CN100368800C - Quantitatively analyzing method for fluohydric acid in lithium ion battery electrolyte - Google Patents
Quantitatively analyzing method for fluohydric acid in lithium ion battery electrolyte Download PDFInfo
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Abstract
The present invention relates to a quantitatively analyzing method for fluohydric acid in lithium ion battery electrolyte, which comprises following steps that lithium ion battery electrolyte is diluted in solvent absolute methanol or ethanol which does not need drying, MOH is used as titrant, and an automatic potentiometric titration method is used; a titration curve is determined by (C0 *V20) /(1000*M), wherein C0 represents titrant concentration, V represents the volume (ml) of the consumed titrant, 20 represents the molecular weight of HF, and M represents the weight (g) of the electrolyte; second order derivation is carried out for the titration curve by a potentiometric titrimeter, and thereby, a titration end point is determined. Compared with the prior art, the measuring accuracy of the present invention is greatly improved, the price of the titrant and the solvent is low, a titrate process does not need carrying out in a glove box, and the present invention is a testing method which is suitable for technical analysis.
Description
Technical field
The present invention relates to the manufacturing technology field of lithium-ion battery electrolytes, specifically be meant the quantitative analysis method of hydrofluorite in a kind of lithium-ion battery electrolytes.
Background technology
Micro-hydrofluorite all has very big influence to capacity, cycle life and the security of battery in the nonaqueous electrolytic solution that lithium ion battery is used.Therefore, in the manufacture process of production, storage, transportation and the battery of lithium-ion battery electrolytes, must carry out strict monitoring to the content of hydrofluorite.But, at present extremely rare in this technology of reporting on the one hand.At present, adopt tetrabutylammonium (NBu usually
4OH) be that titrant, bromthymol blue (BTB) are indicator, in the absolute methanol solvent, the reaction effect that hydrogen fluoride and tetrabutylammonium take place in to the electrolytic solution comes hydrogen fluoride in the non-aqueous system is measured (N according to the observation
+Bu
4OH
-+ HF=N
+Bu
4F
-+ H
2O), but should the reaction simultaneous subsidiary reaction (N
+Bu
4OH
-+ CH
3OH=N
+Bu
4OCH
3 -+ H
2O) bring certain error to analysis result, and the price of tetrabutylammonium also very expensive (for example assay method of MERCK company).For addressing this problem, No. 01130017.5 application for a patent for invention of China discloses a kind of method that adopts sodium methoxide to make titrant again, be detected as this aspect in reduction certain improvement is arranged, but the common ground of this method and said method is all to adopt BTB to make indicator, method by range estimation is judged terminal point, and this can produce certain systematic error.In addition, industrial in order to improve the stability of electrolytic solution, generally can add some stabilizing agents to improve the stability of lithium hexafluoro phosphate, suppress hydrofluoric generation and absorption hydrogen fluoride, and these stabilizing agents are lewis base mostly, make electrolytic solution generally can present faint alkalescence (the pH value is approximately 7～9), and BTB color transition point pH value are approximately 7, so pH value of solution value hop point is inconsistent with the color transition point of BTB probably during titration, brings bigger error to test result.
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part, and the quantitative analysis method of hydrofluorite in a kind of lithium-ion battery electrolytes is provided.This method can overcome the inconsistent problem of color transition point of solution pH value hop point and indicator in the present titration method, thereby has improved the accuracy of measurement result greatly.
The present invention is achieved through the following technical solutions: in the described lithium-ion battery electrolytes quantitative analysis method of hydrofluorite with lithium-ion battery electrolytes by the dilution proportion that adds 2.5～3.0g in every 50ml solvent in need not the solvent absolute methanol or absolute ethyl alcohol of dried, and be titrant with MOH, adopt automatic potentiometric titration to measure titration curve, utilize potentiometric titrimeter that titration curve is carried out the second order differentiate, thereby determine titration end-point; Utilize formula (C
0* V20)/(1000 * m) calculate end point values, wherein C
0Be the concentration mol/L of titrant, V is for consuming the volume ml of titrant, and 20 is the molecular weight of HF, and m is the weight g of electrolytic solution.
In order to realize the present invention better, the M among the described titrant MOH comprises alkaline metal, particularly KOH such as lithium, sodium, potassium; Described titrant concentration is 0.0100mol/L～0.1000mol/L; Described solvent be need not dried absolute ethyl alcohol or absolute methanol (water cut 0.15～0.2%), be preferably especially need not dried absolute ethyl alcohol; Described lithium-ion battery electrolytes comprises organic solvent and lithium salts two parts, described organic solvent comprises that (one or more mixed solvents in γ-BL), dimethoxy-ethane (DME), the tetrahydrofuran (THF), described lithium salts comprises LiCF for ethylene carbonate (EC), carbonic allyl ester (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), gamma-butyrolacton
3SO
3, LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiN (CF
3SO
2)
2In one or more potpourris.
The present invention compared with prior art has following advantage and beneficial effect:
The present invention is studying the influence to the hydrofluorite quantitative test of titrant and solvent respectively, analyze on the basis of the test result that has compared indicator method and automatic potentiometric titration respectively, proposed a kind of accurate analytical approach that is suitable for hydrofluorite in the lithium-ion battery electrolytes.The present invention compared with prior art, measuring accuracy improves greatly that (result that measures of prior art is on the low side, irrelevance is bigger add the organic amine stabilizing agent in electrolytic solution after, and the result who tests in the electrolytic solution big in acidity, that stabiliser content is higher differs very obvious, and deviation reaches 18.2%).
The contrast experiment proves, is that the test result of titrant is bigger than normal than the test result of other titrant with the tetrabutylammonium; It is the mildest to make the titration curve that titrant measures with sodium methoxide, and hop is not obvious, and that the parallel result who is measured departs from is big (this mainly is because a little less than the alkalescence of sodium methoxide, more slowly causes with the reaction of acid); With NaOH and KOH be titrant titration jump all clearly, and replicate determination result's degree of accuracy is better than above-mentioned two kinds of titrant, but because the reactivity of NaOH and solvent is bigger, test result is higher slightly than KOH.The alkalescence of KOH is stronger, and with being swift in response of acid, the hop of curve is apparent in view, and KOH and absolute methanol, absolute ethyl alcohol are all less than reaction.Test shows, titration curve mild than in absolute ethyl alcohol all in absolute methanol; Absolute ethyl alcohol is without further drying, and wherein the existence of micro-moisture does not only influence measurement result, and makes titration jump more obvious, more helps the judgement of terminal point.Therefore, the preferred KOH of the present invention is a titrant, do not make solvent through the absolute ethyl alcohol of further dried, the easiest judgement of titration end-point, test result is the most accurate, and used titrant and solvent low price, titration process need not carry out in glove box, is a kind of method of testing that is suitable for very much technical analysis.
Description of drawings
Fig. 1 is the titration curve of the embodiment of the invention four four kinds of titrant in absolute methanol and two kinds of solvents of absolute ethyl alcohol;
Fig. 2 is the acidity titration curve of the embodiment of the invention four in the alcohol solvent of different moisture content.
Embodiment
Below in conjunction with drawings and Examples, the present invention is done detailed description further.
The part reagent and the instrument that adopt among the embodiment comprise:
Methyl alcohol (chromatographically pure, German Merk company produces); Absolute ethyl alcohol (analyzing pure); The 3A molecular sieve; Benzoic acid (reference material), following dry 8 hours in 80 ℃ in vacuum; Bromthymol blue (BTB), following dry 8 hours in 100 ℃ in vacuum; 0.1mol/L NaOH ethanolic solution (analyze pure, German Merk company produces); 0.1mol/L potassium hydroxide-ethanol solution (analyze pure, German Merk company produces); Tetrabutylammonium; 0.1mol/L aqueous isopropanol (analyze pure, German Merk company produces); Sodium methoxide (analyzing pure).
EC, DMC, EMC: content＞99.95%, water cut＜10ppm.LiPF
6: content＞99.95%, content＜100ppm of HF.Organic base (representing): content＞99.9%, water cut＜100ppm with N.Deionized water.
Metrohm798 type potentiometric titrimeter (production of Switzerland Metrohm company); Compound pH electrode of long-life; Metrohm831KF type moisture teller (production of Switzerland Metrohm company); Electronic balance (degree of accuracy 0.0001g, Sai Duolisi); Glove box: argon gas atmosphere, anhydrous and oxygen-free; The preparation of electrolytic solution and sampling are all carried out in this glove box; 10mlPE material syringe.
Embodiment one
The first step selects for use dry good 10mlPE material syringe to get the 8ml lithium-ion battery electrolytes in glove box, and the syringe needle silica gel sealing is transferred to syringe in the air; Lithium-ion battery electrolytes is by diethyl carbonate (DEC), gamma-butyrolacton (γ-BL) and LiCF
3SO
3, LiBF
4Mix to form, γ-BL: DEC=1: 2 (w) wherein, the concentration of two kinds of lithium salts all is 0.5mol/L;
Second step added 50.0ml absolute methanol (need not dried, water cut 0.15%) with transfer pipet in titration cup, add 2 gram electrolytic solution (weigh with scale and inject the amount of electrolytic solution, be accurate to 0.1mg), started and stirred;
It is that the potassium hydroxide of 0.0100mol/L is titrant that the 3rd step was selected concentration for use, and the beginning titration is input in the potentiometric titrimeter input second order differentiate program (Switzerland Metrohm company provides) and acidity computing formula (C with the consumption of electrolytic solution
0* V20)/(1000 * m), wherein, C
0Be the concentration mol/L of titrant, V is for consuming the volume ml of titrant, and 20 is the molecular weight of HF, and m is the weight g of electrolytic solution; Adjust the titration step-length according to hydrofluoric content in the electrolytic solution, the titration step-length consumes 1/10～1/20 of volume of titrant during for titration end-point, at the uniform velocity titration, to terminal point occur, titration curve very mild after, stop titration, get last hop terminal point;
The 4th step consumed 1/10～1/20 of volume of titrant when seeing the titration step-length whether for titration end-point according to test result, if not, adjust the titration step-length and repeated for the 3rd step; Replicate determination as a result 3 times is averaged.
Embodiment two
The first step selects for use dry good 10mlPE material syringe to get the 8ml lithium-ion battery electrolytes in glove box, and the syringe needle silica gel sealing is transferred to syringe in the air; Lithium-ion battery electrolytes is by carbonic allyl ester (PC), dimethoxy-ethane (DME) and LiClO
4, LiAsF
6Mix to form, PC: DME=1: 2 (w) wherein, the concentration of two kinds of lithium salts all is 0.5mol/L;
Second step added 50.0ml absolute ethyl alcohol (need not dried, water cut 0.2%) with transfer pipet in titration cup, add 2.5 gram electrolytic solution (weigh with scale and inject the amount of electrolytic solution, be accurate to 0.1mg), started and stirred;
It is that the NaOH of 0.0500mol/L is titrant that the 3rd step was selected concentration for use, and the beginning titration is input in the potentiometric titrimeter input second order differentiate program (Switzerland Metrohm company provides) and acidity computing formula (C with the consumption of electrolytic solution
0* V20)/(1000 * m), wherein, C
0Be the concentration mol/L of titrant, V is for consuming the volume ml of titrant, and 20 is the molecular weight of HF, and m is the weight g of electrolytic solution; Adjust the titration step-length according to hydrofluoric content in the electrolytic solution, the titration step-length consumes 1/10～1/20 of volume of titrant during for titration end-point, at the uniform velocity titration, to terminal point occur, titration curve very mild after, stop titration, get last hop terminal point;
The 4th step consumed 1/10～1/20 of volume of titrant when seeing the titration step-length whether for titration end-point according to test result, if not, adjust the titration step-length and repeated for the 3rd step; Replicate determination as a result 3 times is averaged.
Embodiment three
The first step selects for use dry good 10mlPE material syringe to get the 8ml lithium-ion battery electrolytes in glove box, and the syringe needle silica gel sealing is transferred to syringe in the air; Lithium-ion battery electrolytes is by PC, carbonic acid and methyl esters (DMC), tetrahydrofuran (THF) and LiN (CF
3SO
2)
2Mix and form wherein PC: DMC: THF=2: 3: 1 (w), the concentration of lithium salts is 1mol/L;
Second step added 50.0ml absolute ethyl alcohol (need not dried, water cut 0.2%) with transfer pipet in titration cup, add 3 gram electrolytic solution (weigh with scale and inject the amount of electrolytic solution, be accurate to 0.1mg), started and stirred;
It is that the lithium hydroxide of 0.1000mol/L is a titrant that the 3rd step was selected concentration for use, and the beginning titration is input in the potentiometric titrimeter input second order differentiate program (Switzerland Metrohm company provides) and acidity computing formula (C with the consumption of electrolytic solution
0* V20)/(1000 * m), wherein, C
0Be the concentration mol/L of titrant, V is for consuming the volume ml of titrant, and 20 is the molecular weight of HF, and m is the weight g of electrolytic solution; Adjust the titration step-length according to hydrofluoric content in the electrolytic solution, the titration step-length consumes 1/10～1/20 of volume of titrant during for titration end-point, at the uniform velocity titration, to terminal point occur, titration curve very mild after, stop titration, get last hop terminal point;
The 4th step consumed 1/10～1/20 of volume of titrant when seeing the titration step-length whether for titration end-point according to test result, if not, adjust the titration step-length and repeated for the 3rd step; Replicate determination as a result 3 times is averaged.
Embodiment four
For further specifying the present invention, present embodiment adopts the mode that compares with the prior art indicator method to carry out:
The indicator method of contrast: adopt dry good 10mlPE material syringe in glove box, to get 8ml electrolytic solution, the syringe needle silica gel sealing, in titration cup, add 50ml absolute ethyl alcohol and 4～5 BTB with transfer pipet, add electrolytic solution 3～4 grams (being accurate to 0.1mg), mix, shake, up to solution turned blue while dripping, write down the use amount of titrant, replicate determination 3 times.
The following lithium-ion battery electrolytes of preparation in glove box, but be not limited to following prescription:
A, EC: DMC: EMC=1: 1: 1 (w), LiPF
6: 1mol/L (this expression way could)
B, EC: DMC: EMC=1: 1: 1 (w), LiPF
6: 1mol/L adds stabilizing agent N0.1% (w)
C, in A, add minor amount of water, make the about 100ppm of its moisture, and sealing places 45 ℃ after following 24 hours, add stabilizing agent N0.5% (w)
D, EC: PC: DMC: EMC=2: 1: 2: 3 (w), LiPF
6: 1mol/L adds stabilizing agent N1% (w).
In glove box with the ethanolic solution of the ethanolic solution of 0.1mol/L NaOH and potassium hydroxide with the dry ethanol (H that crosses
2O＜20ppm) dilute 10 times, 0.1mol/L tetrabutylammonium aqueous isopropanol dilutes 10 times with methyl alcohol, the methanol solution of the sodium methoxide of preparation 0.01mol/L.Four kinds of solution are demarcated with the benchmark benzoic acid.
The contrast of method of testing: employing KOH is a titrant, and absolute ethyl alcohol is a solvent, replicate determination electrolytic solution B, C each three times, a kind of employing potentiometric titration, the another kind of indicator method that adopts.
The contrast of titrant and solvent: in absolute ethyl alcohol that drying is crossed and methyl alcohol, measure electrolytic solution A respectively with four kinds of titrant: in glove box with the about 6ml sample of syringe of 10ml, with silica gel syringe is sealed, at indoor measurement, each about 2.5g of sample that annotates, replicate determination three times, method of testing are potentiometric titration.Contrast titrant and solvent are to the influence of measurement result.
Employing KOH is a titrant, and (liquid water content～2000ppm) (liquid water content～10ppm) measure electrolytic solution A and D compares the influence of the existence of trace water to test result with the further dry absolute ethyl alcohol of crossing at absolute ethyl alcohol respectively.
The measurement result of hydrofluorite:
(1) concentration calibration of titrant
Concentration (the unit: mol/L) of four kinds of titrant of table 1
| Titrant | 1 | 2 | 3 | Average result |
| NBu 4OH | 0.0098 | 0.0010 | 0.0098 | 0.0099 |
| NaOCH 3 | 0.0097 | 0.0099 | 0.0098 | 0.0098 |
| NaOH | 0.0101 | 0.0102 | 0.0101 | 0.0101 |
| KOH | 0.0102 | 0.0103 | 0.0102 | 0.0102 |
(2) comparison of method of testing
In commercial Application, in order to improve the stability of electrolytic solution, generally all can add a certain amount of lewis base (for example organic amine) used as stabilizers, make electrolytic solution near neutrality or meta-alkalescence (pH
0Therefore 7～9), and prior art is not all considered this problem, adopts terminal point pH that to measure appear in prior art probably not in the color change interval of indicator, bigger error will occur like this, if the alkalescence of stabilizing agent is strong or content is high, the pH of electrolytic solution
0Just bigger, result's deviation may be bigger like this.
Table 2 is that the present invention's (automatic potentiometric titration) compares with prior art (indicator method) test electrolytic solution A and B result, and table 3 is that the electric result of two kinds of methods test electrolytic solution C compares, wherein pH
zPH value when being the test terminal point, titrant is KOH, solvent is undried ethanol, replicate determination 3 times.
Table 2 stabilizing agent is to the influence of hydrofluorite quantitative test
| The electrolytic solution sample | pH 0 | m 1(ppm) | pH Z1 | m 2(ppm) | pH Z2 | (M 2-M 1)/ M 2×100％ |
| A | 5.4 | 13.9 | 6.3 | 15.0 | 6.7 | 8.5 |
| 14.5 | 6.5 | 15.6 | 6.9 | |||
| 14.3 | 6.4 | 16.1 | 6.7 | |||
| B | 6.8 | 14.0 | 7.2 | 16.3 | 7.5 | 8.8 |
| 14.2 | 7.1 | 15.9 | 7.6 | |||
| 15.0 | 7.2 | 15.3 | 7.5 |
Annotate: m
1Be the result of indicator method test, M
1Be its mean value, m
2Be the potentiometric titration test result, M
2Be its mean value.
The result of the electrolytic solution of two kinds of method tests of table 3 electrolytic solution C
| pH 0 | m 1(ppm) | pH Z1 | m 2(ppm) | pH Z2 | (M 2-M 1)/M 2×100％ |
| 7.2 | 259.7 230.4 249.7 | 7.6 7.5 7.6 | 305.6 298.9 300.3 | 7.9 7.8 7.9 | 18.2 |
Annotate: m
1Be the result of indicator method test, M
1Be its mean value, m
2Be the potentiometric titration test result, M
2Be its mean value.
Can find out that from the data of table 2 stabilizing agent adds the back to the almost not influence of electrolytic solution total acidity, has just improved the pH value of electrolytic solution.The result that the data analysis of associative list 3, indicator method are measured is less than normal than the result of potentiometric determination, in low (this deviation less (8.5%) in＜30ppm) the electrolytic solution of acidity content; Add in the electrolytic solution behind the stabilizing agent result of two kinds of method tests differ increase big, particularly acidity big (＞50ppm), the result that tests in the electrolytic solution of stabiliser content higher (〉=0.5) just differs very obviously (18.2%), and the degree of accuracy as a result of indicator method test is very poor, illustrates that indicator method has not been suitable for the test of acidity in the present electrolyte system this moment.
(3) comparative analysis of titrant and solvent
Table 4 is respectively in methyl alcohol and ethanol, adopts the result of 3 parallel testings of tetrabutylammonium, NaOH, potassium hydroxide and four kinds of titrant tests of sodium methoxide electrolytic solution A, and method of testing is an automatic potentiometric titration.As shown in Figure 1, the titration jump in ethanol B is than obvious (a, tetrabutylammonium, b, NaOH, c, potassium hydroxide, d, sodium methoxide) in methyl alcohol A.The data of table 4 show that the degree of accuracy of KOH is best in four kinds of titrant.Tetrabutylammonium is that the result of titrant test is big than the result of other three kinds of titrant tests.The hop of sodium methoxide is very smooth, brings difficulty for the selection of hop terminal point.The degree of accuracy of test result that with KOH is titrant is best, no matter be to make solvent with methyl alcohol or with ethanol, its standard deviation is all less than 1%.
The different titrant of table 4 are the test result (unit: ppm) in methyl alcohol and ethanol respectively
| Titrant | Tetrabutylammonium | NaOH | Potassium hydroxide | Sodium methoxide | |
| Methyl alcohol | Measured value | 28.3，27.7，27.0 | 16.8，21.8，12.4 | 14.4，16.3，15.8 | 15.2，11.0，16.9 |
| Standard deviation S (%) | 0.65 | 4.70 | 0.98 | 3.04 | |
| Ethanol | Measured value | 22.8，18.6，16.9 | 16.5，16.9，17.3 | 11.7，11.3，12.0 | 16.6，18.0，15.1 |
| Standard deviation S (%) | 3.04 | 0.40 | 0.35 | 1.45 | |
(4) micro-moisture is to the influence of test result
Ethanol is handled by molecular sieve drying in the prior art, present embodiment carries out dried with the 3A molecular sieve to ethanol, test as solvent with the ethanol before and after dry respectively, the electrolytic solution of test is A (figure A) and D (figure B), table 5 is test results, the result who shows the ethanol test of dry front and back is more or less the same, and the degree of accuracy of doing the solvent test result with the ethanol of undried is also better.As shown in Figure 2, curve a is to ethanol (H
2O:2171.6ppm) test titration curve; Curve b is to ethanol (H
2O:23.6ppm) test titration curve.As can be seen, the hop of titration curve precipitous than in dried ethanol in undried ethanol, the data of table 5 show that the result who records is accurately also higher in undried ethanol.Can analyze from this result, the micro-moisture of analyzing in the straight alcohol (0.15～0.2%) can be ignored the influence of test result, and experimental result shows that having of these moisture is beneficial to the judgement of terminal point.
Table 5 aqueous solvent content is to the influence of hydrofluorite quantitative test
| Water cut (ppm) | Electrolytic solution | Acidity (ppm) | RSD(％) |
| 2171.6 | A | 15.0，13.0，13.6 | 1.03 |
| D | 115.3，117.1，114.4 | 1.37 | |
| 23.6 | A | 15.2，13.2，14.5 | 1.01 |
| D | 114.0，118.3，116.7 | 2.17 |
As mentioned above, can realize the present invention preferably.
Claims (7)
1. the quantitative analysis method of hydrofluorite in the lithium-ion battery electrolytes, it is characterized in that, with lithium-ion battery electrolytes by the dilution proportion that adds 2.5～3.0g in every 50ml solvent in need not the solvent absolute methanol or absolute ethyl alcohol of dried, and be titrant with alkali-metal oxyhydroxide, adopt automatic potentiometric titration to measure titration curve, utilize potentiometric titrimeter that titration curve is carried out the second order differentiate, thereby determine titration end-point; Utilize formula (C
0* V20)/(1000 * m) calculate end point values, wherein C
0Be the concentration mol/L of titrant, V is for consuming the volume ml of titrant, and 20 is the molecular weight of HF, and m is the weight g of electrolytic solution.
2. the quantitative analysis method of hydrofluorite is characterized in that in a kind of lithium-ion battery electrolytes according to claim 1, and the alkaline metal in the described alkali-metal oxyhydroxide comprises lithium, sodium or potassium.
3. the quantitative analysis method of hydrofluorite is characterized in that in a kind of lithium-ion battery electrolytes according to claim 1, and described titrant is KOH.
4. the quantitative analysis method of hydrofluorite is characterized in that in a kind of lithium-ion battery electrolytes according to claim 1, and described titrant concentration is 0.0100mol/L～0.1000mol/L.
5. the quantitative analysis method of hydrofluorite is characterized in that in a kind of lithium-ion battery electrolytes according to claim 1, and described solvent is absolute ethyl alcohol or the absolute methanol that undried is handled, water cut 0.15～0.2%.
6. the quantitative analysis method of hydrofluorite is characterized in that in a kind of lithium-ion battery electrolytes according to claim 1, described solvent be need not dried absolute ethyl alcohol, water cut 0.15～0.2%.
7. the quantitative analysis method of hydrofluorite in a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that, described electrolytic solution comprises organic solvent and lithium salts two parts composition, described organic solvent comprises one or more mixed solvents in ethylene carbonate, carbonic allyl ester, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, dimethoxy-ethane, the tetrahydrofuran, and described lithium salts comprises LiCF
3SO
3, LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiN (CF
3SO
2)
2In one or more potpourris.
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| CN110501453A (en) * | 2019-08-16 | 2019-11-26 | 武汉工程大学 | The method for analyzing measurement technical grade cis-propene phosphoric acid content using pH meter |
| CN111855650A (en) * | 2020-07-30 | 2020-10-30 | 青岛科技大学 | Method for determining content of fluosilicic acid, hydrofluoric acid and nitric acid in etching acid |
| CN112083121A (en) * | 2020-09-24 | 2020-12-15 | 国联汽车动力电池研究院有限责任公司 | Method for measuring content of free acid in lithium ion battery electrolyte |
| CN114054110B (en) * | 2021-11-17 | 2022-10-11 | 芜湖天弋能源科技有限公司 | Kit and method for testing HF content in electrolyte |
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| CN1283315A (en) * | 1997-12-26 | 2001-02-07 | 东燃珍宝石油株式会社 | Electrolyte for lithium cells and method of producing the same |
| CN1378296A (en) * | 2001-03-27 | 2002-11-06 | 日本电气株式会社 | Anode for secondary battery and secondary battery with such anode |
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