CN103063726A - 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
- Publication number
- CN103063726A CN103063726A CN2013100099972A CN201310009997A CN103063726A CN 103063726 A CN103063726 A CN 103063726A CN 2013100099972 A CN2013100099972 A CN 2013100099972A CN 201310009997 A CN201310009997 A CN 201310009997A CN 103063726 A CN103063726 A CN 103063726A
- Authority
- CN
- China
- Prior art keywords
- lithium
- silver nitrate
- standard solution
- detection method
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Secondary Cells (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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 the lithium ion battery, chlorion has corrosive attack to the positive and negative pole material of battery in the battery material, cause battery capacity to descend, 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 mainly is comprised of carbonic ester and carboxylic acid esters organic solvent, lithium salts, adjuvant, what lithium salts wherein mainly used is lithium hexafluoro phosphate, it can use lithium chloride as raw material in building-up process, mainly by introducing in the raw material, the chlorine ion concentration of controlling in lithium salts and the electrolytic solution by the lithium ion content of analyzing exactly in the electrolytic solution has higher industrial application value to chlorion in the electrolytic solution.
Industry standard " HG/T4067-2008 lithium hexafluoro phosphate and lithium hexafluorophosphate electrolyte solution " is with the chlorion in the mercuric nitrate standard solution titration electrolytic solution of 0.001mol/lL, take bromophenol blue as indicator.Method detects limit for height, can't accurate quantitative analysis for the sample of chlorinity＜1000 μ g/kg, and method error is large, and Repeatability and Reproducibility is all undesirable, and the terminal point variable color is not obvious, and method applicability is not strong.
Summary of the invention
Based on this, the purpose of this invention is to provide a kind of detection method that detects low, the simple to operate fast chloride ion content of lower limit.
Concrete technical scheme is as follows:
The detection method of chloride ion content in a kind of lithium-ion battery electrolytes, adopt non-water potential titrimetry to detect: take non-water silver nitrate standard solution as titrant, silver electrode is indicator electrode, glass electrode is contrast electrode, is calculated as follows afterwards to terminal the content that namely gets chlorion with non-water silver nitrate standard solution titration sample:
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.
Among some embodiment, the solvent of described non-water silver nitrate standard solution is alcohols, ketone, carbonates or carboxylic acid esters therein.
Among some embodiment, described alcohols is methyl alcohol, ethanol, propyl alcohol, butanols or isopropyl alcohol therein.
Among some embodiment, described ketone is acetone or butanone therein.
Among some embodiment, described carbonates is carbon ester dimethyl ester, carbon ester diethylester, carbonic allyl ester, methyl ethyl carbonate therein.
Among some embodiment, described carboxylic acid esters is one or more in methyl formate, ethyl formate, the ethyl acetate therein.
Principle of the present invention is as follows:
The present invention adopts non-water potential titrimetry, Ag in non-aqueous solution
++ Cl
-=AgCl ↓, chlorion can be combined with silver ion and be generated silver nitride precipitation, is indicator electrode with silver electrode, glass electrode is contrast electrode, and electrode is immersed in the solution, in titration process, it is constant that the contrast electrode current potential keeps, and the indicator electrode current potential changes with the Chlorine in Solution ion concentration.Before and after stoichiometric point, the concentration change of Chlorine in Solution ion can cause the rapid variation of indicator electrode, and the hop point of indicator electrode is exactly to measure terminal point.
Lithium-ion battery electrolytes is non-aqueous solution, and lithium hexafluoro phosphate wherein can resolve into HF after meeting water, cause the variation of pH value in the solution, affects the constant of contrast electrode current potential, thereby affects the judgement of terminal point.So select especially non-aqueous organic solvent as solvent.
Advantage of the present invention is:
The present invention detects the method for chloride ion content in the lithium-ion battery electrolytes, simple to operate fast, cost is low, it is low to detect lower limit, for the sample of chloride ion content＜1000 μ g/kg also can accurate quantitative analysis, the detection lower limit of chloride ion content can reach 50 μ g/kg, the as a result precision that obtains is high.
Embodiment
The detection method of chloride ion content in a kind of lithium-ion battery electrolytes of the present invention, adopt non-water potential titrimetry to detect: take non-water silver nitrate standard solution as titrant, silver electrode is indicator electrode, glass electrode is contrast electrode, is calculated as follows afterwards to terminal the content that namely gets chlorion with non-water silver nitrate standard solution titration sample:
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 (being 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); Among some embodiment, described carboxylic acid esters is one or more in methyl formate, ethyl formate, the ethyl acetate therein.
Described lithium-ion battery electrolytes is comprised of organic solvent and the electric conducting lithium salt of carbonic ester and carboxylic acid esters.
Carbon ester ester is selected from least a or several in the 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 a or several in the following material: butyrolactone, valerolactone, caprolactone, methyl formate, ethyl formate, ethyl acetate, propyl acetate, isopropyl acetate.
Described electric conducting lithium salt is selected from least a or several in the following material: lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate.
Employed lithium-ion battery electrolytes Raw is composed as follows in the embodiment of the invention:
Solvent is DMC:EMC:EC=1:1:1; The hexafluorophosphoric acid lithium concentration is 1mol/L.
The present invention is further elaborated by the following examples.
Embodiment 1
A, the preparation of 0.1mol/L silver nitrate standard solution:
Take by weighing the 17.5g silver nitrate, be dissolved in the 1000mL ethanol, shake up.Solution is stored in the brown bottle.
B, 0.1mol/L silver nitrate standard solution are demarcated:
Take by weighing the 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:
Preparation and the good 0.1mol/L silver nitrate standard solution of demarcation are accurately diluted 100 times with ethanol.
The detection of chlorion in E, the electrolytic solution:
Accurately take by weighing approximately 60g lithium-ion battery electrolytes sample (being accurate to 0.01g) in titration cup, stirring rear is the silver nitrate standard titration solution of 0.001mol/lL with concentration, use Switzerland's ten thousand logical 848 automatical potentiometric titrimeters of silver/silver chloride electrode, open the instrument automatic Titration, test is finished, stop titration, by following formula result of calculation.
X---chloride ion content, μ g/kg
C---the concentration of 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 by weighing 100g electrolytic solution sample, accurately add the chlorion (sodium chloride) of 10 μ g, detect the chlorion result of adding, calculate recovery rate.
The recovery more is tending towards 100%, and result's accuracy is higher, and the recovery of the present invention can satisfy the measurement requirement at 84%-118% fully 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.
The sample survey result:
The 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.
The sample survey result:
The 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.
The sample survey result:
The recovery test result:
Comparative Examples 1:
Mercuric nitrate indicator titration method and the present invention contrast test in the chlorion of lithium-ion battery electrolytes detects in the industry standard " HG/T4067-2008 lithium hexafluoro phosphate and lithium hexafluorophosphate electrolyte solution ":
Prepare respectively chloride ion content at three lithium-ion battery electrolytes samples of 50 μ g/kg, 500 μ g/kg, 1000 μ g/kg, test respectively by mercuric nitrate indicator titration method in the 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 is much better than the 1000ug/kg of industry standard below 50ug/kg, and the present invention also obviously is being better than industry standard aspect repeatability and the accuracy.Analysis cost of the present invention is low in addition, rejects the input cost (potentiometric titrimeter does not wait to units up to ten thousand from hundreds of unit according to brand and model) of Instrument purchase, and single sample only need consume several milliliters of silver nitrate standard solution, and cost is less than a yuan.Except using the mercuric nitrate standard solution, also to use indicator in the industry standard, and mercurous in the waste liquid, the expense that also will dispose waste liquid in addition, the cost of single sample is about 10 yuan.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.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 (6)
1. the detection method of chloride ion content in the lithium-ion battery electrolytes, it is characterized in that, adopt non-water potential titrimetry to detect: take non-water silver nitrate standard solution as titrant, silver electrode is indicator electrode, glass electrode is contrast electrode, is calculated as follows afterwards to terminal the content that namely gets chlorion with non-water silver nitrate standard solution titration sample:
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.
2. the detection method of chloride ion content in the lithium-ion battery electrolytes according to claim 1 is characterized in that, the solvent of described non-water silver nitrate standard solution is alcohols, ketone, carbonates or carboxylic acid esters.
3. the detection method of chloride ion content in the lithium-ion battery electrolytes according to claim 2 is characterized in that, described alcohols is methyl alcohol, ethanol, propyl alcohol, butanols or isopropyl alcohol.
4. the detection method of chloride ion content in the lithium-ion battery electrolytes according to claim 2 is characterized in that, described ketone is acetone or butanone.
5. the detection method of chloride ion content in the lithium-ion battery electrolytes according to claim 2 is characterized in that, described carbonates is carbon ester dimethyl ester, carbon ester diethylester, carbonic allyl ester or methyl ethyl carbonate.
6. the detection method of chloride ion content in the lithium-ion battery electrolytes according to claim 2 is characterized in that, described carboxylic acid esters is one or more in methyl formate, ethyl formate, the ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310009997.2A CN103063726B (en) | 2013-01-10 | 2013-01-10 | Detection method for chlorine ion content in lithium-ion battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310009997.2A CN103063726B (en) | 2013-01-10 | 2013-01-10 | Detection method for chlorine ion content in lithium-ion battery electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103063726A true CN103063726A (en) | 2013-04-24 |
| CN103063726B CN103063726B (en) | 2015-01-07 |
Family
ID=48106438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310009997.2A Expired - Fee Related CN103063726B (en) | 2013-01-10 | 2013-01-10 | Detection method for chlorine ion content in lithium-ion battery electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103063726B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103645274A (en) * | 2013-12-03 | 2014-03-19 | 河北钢铁股份有限公司邯郸分公司 | Method for determining content of chlorine ion in cold-rolled emulsified liquid |
| 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 |
| 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 |
| 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 |
| 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 |
| CN111735907A (en) * | 2020-08-04 | 2020-10-02 | 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 |
| CN112345691A (en) * | 2020-12-07 | 2021-02-09 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1423127A (en) * | 2001-12-04 | 2003-06-11 | 比亚迪股份有限公司 | Nonaqueous titration determination method of hydrogen fluoride in electrolyte of lithium ion cell |
| CN101587093A (en) * | 2008-05-23 | 2009-11-25 | 上海宝钢工业检测公司 | Method for measuring content of chloridion in wet flat liquid |
| CN101650337A (en) * | 2009-09-11 | 2010-02-17 | 河北省电力研究院 | Method for testing chloride content in smoke gas desulfurization system |
| CN102590316A (en) * | 2011-11-07 | 2012-07-18 | 郑州飞机装备有限责任公司 | Method for detecting chloride ion impurities in high concentration chromic anhydride solution |
-
2013
- 2013-01-10 CN CN201310009997.2A patent/CN103063726B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1423127A (en) * | 2001-12-04 | 2003-06-11 | 比亚迪股份有限公司 | Nonaqueous titration determination method of hydrogen fluoride in electrolyte of lithium ion cell |
| CN101587093A (en) * | 2008-05-23 | 2009-11-25 | 上海宝钢工业检测公司 | Method for measuring content of chloridion in wet flat liquid |
| CN101650337A (en) * | 2009-09-11 | 2010-02-17 | 河北省电力研究院 | Method for testing chloride content in smoke gas desulfurization system |
| CN102590316A (en) * | 2011-11-07 | 2012-07-18 | 郑州飞机装备有限责任公司 | Method for detecting chloride ion impurities in high concentration chromic anhydride solution |
Non-Patent Citations (1)
| Title |
|---|
| 白小叶: "酸性镀铜溶液中氯离子的测定", 《有色矿冶》, vol. 22, no. 3, 30 June 2006 (2006-06-30), pages 70 - 72 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103645274A (en) * | 2013-12-03 | 2014-03-19 | 河北钢铁股份有限公司邯郸分公司 | Method for determining content of chlorine ion in cold-rolled emulsified liquid |
| 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 |
| CN111735907A (en) * | 2020-08-04 | 2020-10-02 | 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 |
| CN112345691A (en) * | 2020-12-07 | 2021-02-09 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103063726B (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103063726B (en) | Detection method for chlorine ion content in lithium-ion battery electrolyte | |
| CN103645226A (en) | Method for detecting free acids in boracic lithium salt and electrolyte of boracic lithium salt | |
| CN104792901A (en) | Quantitative measuring method of lithium ion battery electrolyte solvent | |
| CN103604856A (en) | Potentiometric titration method of acid mixture solution | |
| CN110261464A (en) | The method of free acid content in lithium hexafluoro phosphate product is quickly measured in non-aqueous system | |
| CN106404995A (en) | Method for measuring content of chlorine in mixed acid electrolyte through potentiometric titration | |
| CN103913458A (en) | Detection method for trace free acid in electrolyte lithium salt | |
| KR20130076700A (en) | Method for measuring hf content in lithium secondary battery electrolyte and analytical reagent composition used in the same | |
| CN101825579A (en) | Method for measuring concentration of polyacrylamide solution | |
| CN109668941A (en) | A kind of method of sulfuric acid and manganese sulfate concentration in measurement electrolyte aqueous solution | |
| CN107703138A (en) | The detection method of acidity in lithium ion battery electrolyte lithium salts and electrolyte | |
| CN109142617A (en) | The nonaqueous titration determination method of Free HF in lithium-ion electrolyte | |
| CN104792833A (en) | Method of quickly detecting heavy metal ions lead and cadmium in water | |
| US20180238828A1 (en) | Method for detecting surface coating performance of cathode active material | |
| JPWO2011007384A1 (en) | Sensitive membrane for ion-selective electrode | |
| Wilken et al. | A fluoride-selective electrode (Fse) for the quantification of fluoride in lithium-ion battery (Lib) electrolytes | |
| CN111505200A (en) | Method for detecting trace free acid in electrolyte additive | |
| CN107807150A (en) | A kind of detection method of inorganic electrolyte lithium salt content | |
| CN105466982A (en) | Method for detecting heavy metal in water | |
| CN102901765B (en) | Potentiometric titration method for measuring content of Hg<2+> in solution | |
| CN101957336A (en) | Method for improving detection accuracy of electrochemical active metal ions | |
| CN113049585A (en) | Analysis method of sulfate ions in additive for lithium ion battery electrolyte | |
| CN104062396A (en) | Method for measuring content of nitrogen in metal lithium and lithium alloy | |
| JP6849276B2 (en) | Solution analysis method | |
| KR101425997B1 (en) | Method of measuring moisture content in lithium secondary battery electrolyte and analytical reagent composition used in the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150107 Termination date: 20220110 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |