技术领域technical field
本发明涉及化学分析领域，特别是涉及一种锂离子电池电解液中氯离子含量的检测方法。The invention relates to the field of chemical analysis, in particular to a method for detecting chloride ion content in lithium-ion battery electrolyte.
背景技术Background technique
电解液是锂离子电池中的重要组成部分，电池材料中氯离子对电池的正负极材料具有腐蚀作用，造成电池容量下降，严重的造成极片穿孔，破坏整个电池，在行业标准《HG/T4067-2008六氟磷酸锂和六氟磷酸锂电解液》中要求其含量≤1000μg/kg。Electrolyte is an important part of lithium-ion batteries. Chloride ions in battery materials have a corrosive effect on the positive and negative electrode materials of the battery, resulting in a decrease in battery capacity, and serious perforation of the pole piece, destroying the entire battery. In the industry standard "HG/ T4067-2008 Lithium Hexafluorophosphate and Lithium Hexafluorophosphate Electrolyte requires its content to be ≤1000μg/kg.
电解液的原料主要由碳酸酯和羧酸酯类有机溶剂、锂盐、添加剂组成，其中的锂盐主要使用的是六氟磷酸锂，其在合成过程中会使用氯化锂做为原料，电解液中的氯离子主要是由原料中引入的，通过准确地分析电解液中的锂离子含量来控制锂盐和电解液中的氯离子浓度具有较高的工业应用价值。The raw materials of the electrolyte are mainly composed of carbonate and carboxylate organic solvents, lithium salts, and additives. The lithium salt is mainly lithium hexafluorophosphate, which uses lithium chloride as a raw material in the synthesis process. Chloride ions are mainly introduced from the raw materials, and it has high industrial application value to control lithium salt and chloride ion concentration in the electrolyte by accurately analyzing the lithium ion content in the electrolyte.
行业标准《HG/T4067-2008六氟磷酸锂和六氟磷酸锂电解液》用0.001mol/lL的硝酸汞标准溶液滴定电解液中的氯离子，以溴酚蓝为指示剂。方法检出限高，对于氯含量＜1000μg/kg的样品无法准确定量，且方法误差大，重复性和再现性都不理想，终点变色不明显，方法适用性不强。The industry standard "HG/T4067-2008 Lithium Hexafluorophosphate and Lithium Hexafluorophosphate Electrolyte" uses 0.001mol/lL mercury nitrate standard solution to titrate chloride ions in the electrolyte, using bromophenol blue as the indicator. The detection limit of the method is high, the sample with chlorine content <1000μg/kg cannot be accurately quantified, and the method has large errors, the repeatability and reproducibility are not ideal, the end point is not obvious, and the applicability of the method is not strong.
发明内容Contents of the invention
基于此，本发明的目的是提供一种检测下限低、操作简单快速的氯离子含量的检测方法。Based on this, the purpose of the present invention is to provide a detection method for chloride ion content with low detection limit, simple and rapid operation.
具体的技术方案如下：The specific technical scheme is as follows:
一种锂离子电池电解液中氯离子含量的检测方法，采用非水电位滴定法进行检测：以非水硝酸银标准溶液为滴定剂，银电极为指示电极，玻璃电极为参比电极，用非水硝酸银标准溶液滴定被测样品至终点后按下式计算即得氯离子的含量：A method for detecting the content of chloride ions in the electrolyte of a lithium-ion battery, using a non-aqueous potentiometric titration method for detection: using a non-aqueous silver nitrate standard solution as a titrant, a silver electrode as an indicator electrode, and a glass electrode as a reference electrode. Titrate the tested sample to the end point with the standard solution of silver nitrate in water, and then calculate the content of chloride ion according to the following formula:
X——氯离子含量，μg/kg；X——chloride ion content, μg/kg;
c——非水硝酸银标准溶液的浓度，mol/L；c—concentration of non-aqueous silver nitrate standard solution, mol/L;
v——滴定消耗非水硝酸银标准溶液的体积，mL；v——the volume of non-aqueous silver nitrate standard solution consumed by titration, mL;
m——样品的质量，g。m—the mass of the sample, g.
在其中一些实施例中，所述非水硝酸银标准溶液的溶剂为醇类、酮类、碳酸酯类或羧酸酯类。In some of these embodiments, the solvent of the non-aqueous silver nitrate standard solution is alcohols, ketones, carbonates or carboxylates.
在其中一些实施例中，所述醇类为甲醇、乙醇、丙醇、丁醇或异丙醇。In some of these embodiments, the alcohols are methanol, ethanol, propanol, butanol or isopropanol.
在其中一些实施例中，所述酮类为丙酮或丁酮。In some of these embodiments, the ketones are acetone or butanone.
在其中一些实施例中，所述碳酸酯类为碳酯二甲酯、碳酯二乙酯、碳酸丙烯酯、碳酸甲乙酯。In some of these embodiments, the carbonates are dimethyl carbonate, diethyl carbonate, propylene carbonate, and ethyl methyl carbonate.
在其中一些实施例中，所述羧酸酯类为甲酸甲酯、甲酸乙酯、乙酸乙酯中的一种或几种。In some of these embodiments, the carboxylic acid esters are one or more of methyl formate, ethyl formate, and ethyl acetate.
本发明的原理如下：Principle of the present invention is as follows:
本发明采用非水电位滴定法，在非水溶液中Ag++Cl-=AgCl↓，氯离子可与银离子结合生成氯化银沉淀，用银电极为指示电极，玻璃电极为参比电极，并将电极浸入溶液中，在滴定过程中，参比电极电位保持恒定，指示电极电位随溶液中氯离子浓度变化而变化。在化学计量点前后，溶液中氯离子的浓度变化，会引起指示电极的急剧变化，指示电极的突跃点就是测量终点。The present invention adopts the non-aqueous potentiometric titration method. In the non-aqueous solution, Ag+ + Cl- = AgCl↓, chloride ions can be combined with silver ions to form silver chloride precipitation, and the silver electrode is used as the indicating electrode, the glass electrode is used as the reference electrode, and The electrode is immersed in the solution. During the titration process, the potential of the reference electrode remains constant, indicating that the potential of the electrode changes with the concentration of chloride ions in the solution. Before and after the stoichiometric point, the concentration of chloride ions in the solution changes, which will cause a sharp change in the indicator electrode, and the jump point of the indicator electrode is the measurement end point.
锂离子电池电解液为非水溶液，其中的六氟磷酸锂在遇水后会分解成HF，造成溶液中PH值的变化，影响参比电极电位的恒定，从而影响终点的判断。所以特别选择非水有机溶剂做为溶剂。Lithium-ion battery electrolyte is a non-aqueous solution, and the lithium hexafluorophosphate in it will decompose into HF after encountering water, which will cause a change in the pH value of the solution, affect the constant reference electrode potential, and thus affect the judgment of the end point. Therefore, non-aqueous organic solvents are specially selected as solvents.
本发明的优点是：The advantages of the present invention are:
本发明检测锂离子电池电解液中氯离子含量的方法，操作简单快速、成本低、检测下限低，对于氯离子含量＜1000μg/kg的样品也能够准确定量、氯离子含量的检测下限可达50μg/kg，得到的结果精度高。The method for detecting the chloride ion content in the lithium-ion battery electrolyte of the present invention has the advantages of simple and fast operation, low cost, and low detection limit, and can accurately quantify samples with the chloride ion content <1000 μg/kg, and the detection limit of the chloride ion content can reach 50 μg. /kg, the obtained result has high precision.
具体实施方式Detailed ways
本发明一种锂离子电池电解液中氯离子含量的检测方法，采用非水电位滴定法进行检测：以非水硝酸银标准溶液为滴定剂，银电极为指示电极，玻璃电极为参比电极，用非水硝酸银标准溶液滴定被测样品至终点后按下式计算即得氯离子的含量：The detection method of chloride ion content in the electrolyte of a kind of lithium ion battery of the present invention adopts non-aqueous potentiometric titration method to detect: with non-aqueous silver nitrate standard solution as titrant, silver electrode as indicator electrode, glass electrode as reference electrode, Titrate the tested sample to the end point with non-aqueous silver nitrate standard solution and then calculate the chloride ion content according to the following formula:
X——氯离子含量，μg/kg；X——chloride ion content, μg/kg;
c——非水硝酸银标准溶液的浓度，mol/L；c—concentration of non-aqueous silver nitrate standard solution, mol/L;
v——滴定消耗非水硝酸银标准溶液的体积，mL；v——the volume of non-aqueous silver nitrate standard solution consumed by titration, mL;
m——样品的质量，g。m—the mass of the sample, g.
所述非水硝酸银标准溶液的溶剂为醇类、酮类、碳酸酯类或羧酸酯类，所述醇类为甲醇、乙醇、丙醇、丁醇或异丙醇（优选为乙醇）；所述酮类为丙酮或丁酮（优选为丙酮）；所述碳酸酯类为碳酯二甲酯、碳酯二乙酯、碳酸丙烯酯、碳酸甲乙酯（优选碳酯二甲酯）；在其中一些实施例中，所述羧酸酯类为甲酸甲酯、甲酸乙酯、乙酸乙酯中的一种或几种。The solvent of the non-aqueous silver nitrate standard solution is alcohols, ketones, carbonates or carboxylates, and the alcohols are methanol, ethanol, propanol, butanol or isopropanol (preferably ethanol); The ketones are acetone or butanone (preferably acetone); the carbonates are dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl methyl carbonate (dimethyl carbide is preferred); In some of these embodiments, the carboxylic acid esters are one or more of methyl formate, ethyl formate, and ethyl acetate.
所述锂离子电池电解液是由碳酸酯和羧酸酯类的有机溶剂和导电锂盐组成。The lithium ion battery electrolyte is composed of organic solvents of carbonates and carboxylates and conductive lithium salts.
碳酯酯选自下列物质中的至少一种或几种：碳酯乙烯酯、碳酯丙烯酯、碳酯丁烯酯、碳酯二甲酯、碳酯二乙酯、碳酸甲丁酯、碳酸乙丁酯、碳酸二丁酯、氯代乙烯碳酸酯、碳酸甲乙酯、碳酸乙丙酯、碳酸乙异丙酯、碳酸甲丙酯、碳酸甲异丙酯、碳酸亚乙烯酯、氯代碳酸乙烯酯。Carbon esters are selected from at least one or more of the following substances: carbon ester vinyl ester, carbon ester propylene ester, carbon ester butenyl ester, carbon ester dimethyl ester, carbon ester diethyl ester, methyl butyl carbonate, carbonic acid ester Ethyl butyl carbonate, dibutyl carbonate, chloroethylene carbonate, ethyl methyl carbonate, ethylene propyl carbonate, ethyl isopropyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, vinylene carbonate, chlorocarbonic acid vinyl ester.
羟酸酯选自下列物质中的至少一种或几种：丁内酯、戊内酯、已内酯、甲酸甲酯、甲酸乙酯、乙酸乙酯、乙酸丙酯、乙酸异丙酯。The hydroxy acid ester is selected from at least one or more of the following substances: butyrolactone, valerolactone, caprolactone, methyl formate, ethyl formate, ethyl acetate, propyl acetate, and isopropyl acetate.
所述的导电锂盐选自下列物质中的至少一种或几种：六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂。The conductive lithium salt is selected from at least one or more of the following substances: lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalate borate.
本发明实施例中所使用的锂离子电池电解液中原料组成如下：The composition of raw materials in the lithium-ion battery electrolyte used in the embodiments of the present invention is as follows:
溶剂为DMC：EMC：EC=1：1：1；六氟磷酸锂浓度为1mol/L。The solvent is DMC:EMC:EC=1:1:1; the concentration of lithium hexafluorophosphate is 1mol/L.
以下通过实施例对本发明做进一步的阐述。The present invention is described further below by embodiment.
实施例1Example 1
A、0.1mol/L硝酸银标准溶液配制：A. Preparation of 0.1mol/L silver nitrate standard solution:
称取17.5g硝酸银，溶于1000mL乙醇中，摇匀。溶液贮存于棕色瓶中。Weigh 17.5g of silver nitrate, dissolve in 1000mL of ethanol, and shake well. The solution is stored in a brown bottle.
B、0.1mol/L硝酸银标准溶液标定：B. Calibration with 0.1mol/L silver nitrate standard solution:
称取0.22g基准试剂氯化钠，采用电位滴定仪（银电极为指示电极，玻璃电极为参比电极）进行标定。Weigh 0.22g of the reference reagent sodium chloride, and use a potentiometric titrator (the silver electrode is the indicator electrode, and the glass electrode is the reference electrode) for calibration.
D、0.001mol/L硝酸银标准溶液的配制：D. Preparation of 0.001mol/L silver nitrate standard solution:
将配制且标定好的0.1mol/L硝酸银标准溶液用乙醇准确稀释100倍。The prepared and calibrated 0.1mol/L silver nitrate standard solution was accurately diluted 100 times with ethanol.
E、电解液中氯离子的检测：E. Detection of chloride ions in the electrolyte:
准确称取约60g锂离子电池电解液样品（精确至0.01g）于往滴定杯中，搅拌后用浓度为0.001mol/lL的硝酸银标准滴定溶液，使用银/氯化银电极的瑞士万通848自动电位滴定仪，开启仪器自动滴定，试验完成，停止滴定，按下列公式计算结果。Accurately weigh about 60g of lithium-ion battery electrolyte sample (accurate to 0.01g) into the titration cup, and after stirring, titrate the solution with standard silver nitrate with a concentration of 0.001mol/lL, and use Metrohm with silver/silver chloride electrode 848 automatic potentiometric titrator, start the automatic titration of the instrument, stop the titration after the test is completed, and calculate the result according to the following formula.
X——氯离子含量，μg/kgX——chloride ion content, μg/kg
C——硝酸银标准溶液的浓度，mol/LC—concentration of silver nitrate standard solution, mol/L
V——滴定消耗硝酸银标准溶液的体积，mLV——The volume of silver nitrate standard solution consumed by titration, mL
m——样品的质量，g。m—the mass of the sample, g.
F、样品检验结果：F. Sample inspection results:
G、回收率试验G. Recovery rate test
准确称取100g电解液样品,准确加入10μg的氯离子（氯化钠），检测出加入的氯离子结果，计算回收率。Accurately weigh 100g of electrolyte sample, accurately add 10μg of chloride ion (sodium chloride), detect the result of added chloride ion, and calculate the recovery rate.
回收率越趋于100%，结果的准确性越高，本发明回收率在84%-118%，对于痕量分析完全可以满足测量要求。The closer the recovery rate is to 100%, the higher the accuracy of the result is. The recovery rate of the present invention is 84%-118%, which can fully meet the measurement requirements for trace analysis.
实施例2：Example 2:
参照实施例1实验步骤，将硝酸银标准溶液的溶剂乙醇换成丙酮，其它步骤相同。With reference to the experimental procedure of Example 1, the solvent ethanol of the silver nitrate standard solution was replaced with acetone, and the other steps were the same.
样品检验结果：Sample inspection results:
回收率试验结果:Recovery test results:
实施例3：Example 3:
参照实施例1实验步骤，将硝酸银标准溶液的溶剂乙醇换成乙酸乙酯，其它步骤相同。With reference to the experimental procedure of Example 1, the solvent ethanol of the silver nitrate standard solution was replaced with ethyl acetate, and the other steps were the same.
样品检验结果：Sample inspection results:
回收率试验结果:Recovery test results:
实施例4：Example 4:
参照实施例1实验步骤，将硝酸银标准溶液的溶剂乙醇换成碳酸二甲酯，其它步骤相同。With reference to the experimental procedure of Example 1, the solvent ethanol of the silver nitrate standard solution was replaced with dimethyl carbonate, and the other steps were the same.
样品检验结果：Sample inspection results:
回收率试验结果:Recovery test results:
对比例1：Comparative example 1:
行业标准《HG/T4067-2008六氟磷酸锂和六氟磷酸锂电解液》中硝酸汞指示剂滴定法与本发明在锂离子电池电解液的氯离子检测中的对比试验：Contrast test between mercury nitrate indicator titration method in the industry standard "HG/T4067-2008 Lithium Hexafluorophosphate and Lithium Hexafluorophosphate Electrolyte" and the present invention in chloride ion detection of lithium ion battery electrolyte:
分别配制氯离子含量在50μg/kg、500μg/kg、1000μg/kg的三个锂离子电池电解液样品，按行业标准《HG/T4067-2008六氟磷酸锂和六氟磷酸锂电解液》中硝酸汞指示剂滴定法与本发明的方法分别进行试验，试验结果对比如下：Prepare three lithium-ion battery electrolyte samples with chloride ion contents of 50 μg/kg, 500 μg/kg, and 1000 μg/kg respectively, according to the industry standard "HG/T4067-2008 Lithium Hexafluorophosphate and Lithium Hexafluorophosphate Electrolyte" with mercury nitrate indicator titration and Method of the present invention carries out test respectively, and test result contrast is as follows:
本发明定量限在50ug/kg以下，远优于行业标准的1000ug/kg，且本发明在重复性和准确性方面也明显优于行业标准。另外本发明分析成本低，剔除仪器购置的投入成本（电位滴定仪依品牌和型号从几百元到上万元不等），单个样品只需消耗几毫升硝酸银标准溶液，成本不到一元钱。行业标准中除用到硝酸汞标准溶液外还要用到指示剂，且废液中含汞，还要另外处理废液的费用，单个样品的成本在10元左右。The quantitative limit of the present invention is below 50ug/kg, which is far better than the industry standard of 1000ug/kg, and the present invention is also obviously better than the industry standard in terms of repeatability and accuracy. In addition, the analysis cost of the present invention is low, eliminating the input cost of instrument purchase (potentiometric titrators range from a few hundred yuan to tens of thousands of yuan according to the brand and model), and a single sample only needs to consume a few milliliters of silver nitrate standard solution, and the cost is less than one yuan. . In addition to the mercury nitrate standard solution, the industry standard also uses an indicator, and the waste liquid contains mercury, and there is an additional cost for the waste liquid treatment. The cost of a single sample is about 10 yuan.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.
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| CN201310009997.2ACN103063726B (en) | 2013-01-10 | 2013-01-10 | Detection method for chlorine ion content in lithium-ion battery electrolyte |
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