高，锂离子电池的性能越优异；纯度越低，锂离子电池的性能越差，但是目前对双氟磺酰亚胺碱金属盐的纯度的检测精度较差，仍有待提高。
发明内容
本申请提供一种测定双氟磺酰亚胺碱金属盐纯度的方法，能够提高双氟磺酰亚胺碱金属盐的检测精度。
本申请实施方式提出了一种测定双氟磺酰亚胺碱金属盐纯度的方法，所述方法包括：将一系列不同质量的双氟磺酰亚胺有机胺盐采用顶空-气相色谱进行分析检测，并将所得到的色谱峰面积信号值与双氟磺酰亚胺有机胺盐的质量相关联建立标准曲线；将待测双氟磺酰亚胺碱金属盐与碱性溶液混合，以得到含有机胺的混合溶液；于密封条件下加热混合溶液，以使混合溶液中的有机胺挥发为气态有机胺；采用气相色谱法检测气态有机胺的色谱峰面积信号值，并将色谱峰面积信号值与标准曲线进行比对，得到双氟磺酰亚胺有机铵盐的质量。
由此，本申请实施方式的双氟磺酰亚胺有机铵盐与碱性溶液混合，双氟磺酰亚胺有机铵盐中的有机胺以气态方式挥发，通过气相色谱测定有机胺的含量从而计算得到双氟磺酰亚胺有机铵盐的含量，提高双氟磺酰亚胺碱金属盐纯度的检测精度。
在一些实施方式中，待测双氟磺酰亚胺碱金属盐和碱性溶液的摩尔比为1：(1～10)。
由此，本申请实施方式的双氟磺酰亚胺碱金属盐与碱性溶液满足上述范围的质量比，碱性溶液能够将双氟磺酰亚胺有机胺盐中的有机胺充分解离出，从而提高双氟磺酰亚胺碱金属盐纯度的检测精度。
在一些实施方式中，待测双氟磺酰亚胺碱金属盐和碱性溶液的摩尔比为1：(2～8)。
由此，本申请实施方式的双氟磺酰亚胺碱金属盐与碱性溶液满足上述范围的质量比，可以进一步提高双氟磺酰亚胺碱金属盐纯度的检测精度。
在一些实施方式中，碱性溶液包括氢氧化钾水溶液、氢氧化钠水溶液、氢氧化锂水溶液、氢氧化钙水溶液、碳酸钠水溶液和碳酸氢钠水溶液中的一种或多种。
由此，本申请实施方式的碱性溶液的碱性相对较强，能够将双氟磺酰亚胺有机胺盐中的有机胺充分解离，从而提高检测精度。
在一些实施方式中，基于碱性溶液的质量计，碱性溶液中溶质的含量为3％～10％。
由此，本申请实施方式的碱性溶液中的溶质的含量在上述范围时，碱性溶液能够在一定程度上抑制有机胺的水解，并且有机胺电离作用不明显，活度系数相对较高，有机胺容易挥发。
在一些实施方式中，基于碱性溶液的质量计，碱性溶液中溶质的含量为5％～7％。
由此，本申请实施方式的碱性溶液中的溶质的含量在上述范围时，能够进一步促使有机胺挥发，提高检测精度。
在一些实施方式中，加热的时间为20min～50min；可选地，加热的时间为30min～40min。
由此，本申请实施方式的加热的时间控制在上述范围时，有机胺处于气液平衡，从而可以进一步提高有机胺的检测精度。
在一些实施方式中，加热的温度为T0～T0+100℃，其中，T0表示有机胺的沸点。
由此，本申请实施方式的加热的温度控制在上述范围内，可以使得有机胺充分发挥为气态，有利于提高检测精度，且基本不会对其他物质造成影响，
在一些实施方式中，双氟磺酰亚胺有机胺盐包括双氟磺酰亚胺三乙胺盐、双氟磺酰亚胺三甲胺盐、双氟磺酰亚胺三丙胺盐和双氟磺酰亚胺吡啶盐中的一种或多种；可选地，双氟磺酰亚胺有机胺盐包括双氟磺酰亚胺三乙胺盐。
由此，本申请实施方式的双氟磺酰亚胺有机胺盐更容易解离出有机 胺，从而提高检测精度。
在一些实施方式中，双氟磺酰亚胺碱金属盐的质量含量≤10％；可选地，双氟磺酰亚胺碱金属盐的质量含量≤6％。
由此，本申请实施方式的双氟磺酰亚胺碱金属盐的质量含量过高时，双氟磺酰亚胺碱金属盐可能会发生分解产生酸，从而导致体系中酸性增强，pH值下降，不利于有机胺的挥发，从而降低检测精度。双氟磺酰亚胺碱金属盐的质量含量在上述范围时，其检测精度相对较高。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，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，还可以根据附图获得其他的附图。
图1是本申请一些实施例提供的测定双氟磺酰亚胺碱金属盐的流程示意图；
图2是本申请实施例1所得到的线性回归方程；
图3是本申请实施例1中待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐的色谱图；
图4是本申请实施例1中待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐的平行测试谱图；
图5是本申请实施例2中待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐的色谱图。
具体实施方式
下面结合附图和实施例对本申请的实施方式作进一步详细描述。以 下实施例的详细描述和附图用于示例性地说明本申请的原理，但不能用来限制本申请的范围，即本申请不限于所描述的实施例。
以下，适当地参照附图详细说明具体公开了双氟磺酰亚胺锂和提纯双氟磺酰亚胺锂的方法的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随 机进行，优选是顺序进行的。例如，方法包括步骤(a)和(b)，表示方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到方法，例如，方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
双氟磺酰亚胺碱金属盐中的氟离子具有较强的吸电子性，使双氟磺酰亚胺碱金属盐的阴阳离子间配位作用减弱，碱金属离子的活动性很强，导电性、热稳定性、电化学稳定性高，基本不会生成氢氟酸等腐蚀性气体。鉴于双氟磺酰亚胺碱金属盐优异的特性，其应用于二次电池的电解液时，可以改善二次电池的倍率性能、循环寿命和安全性等。在本文中，碱金属离子可以为锂离子、钠离子、钾离子、铷离子、铯离子等。
双氟磺酰亚胺有机铵盐生产双氟磺酰亚胺碱金属盐的过程中，因为复分解反应无法完全转化为双氟磺酰亚胺碱金属盐，导致部分双氟磺酰亚胺有机胺盐可能残留在产品中，如双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐的含量过高，可能会对产品的性能造成不利影响。示例性地，在将双氟磺酰亚胺碱金属盐应用于二次电池的电解液时，如果双氟磺酰亚胺碱金属盐中包含的双氟磺酰亚胺有机铵盐的含量较高，则可能因为双氟磺酰亚胺有机铵盐所包含的有机胺的性能不稳定发生变色，且在电能作用 下发生分解，从而对二次电池造成安全隐患。故，需要对双氟磺酰亚胺碱金属盐的纯度进行检测，以保证双氟磺酰亚胺碱金属盐的产品性能。
双氟磺酰亚胺碱金属盐结构式如下：
式中，M表示Li、Na、K、Rb或Cs。
双氟磺酰亚胺有机铵盐结构式如下：
式中，R表示有机胺，示例性地，R表示三甲胺、三乙胺、三丙胺或吡啶。
发明人发现，双氟磺酰亚胺碱金属盐和双氟磺酰亚胺有机铵盐的阳离子不同，但是阴离子结构完全相同，这给检测双氟磺酰亚胺碱金属盐的浓度造成了很大困难，很难通过离子色谱等方法进行定量分析检测。
鉴于此，发明人提出了一种测定双氟磺酰亚胺碱金属盐纯度的方法。
如图1所示，该方法包括：
S100，将一系列不同质量的双氟磺酰亚胺有机胺盐采用顶空-气相色谱进行分析检测，并将所得到的色谱峰面积信号值与双氟磺酰亚胺有机胺盐的质量相关联建立标准曲线。
步骤S100主要为建立标准曲线，在一些实施例中，步骤S100可以包括：
S110，将一系列不同质量的双氟磺酰亚胺有机胺盐与碱性溶液混合，以得到一系列含有机胺的标准混合溶液。
碱性溶液与双氟磺酰亚胺有机胺盐反应，能够将双氟磺酰亚胺有机铵盐中的有机胺解离出来，以便于后续的检测。
可选地，双氟磺酰亚胺有机铵盐可以包括双氟磺酰亚胺三乙胺盐、双氟磺酰亚胺三甲胺盐、双氟磺酰亚胺三丙胺盐和双氟磺酰亚胺吡啶盐中的一种或多种。建立标准曲线所选取的双氟磺酰亚胺有机铵盐的种类根据待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐的种类确定。
可选地，碱性溶液可以看氢氧化钾水溶液、氢氧化钠水溶液、氢氧化锂水溶液、氢氧化钙水溶液、碳酸钠水溶液和碳酸氢钠水溶液中的一种或多种。该类碱性溶液的碱性相对较强，能够将双氟磺酰亚胺有机胺盐中的有机胺充分解离，从而提高检测精度。
可选地，基于碱性溶液的质量计，碱性溶液中溶质的含量可以为3％～10％，在本文中，碱性溶液中溶质的含量是指溶质的质量与溶液总质量的比值。碱性溶液中的溶质的含量在上述范围时，碱性溶液能够在一定程度上抑制有机胺的水解，并且有机胺电离作用不明显，活度系数相对较高，有机胺容易挥发，换言之，碱性溶液能够将有机胺充分解离出，且有机胺容易以气态形式存在。可选地，碱性溶液中溶质的含量可以为5％～7％；示例性地，碱性溶液的浓度可以为3％、4％、5％、6％、7％、8％、9％或10％。故，本申请实施例能够通过调控碱性溶液的浓度调节双氟磺酰亚胺盐的检出限。
S120，于密封条件下分别加热一系列标准混合溶液，以使标准混合溶液中的有机胺挥发为一系列标准气态有机胺；将一系列标准气态有机胺采用气相色谱进行分析检测，并将所得到的色谱峰面积信号值与双氟磺酰亚胺有机胺盐的质量相关联建立标准曲线。
将标准混合溶液加热，以使标准混合溶液中的有机胺挥发为气态，从而对气态的有机胺进行含量检测。加热的时间可以为20min～50min，有 机胺处于气液平衡，从而可以进一步提高有机胺的检测精度。可选地，加热的时间可以为30min～40min；示例性地，加热的时间可以为20min、25min、30min、35min、40min、45min或50min。
S200，将待测双氟磺酰亚胺碱金属盐与碱性溶液混合，以得到含有机胺的混合溶液。
步骤S200将待测双氟磺酰亚胺碱金属盐中的有机胺解离出，从而通过测定有机胺的含量检测双氟磺酰亚胺有机胺盐的含量。步骤S200中的碱性溶液可以采用与步骤S110相同的碱性溶液，在此不再赘述。
在一些实施例中，双氟磺酰亚胺碱金属盐的质量含量≤10％。在本文中，双氟磺酰亚胺碱金属盐的质量含量是指稀释定容后的待测试溶液的质量含量，例如称取3克双氟磺酰亚胺碱金属盐定容到100ml，代表待测试溶液中的双氟磺酰亚胺碱金属盐质量含量为3％。
双氟磺酰亚胺碱金属盐的质量含量过高时，双氟磺酰亚胺碱金属盐可能会发生分解产生酸，从而导致体系中酸性增强，pH值下降，不利于有机胺的挥发，从而降低检测精度。可选地，双氟磺酰亚胺碱金属盐的质量含量≤6％。示例性地，双氟磺酰亚胺碱金属盐的质量含量可以为10％、9％、8％、7％、6％、5％、4％、3％或2％等。
换言之，本申请的测试方法更适用于双氟磺酰亚胺碱金属盐的质量含量为小于或等于10％的样品。
在一些实施例中，双氟磺酰亚胺碱金属盐与碱性溶液的摩尔比为1：(1～10)。
双氟磺酰亚胺碱金属盐与碱性溶液满足上述范围的质量比，碱性溶液能够将双氟磺酰亚胺有机胺盐中的有机胺充分解离出，从而提高双氟磺酰亚胺碱金属盐纯度的检测精度。可选地，双氟磺酰亚胺碱金属盐与碱性溶液的摩尔比为1：(2～8)。
S300，于密封条件下加热混合溶液，以使混合溶液中的有机胺挥发为气态有机胺。
加热温度应控制在大于或等于有机胺的沸点，能够使得有机胺挥发为气态，示例性地，加热的温度可以为T0～T0+100℃，其中，T0表示有机胺的沸点。加热温度控制在上述范围内，可以使得有机胺充分发挥为气态，有利于提高检测精度，且基本不会对其他物质造成影响，例如不会使得双氟磺酰亚胺碱金属盐分解。可选地，加热的温度可以为T0～T0+50℃，示例性地，加热的温度可以为T0、T0+5℃、T0+10℃、T0+15℃、T0+20℃、T0+25℃、T0+30℃、T0+35℃、T0+40℃、T0+45℃、T0+50℃、T0+60℃、T0+70℃、T0+80℃、T0+90℃或T0+90℃。
在恒温条件下加热，可以使得有机胺稳定挥发。并可以在恒温条件下，调控加热时间，以使有机胺充分挥发且处于气液平衡状态。步骤S300的加热条件与步骤S120的加热条件可以相同，在此不再赘述。
S400，采用气相色谱法检测气态有机胺的色谱峰面积信号值，并将色谱峰面积信号值与标准曲线进行比对，得到双氟磺酰亚胺有机铵盐的质量。
有机胺挥发为气态有机胺后，将气态有机胺进行气相色谱检测，然后计算得到双氟磺酰亚胺有机铵盐的质量，进而得到待测双氟磺酰亚胺碱金属盐的纯度。
根据本申请实施例的方法，双氟磺酰亚胺有机铵盐与碱性溶液混合，双氟磺酰亚胺有机铵盐中的有机胺以气态方式挥发，通过气相色谱测定有机胺的含量从而计算得到双氟磺酰亚胺有机铵盐的含量，提高双氟磺酰亚胺碱金属盐纯度的检测精度。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
1、色谱条件
色谱柱:SH-624毛细管柱(60m×0.32mm×1.80μm)；气化温度:200℃；FID检测器温度:240℃。载气:N2(压力80.0kPa)；燃烧气体:H2(流量40mL/min)和空气(流量400mL/min)；柱温:采用程序升温，起始温度50℃，保持3min，以10℃/min升温速度升至210℃，保持5min。
2、顶空条件
恒温炉温度：85℃，样品流路温度：100℃，传输线温度：120℃，样品瓶恒温时间:30min，样品瓶加压用气压：160kPa，样品瓶加压时间：1.00min，加压平衡时间：0.10min，导入时间：0.50min，导入平衡时间：0.10min，进样时间：1.00min，定量管体积：1ml。
3、实验步骤
3.1标准曲线的制定
准确称取0.2000克双氟磺酰亚胺三乙胺盐于试剂瓶中，加入纯水到100.0000克，得浓度为2000μg/g的标准储备液。分别称取0.2975、0.5700、1.0440、2.0565、3.1370、4.1430、6.1095g的标准储备液于100ml容量瓶中，用5％的氢氧化钾水溶液定容，配制成双氟磺酰亚胺三乙胺盐浓度为5.95、11.40、20.88、41.13、62.74、82.86、122.19μg/ml的标准液。
分别移取5ml标准液于20ml的顶空瓶，压盖密封，按步骤1和2 的仪器条件进行顶空气相分析，以峰面积响应值对双氟磺酰亚胺有机胺盐的质量浓度进行线性回归，通过线性回归方程定量样品中双氟磺酰亚胺有机胺盐的含量。记录色谱数据并绘制标准曲线，如图2所示，由此得到线性回归方程Y＝14023.0X+30935.7,线性相关系数为0.9991，检出限：0.03ug/ml,定量限:0.10ug/ml。Y表示面积，X表示浓度(即双氟磺酰亚胺有机铵盐的质量含量)。在以上条件下测试双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐含量具有良好线性关系，相关系数大于0.999，相对标准偏差约为2.42％。该方法稳定性好，准确度高，结果可靠。
3.2样品预处理
准确称取3g待测双氟磺酰亚胺碱金属盐，置于100ml容量瓶中，用5％氢氧化钾水溶液定容，待测双氟磺酰亚胺碱金属盐和氢氧化钾水溶液的摩尔比约为1:7，用移液枪移5ml定容后的溶液于顶空瓶中，快速压盖密封，按步骤1和2的仪器条件进行顶空气相色谱分析。
检测得到的待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐含量为25.077μg/g，待测双氟磺酰亚胺碱金属盐加标10.00μg/g测出双氟磺酰亚胺有机胺盐含量为35.989μg/g，回收率为109.12％。图3中示出了实施例1的色谱图。
对实施例1的待测双氟磺酰亚胺碱金属盐进行6次平行测试，测得的双氟磺酰亚胺有机胺盐含量分别为45.348μg/g、47.561μg/g、45.204μg/g、47.356μg/g、47.152μg/g、47.740μg/g，相对标准偏差2.42％。图4示出了平行测试谱图。由图3可以看出，该方法检测的精密度较高。
实施例2
与实施例1不同的是，采用4％氢氧化钠水溶液将双氟磺酰亚胺碱金属盐定容，待测双氟磺酰亚胺碱金属盐和氢氧化钠水溶液的摩尔比约为1:6。
检测得到的待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐含量为61.391μg/g，待测双氟磺酰亚胺碱金属盐加标30.00μg/g测出双氟磺酰亚胺有机胺盐含量91.419μg/g，回收率为100.09％。图5中示出了实施例2的色谱图。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件，尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (10)

  1. 一种测定双氟磺酰亚胺碱金属盐纯度的方法，包括：
    将一系列不同质量的双氟磺酰亚胺有机胺盐采用顶空-气相色谱进行分析检测，并将所得到的色谱峰面积信号值与所述双氟磺酰亚胺有机胺盐的质量相关联建立标准曲线；
    将待测双氟磺酰亚胺碱金属盐与碱性溶液混合，以得到含有机胺的混合溶液；
    于密封条件下加热所述混合溶液，以使所述混合溶液中的有机胺挥发为气态有机胺；
    采用气相色谱法检测所述气态有机胺的色谱峰面积信号值，并将所述色谱峰面积信号值与所述标准曲线进行比对，得到所述有机胺的体积；
    根据所述有机胺的体积计算得到所述待测双氟磺酰亚胺碱金属盐中的双氟磺酰亚胺有机胺盐含量。
  2. 根据权利要求1所述的方法，其中，所述待测双氟磺酰亚胺碱金属盐和所述碱性溶液的摩尔比为1：(1～10)。
  3. 根据权利要求2所述的方法，其中，所述待测双氟磺酰亚胺碱金属盐和所述碱性溶液的摩尔比为1：(2～8)。
  4. 根据权利要求1至3中任一项所述的方法，其中，所述碱性溶液包括氢氧化钾水溶液、氢氧化钠水溶液、氢氧化锂水溶液、氢氧化钙水溶液、碳酸钠水溶液和碳酸氢钠水溶液中的一种或多种。
  5. 根据权利要求1至4中任一项所述的方法，其中，基于所述碱性溶液的质量计，所述碱性溶液中溶质的含量为3％～10％。
  6. 根据权利要求5所述的方法，其中，基于所述碱性溶液的质量计， 所述碱性溶液中溶质的含量为5％～7％。
  7. 根据权利要求1至6中任一项所述的方法，其中，
    所述加热的时间为20min～50min；
    可选地，所述加热的时间为30min～40min。
  8. 根据权利要求1至7中任一项所述方法，其中，所述加热的温度为T0～T0+100℃，其中，T0表示有机胺的沸点。
  9. 根据权利要求1至8中任一项所述的方法，其中，所述双氟磺酰亚胺有机胺盐包括双氟磺酰亚胺三乙胺盐、双氟磺酰亚胺三甲胺盐、双氟磺酰亚胺三丙胺盐和双氟磺酰亚胺吡啶盐中的一种或多种；
    可选地，所述双氟磺酰亚胺有机胺盐包括双氟磺酰亚胺三乙胺盐。
  10. 根据权利要求1至9中任一项所述方法，其中，
    所述双氟磺酰亚胺碱金属盐的质量含量≤10％；
    可选地，所述双氟磺酰亚胺碱金属盐的质量含量≤6％。
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