CN1322326C - Method for detecting water content of lithium ion cell electrolyte by gas chromatograply - Google Patents
Method for detecting water content of lithium ion cell electrolyte by gas chromatograply Download PDFInfo
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- CN1322326C CN1322326C CNB2004100938225A CN200410093822A CN1322326C CN 1322326 C CN1322326 C CN 1322326C CN B2004100938225 A CNB2004100938225 A CN B2004100938225A CN 200410093822 A CN200410093822 A CN 200410093822A CN 1322326 C CN1322326 C CN 1322326C
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Abstract
The present invention relates to a method for measuring the water content of lithium ion battery electrolyte via a gas chromatographic method. Owing to the separation of water peak and all other substances, the present invention comprises a gas chromatograph of temperature programming, a Paropak Q80 to 100 meshes of packed column with the length of 2.5 feet, a thermal conductivity detector, dry super pure hydrogen as carrier gas and a balance with of 10 mcg sensitivity. The present invention has the chromatographic analysis conditions of 75ml/min of carrier gas flow capacity, 200 DEG C of vaporizing chamber temperature, 200 DEG C of detector temperature and automatic heater current adjustment, and a post box adopts the temperature programming method. The present invention has an operation method of the combination of a weighing method and a chromatography method so as to attain the purpose of accurate moisture measurement, and the measuring method has the advantages of simplicity, high measuring speed, good repeatability and high precision and is widely used. The present invention is used for measuring the moisture of organic matter, sensitivity can reach 1 ppm and can reach the requirements of measuring electrolyte, and the moisture of general electrolysis requirements is < =20 ppm.
Description
Technical field
The invention belongs to the electrolytic solution liquid water content and measure, particularly a kind of vapor-phase chromatography is measured the method for lithium-ion battery electrolytes moisture.
Background technology
Lithium-ion battery electrolytes is one of critical material of lithium ion battery, and its moisture is an important techniques index, and this is a kind of technology of measuring the electrolytic solution micro-moisture, also is a kind of method that the lithium ion battery starting material detect.
The electrolytic solution of lithium ion battery is a kind of organic solution that contains lithium salts, usually wants strict its moisture of control, wherein has reason to have: 1) moisture can with electrolytic solution in have lithium salts to react, produce free acid (LiPF
6+ H
2O → 2HF+LiF+POF
3); 2) existence of moisture also makes the organic carbonate hydrolysis, produces proton solvent, and this is dangerous in lithium ion battery; 3) electrochemical window of water is narrower, and electrochemical reaction takes place in battery, makes battery generation performance change, as capacity reduction, bulging, cycle performance difference etc.; 4) the lithium metal reaction that may occur in moisture and the lithium ion battery has potential danger.So the control of the moisture of the electrolytic solution of lithium ion battery is very important, particularly in the lithium ion battery storage process.
Usually, the measurement of lithium ion battery moisture is that its principle is that Karl Fischer reagent reacts with moisture quantitatively with Karl Fischer method, and the power consumption method is determined the terminal point of reaction.The moisture of measuring electrolytic solution in this way has certain disadvantages: 1) need to consume the higher Karl Fischer reagent of price; 2) effect of some electrolysis additives and Karl Fischer reagent is unknown, and the solid particle that reaction sometimes produces will produce bigger influence to measuring; 3) the power consumption method is determined terminal point, might make the ion of electrolytic solution participate in electrochemical reaction, may bring error to measurement.
Gas chromatographic technique is since it is used, with its fast, reappears, precision is high and be subjected to application widely, is applied to measure organic moisture, sensitivity can reach 1ppm, reached the requirement of measuring electrolytic solution, and general electrolysis requires moisture≤20ppm.
Summary of the invention
Technical matters to be solved by this invention is: provide a kind of vapor-phase chromatography to measure the method for lithium-ion battery electrolytes moisture.
The electrolytic solution of lithium ion battery is made of lithium salts and organic solution, and lithium salts wherein commonly used at present is LiPF
6, solvent has propylene carbonate (PC), vinyl carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate ring-types such as (DEC) and linear carbonate and some organic adjuvants, and these complex materials will fully separately be comparatively difficult, also have LiPF in addition
6Decomposition.This method is only considered separating of water peak and other all substances, and other material only needs go out to get final product in the corresponding time.
Hardware condition is:
But the gas chromatograph of temperature programme is furnished with 2.5 feet long Paropak Q (80-100 order) packed column; Thermal conductivity cell detector; Dried ultra-pure hydrogen is done carrier gas; 100,000/ balance.
The analysis condition of chromatogram:
Carrier gas flux: 75ml/min; Temperature of vaporization chamber: 200 degree; Detector temperature: 200 degree (heater current is regulated automatically); The post case adopts temperature-programmed mode: 140 degree constant temperature 3 minutes-be warmed up to 200 degree-constant temperature 5 minutes with the speed of 10 degree/per minutes.The separating effect of moisture and other component is seen Fig. 1 in the sample.
Method of operating is that weighing method is used in combination with chromatography, reaches the purpose that measure water is divided: the 1) mensuration of the absolute correction factor of water: with 100,000/balance, adopt the loss of weight method to measure the absolute correction factor of water, the results are shown in accompanying drawing 1; 2) measure the sample size of sample with the loss of weight method, measure the area at sample Zhong Shui peak, with 1) correction factor of measuring calculates the absolute magnitude of moisture in the sample; 3) the sample introduction product per sample and the absolute magnitude of moisture calculate the content of the moisture of sample.
Result's influence that operating environment is measured this method is very big, this method just should be carried out drying room from the sampling beginning, and the relative humidity of drying room is less than 2%, and dewpoint temperature is-27 degree, in sampling and weighing process, environment can be ignored the influence of the moisture of sample like this.In order to prevent that carrier gas from bringing moisture into, before chromatographic column is advanced in carrier gas, need through drying tower, the drying agent of drying tower will often be changed.
Effect of the present invention is:
This measuring method, simple, measuring speed is fast, favorable reproducibility, precision is high and be subjected to using widely, is applied to measure organic moisture, and sensitivity can reach 1ppm, has reached the requirement of measuring electrolytic solution, and general electrolysis requires moisture≤20ppm.
Description of drawings
Fig. 1 is the separating effect figure of moisture and other component in the sample
Moisture is the separating resulting of 300ppm sample, and retention time is that 0.288 peak is the water peak
Specific embodiment
On homemade GC2003, be equipped with the same hardware mentioned with summary of the invention and, the electric liquid of a kind of import carried out moisture measurement, and compare with the measurement result of the Karl Fischer method of standard with identical experiment condition, confirmed chromatographic correctness.
Import electricity liquid is the LiPF that contains 1mol
6EC, EMC, PC electrolytic solution, its measurement result sees Table 1.
The result of table 1 chromatography determination of moisture result and Karl Fischer method relatively
| Sequence number | W 2 | W 3 | W 2-W 3 | Peak area | Moisture ppm | KF is ppm as a result |
| 1 | 11.08071 | 11.07671 | 0.00400 | 3738.4 | 60 | 61 |
| 2 | 11.52010 | 11.51481 | 0.00531 | 5142.2 | 63 | 60 |
| 3 | 11.52221 | 11.51840 | 0.00379 | 3676.1 | 62 | 63 |
| 4 | 11.52210 | 11.51911 | 0.00301 | 2741.8 | 59 | |
| 5 | 11.52062 | 11.51902 | 0.00160 | 1500.2 | 60 | |
| 6 | 11.52204 | 11.51964 | 0.00240 | 2380 | 64 |
Wherein moisture is 1.5520 * 10 than positive divisor definitely
-4g
-1
Claims (1)
1. a vapor-phase chromatography is measured the method for lithium-ion battery electrolytes moisture, it is characterized in that:
Use equipment: but the gas chromatograph of temperature programme, and be furnished with 2.5 feet long 80-100 order Paropak Q packed column; Thermal conductivity cell detector; Dried ultra-pure hydrogen is done carrier gas; 100,000/ balance;
The analysis condition of chromatogram:
Carrier gas flux: 75ml/min;
Temperature of vaporization chamber: 200 degree; Detector temperature: 200 degree, heater current is regulated automatically;
The post case adopts temperature-programmed mode: 140 degree constant temperature 3 minutes-be warmed up to 200 degree-constant temperature 5 minutes with the speed of 10 degree/per minutes;
Method of operating is that weighing method is used in combination with chromatography, reaches the purpose that measure water is divided: the 1) mensuration of the absolute correction factor of water: with 100,000/balance, adopt the loss of weight method to measure the absolute correction factor of water;
2) measure the sample size of sample with the loss of weight method, measure the area at sample Zhong Shui peak, with 1) correction factor of measuring calculates the absolute magnitude of moisture in the sample;
3) absolute magnitude of sample size per sample and moisture calculates the content of the moisture of sample;
Result's influence that operating environment is measured this method is very big, this method just should be carried out drying room from the sampling beginning, and the relative humidity of drying room is less than 2%, and dewpoint temperature is-27 degree, in sampling and weighing process, environment can be ignored the influence of the moisture of sample like this; In order to prevent that carrier gas from bringing moisture into, before chromatographic column is advanced in carrier gas, need through drying tower, the drying agent of drying tower will often be changed;
This method is only considered separating of water peak and other all substances, thereby other material only needs go out to get final product in the corresponding time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100938225A CN1322326C (en) | 2004-12-01 | 2004-12-01 | Method for detecting water content of lithium ion cell electrolyte by gas chromatograply |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100938225A CN1322326C (en) | 2004-12-01 | 2004-12-01 | Method for detecting water content of lithium ion cell electrolyte by gas chromatograply |
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| Publication Number | Publication Date |
|---|---|
| CN1782704A CN1782704A (en) | 2006-06-07 |
| CN1322326C true CN1322326C (en) | 2007-06-20 |
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| CNB2004100938225A Expired - Fee Related CN1322326C (en) | 2004-12-01 | 2004-12-01 | Method for detecting water content of lithium ion cell electrolyte by gas chromatograply |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106468644A (en) * | 2015-08-20 | 2017-03-01 | 中信国安盟固利动力科技有限公司 | A kind of method of testing of lithium ion battery cell moisture |
| CN109541061A (en) * | 2018-11-30 | 2019-03-29 | 大同新成新材料股份有限公司 | A kind of lithium-ion battery electrolytes measured portions analysis method |
| CN109459539B (en) * | 2018-12-29 | 2024-03-22 | 金宏气体股份有限公司 | Method and system for detecting trace moisture in high-purity ethyl silicate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2080390A5 (en) * | 1970-02-02 | 1971-11-12 | California Inst Tech | Electrolytic auxiliary analyzer for gas chromatographs |
| US4459357A (en) * | 1981-07-08 | 1984-07-10 | Jansen Karl Heinz | Process and apparatus for the quantitative determination of cations or anions by ion chromatography |
| SU1138727A1 (en) * | 1983-03-17 | 1985-02-07 | Херсонский Индустриальный Институт | Coulometric detector of flow-through type and composition of electrolyte for application thereof |
| CN1487293A (en) * | 2002-07-16 | 2004-04-07 | 海南碧凯药业有限公司 | Measuring method of zedoary oil and borneol content in suppository |
-
2004
- 2004-12-01 CN CNB2004100938225A patent/CN1322326C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2080390A5 (en) * | 1970-02-02 | 1971-11-12 | California Inst Tech | Electrolytic auxiliary analyzer for gas chromatographs |
| US4459357A (en) * | 1981-07-08 | 1984-07-10 | Jansen Karl Heinz | Process and apparatus for the quantitative determination of cations or anions by ion chromatography |
| SU1138727A1 (en) * | 1983-03-17 | 1985-02-07 | Херсонский Индустриальный Институт | Coulometric detector of flow-through type and composition of electrolyte for application thereof |
| CN1487293A (en) * | 2002-07-16 | 2004-04-07 | 海南碧凯药业有限公司 | Measuring method of zedoary oil and borneol content in suppository |
Non-Patent Citations (1)
| Title |
|---|
| 两种定量分析法的比较 郑清芬，焦作大学学报，第3期 2004 * |
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| CN1782704A (en) | 2006-06-07 |
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