CN103063726B - Detection method for chlorine ion content in lithium-ion battery electrolyte - Google Patents
Detection method for chlorine ion content in lithium-ion battery electrolyte Download PDFInfo
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- CN103063726B CN103063726B CN201310009997.2A CN201310009997A CN103063726B CN 103063726 B CN103063726 B CN 103063726B CN 201310009997 A CN201310009997 A CN 201310009997A CN 103063726 B CN103063726 B CN 103063726B
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Abstract
The invention discloses a detection method for chlorine ion content in lithium-ion battery electrolyte. A non-aqueous potentiometric titration method is adopted for detection. Non-aqueous silver nitrate standard solution is taken as titrant; a silver electrode is an indicating electrode and a glass electrode is a reference electrode; a detected sample is titrated to an end point by the non-aqueous silver nitrate standard solution; and the chlorine ion content in the sample can be obtained by calculation according to the size of the detected sample, the concentration of the silver nitrate standard solution and the titration volume. The method has the advantages of simplicity and rapidness in operation, low cost, low detection limit and high result precision.
Description
Technical field
The present invention relates to chemical analysis field, particularly relate to the detection method of chloride ion content in a kind of lithium-ion battery electrolytes.
Background technology
Electrolytic solution is the important component part in lithium ion battery, in battery material, the positive and negative pole material of chlorion to battery has corrosive attack, battery capacity is caused to decline, the serious pole piece that causes is bored a hole, destroy whole battery, in industry standard " HG/T4067-2008 lithium hexafluoro phosphate and lithium hexafluorophosphate electrolyte solution ", require its content≤1000 μ g/kg.
The raw material of electrolytic solution is primarily of carbonic ester and carboxylic acid esters organic solvent, lithium salts, adjuvant composition, lithium salts wherein mainly uses lithium hexafluoro phosphate, it can use lithium chloride as raw material in building-up process, chlorion in electrolytic solution mainly by what introduce in raw material, has higher industrial application value by the lithium ion content analyzed exactly in the electrolytic solution chlorine ion concentration controlled in lithium salts and electrolytic solution.
The chlorion of industry standard " HG/T4067-2008 lithium hexafluoro phosphate and lithium hexafluorophosphate electrolyte solution " in the mercuric nitrate standard solution titration electrolytic solution of 0.001mol/lL take bromophenol blue as indicator.Method detects limit for height, and the sample for chlorinity < 1000 μ g/kg cannot accurate quantitative analysis, and method error is large, and Repeatability and Reproducibility is all undesirable, and terminal variable color is not obvious, and method applicability is not strong.
Summary of the invention
Based on this, the object of this invention is to provide the detection method of low, the simple to operate chloride ion content fast of a kind of Monitoring lower-cut.
Concrete technical scheme is as follows:
The detection method of chloride ion content in a kind of lithium-ion battery electrolytes, non-hyperbolic curve method is adopted to detect: with non-water silver nitrate standard solution for titrant, silver electrode is indicator electrode, glass electrode is contrast electrode, is calculated as follows afterwards to terminal with non-water silver nitrate standard solution titration sample and obtains the content of chlorion:
X---chloride ion content, μ g/kg;
C---the concentration of non-water silver nitrate standard solution, mol/L;
V---titration consumes the volume of non-water silver nitrate standard solution, mL;
The quality of m---sample, g.
Wherein in some embodiments, the solvent of described non-water silver nitrate standard solution is alcohols, ketone, carbonates or carboxylic acid esters.
Wherein in some embodiments, described alcohols is methyl alcohol, ethanol, propyl alcohol, butanols or isopropyl alcohol.
Wherein in some embodiments, described ketone is acetone or butanone.
Wherein in some embodiments, described carbonates is carbon ester dimethyl ester, carbon ester diethylester, carbonic allyl ester, methyl ethyl carbonate.
Wherein in some embodiments, described carboxylic acid esters is one or more in methyl formate, ethyl formate, ethyl acetate.
Principle of the present invention is as follows:
The present invention adopts non-hyperbolic curve method, Ag in non-aqueous solution
++ Cl
-=AgCl ↓, chlorion can be combined with silver ion and generate silver nitride precipitation, is indicator electrode by silver electrode, glass electrode is contrast electrode, and immerses in solution by electrode, in titration process, contrast electrode current potential keeps constant, and indicator electrode current potential changes with the change of Chlorine in Solution ion concentration.Before and after stoichiometric point, the concentration change of Chlorine in Solution ion, can cause the sharply change of indicator electrode, and the hop point of indicator electrode measures terminal exactly.
Lithium-ion battery electrolytes is non-aqueous solution, and lithium hexafluoro phosphate wherein can resolve into HF after chance water, causes the change of pH value in solution, affects the constant of contrast electrode current potential, thus affect the judgement of terminal.Select non-aqueous organic solvent as solvent so special.
Advantage of the present invention is:
The present invention detects the method for chloride ion content in lithium-ion battery electrolytes, simple to operate fast, cost is low, Monitoring lower-cut is low, for chloride ion content < 1000 μ g/kg sample also can accurate quantitative analysis, chloride ion content Monitoring lower-cut can reach 50 μ g/kg, the result precision obtained is high.
Embodiment
The detection method of chloride ion content in a kind of lithium-ion battery electrolytes of the present invention, non-hyperbolic curve method is adopted to detect: with non-water silver nitrate standard solution for titrant, silver electrode is indicator electrode, glass electrode is contrast electrode, is calculated as follows afterwards to terminal with non-water silver nitrate standard solution titration sample and obtains the content of chlorion:
X---chloride ion content, μ g/kg;
C---the concentration of non-water silver nitrate standard solution, mol/L;
V---titration consumes the volume of non-water silver nitrate standard solution, mL;
The quality of m---sample, g.
The solvent of described non-water silver nitrate standard solution is alcohols, ketone, carbonates or carboxylic acid esters, and described alcohols is methyl alcohol, ethanol, propyl alcohol, butanols or isopropyl alcohol (preferably ethanol); Described ketone is acetone or butanone (being preferably acetone); Described carbonates is carbon ester dimethyl ester, carbon ester diethylester, carbonic allyl ester, methyl ethyl carbonate (preferred carbon ester dimethyl ester); Wherein in some embodiments, described carboxylic acid esters is one or more in methyl formate, ethyl formate, ethyl acetate.
Described lithium-ion battery electrolytes is made up of the organic solvent of carbonic ester and carboxylic acid esters and electric conducting lithium salt.
Carbon ester ester is selected from least one or several in following material: carbon ester vinyl acetate, carbon ester propylene, carbon ester butene esters, carbon ester dimethyl ester, carbon ester diethylester, carbonic acid first butyl ester, ethyl butyl carbonate, dibutyl carbonate, chloro-ethylene carbonate, methyl ethyl carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, methyl propyl carbonate, carbonic acid first isopropyl ester, vinylene carbonate, chlorocarbonic acid vinyl acetate.
Carboxylic esters is selected from least one or several in following material: butyrolactone, valerolactone, caprolactone, methyl formate, ethyl formate, ethyl acetate, propyl acetate, isopropyl acetate.
Described electric conducting lithium salt is selected from least one or several in following material: lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate.
The lithium-ion battery electrolytes Raw used in the embodiment of the present invention is composed as follows:
Solvent is DMC:EMC:EC=1:1:1; Hexafluorophosphoric acid lithium concentration is 1mol/L.
The present invention is further elaborated by the following examples.
Embodiment 1
A, 0.1mol/L silver nitrate standard solution is prepared:
Take 17.5g silver nitrate, be dissolved in 1000mL ethanol, shake up.Solution is stored in brown bottle.
B, 0.1mol/L silver nitrate standard solution is demarcated:
Take 0.22g primary standard reagent sodium chloride, adopt potentiometric titrimeter (silver electrode is indicator electrode, and glass electrode is contrast electrode) to demarcate.
The preparation of D, 0.001mol/L silver nitrate standard solution:
To prepare and the 0.1mol/L silver nitrate standard solution ethanol accurate dilutions 100 times demarcated.
The detection of chlorion in E, electrolytic solution:
Accurately take about 60g lithium-ion battery electrolytes sample (being accurate to 0.01g) in toward in titration cup, stir the silver nitrate standard titration solution that rear concentration is 0.001mol/lL, use logical 848 automatical potentiometric titrimeters of Switzerland ten thousand of silver/silver chloride electrode, open instrument automatic Titration, test completes, stop titration, by following formulae discovery result.
X---chloride ion content, μ g/kg
The concentration of C---silver nitrate standard solution, mol/L
V---titration consumes the volume of silver nitrate standard solution, mL
The quality of m---sample, g.
F, sample survey result:
G, recovery test
Accurately take 100g electrolytic solution sample, accurately add the chlorion (sodium chloride) of 10 μ g, detect the chlorion result added, calculate the recovery.
The recovery is more tending towards 100%, and the accuracy of result is higher, and the recovery of the present invention, at 84%-118%, can meet measurement requirement completely for trace analysis.
Embodiment 2:
With reference to embodiment 1 experimental procedure, change the etoh solvent of silver nitrate standard solution into acetone, other step is identical.
Sample survey result:
Recovery test result:
Embodiment 3:
With reference to embodiment 1 experimental procedure, change the etoh solvent of silver nitrate standard solution into ethyl acetate, other step is identical.
Sample survey result:
Recovery test result:
Embodiment 4:
With reference to embodiment 1 experimental procedure, change the etoh solvent of silver nitrate standard solution into dimethyl carbonate, other step is identical.
Sample survey result:
Recovery test result:
Comparative example 1:
Mercuric nitrate indicator titration method and the contrast test of the present invention in the chloride test of lithium-ion battery electrolytes in industry standard " HG/T4067-2008 lithium hexafluoro phosphate and lithium hexafluorophosphate electrolyte solution ":
Prepare three the lithium-ion battery electrolytes samples of chloride ion content at 50 μ g/kg, 500 μ g/kg, 1000 μ g/kg respectively, test respectively by mercuric nitrate indicator titration method in industry standard " HG/T4067-2008 lithium hexafluoro phosphate and lithium hexafluorophosphate electrolyte solution " and method of the present invention, comparison of test results is as follows:
Quantitative limit of the present invention, at below 50ug/kg, is much better than the 1000ug/kg of industry standard, and the present invention is also obviously better than industry standard in repeatability and accuracy.Analysis cost of the present invention is low in addition, and reject the input cost (potentiometric titrimeter is not according to brand and model from hundreds of unit to unit up to ten thousand etc.) of Instrument purchase, single sample only need consume several milliliters of silver nitrate standard solution, and cost is less than a yuan.Except using mercuric nitrate standard solution, also will indicator be used in industry standard, and mercurous in waste liquid, the expense that also will dispose waste liquid in addition, the cost of single sample is at about 10 yuan.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (5)
1. the detection method of chloride ion content in a lithium-ion battery electrolytes, it is characterized in that, non-hyperbolic curve method is adopted to detect: with non-water silver nitrate standard solution for titrant, silver electrode is indicator electrode, glass electrode is contrast electrode, is calculated as follows afterwards to terminal with non-water silver nitrate standard solution titration sample and obtains the content of chlorion:
X---chloride ion content, μ g/kg;
C---the concentration of non-water silver nitrate standard solution, mol/L;
V---titration consumes the volume of non-water silver nitrate standard solution, mL;
The quality of m---sample, g;
The solvent of described non-water silver nitrate standard solution is alcohols, ketone, carbonates or carboxylate.
2. the detection method of chloride ion content in lithium-ion battery electrolytes according to claim 1, it is characterized in that, described alcohols is methyl alcohol, ethanol, propyl alcohol, butanols or isopropyl alcohol.
3. the detection method of chloride ion content in lithium-ion battery electrolytes according to claim 1, it is characterized in that, described ketone is acetone or butanone.
4. the detection method of chloride ion content in lithium-ion battery electrolytes according to claim 1, it is characterized in that, described carbonates is carbon ester dimethyl ester, carbon ester diethylester, carbonic allyl ester or methyl ethyl carbonate.
5. the detection method of chloride ion content in lithium-ion battery electrolytes according to claim 1, it is characterized in that, described carboxylate is one or more in methyl formate, ethyl formate, ethyl acetate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103645274B (en) * | 2013-12-03 | 2016-02-24 | 河北钢铁股份有限公司邯郸分公司 | Measure the method for chloride ion content in cold-rolling emulsion |
| CN103645226A (en) * | 2013-12-26 | 2014-03-19 | 东莞市杉杉电池材料有限公司 | Method for detecting free acids in boracic lithium salt and electrolyte of boracic lithium salt |
| CN103926300A (en) * | 2014-04-09 | 2014-07-16 | 北京工业大学 | Improved method for determining free chlorine ions in cement paste or mortar |
| CN105092776A (en) * | 2015-08-13 | 2015-11-25 | 超威电源有限公司 | Method for measuring chlorine content in industrial barium sulfate through full-automatic potenitiometric titration |
| RU2707580C1 (en) * | 2018-08-10 | 2019-11-28 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Method for quantitative determination of chlorides in concentrate of tetramethylammonium hydroxide |
| CN110361339A (en) * | 2019-05-31 | 2019-10-22 | 衢州康鹏化学有限公司 | The detection method of chloride in imidodisulfuryl fluoride lithium salt |
| CN111007133A (en) * | 2019-12-25 | 2020-04-14 | 江苏国泰超威新材料有限公司 | Method for determining chloride ions in electrolyte for aluminum electrolytic capacitor |
| CN111735907B (en) * | 2020-08-04 | 2020-12-08 | 湖南航天磁电有限责任公司 | Method for measuring chloride ion content in industrial lanthanum oxide by potentiometric titration |
| CN112180008A (en) * | 2020-09-16 | 2021-01-05 | 合肥国轩高科动力能源有限公司 | Sample pretreatment method for determining content of chloride ions in lithium ion battery electrolyte |
| CN112345691B (en) * | 2020-12-07 | 2022-08-19 | 武汉海斯普林科技发展有限公司 | Method for detecting content of chloride ions in electrolyte solute of aluminum electrolytic capacitor |
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