CN102937614A - Method for analyzing content of free fluorin in lithium ion battery electrolyte salt LiBF4 - Google Patents
Method for analyzing content of free fluorin in lithium ion battery electrolyte salt LiBF4 Download PDFInfo
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- CN102937614A CN102937614A CN2012104560018A CN201210456001A CN102937614A CN 102937614 A CN102937614 A CN 102937614A CN 2012104560018 A CN2012104560018 A CN 2012104560018A CN 201210456001 A CN201210456001 A CN 201210456001A CN 102937614 A CN102937614 A CN 102937614A
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Abstract
The invention relates to a method for analyzing the content of free fluorin in lithium ion battery electrolyte salt LiBF4. The method includes steps of: preparing a total ionic strength adjustment buffer; preparing a fluoride ion standard series solution; preparing a sample LiBF4 solution to be tested; preparing a standard curve: a fluoride ion selective electrode and a calomel reference electrode are combined to form an electrode couple which is connected with an ion meter, a power source is started, preheating is performed for 20 minutes to 40 minutes, and a potential value is stabilized at 0.1mV; and potential values of the fluoride ion standard series solution are tested for five times in parallel, the potential values are recorded to obtain an average value, the standard curve is made, and simultaneously, the slope of the curve is obtained; and testing the sample to be tested: the total ionic strength adjustment buffer is added in the sample solution to be tested, the volume of the solution is metered at 50mL, and the solution is tested by the activated electrode couple to obtain a corresponding potential value; and the content of free fluorin in the solution is calculated according to an ion selective electrode membrane potential calculation formula. According to the method, the operation is simple and rapid, and high precision and accuracy are provided.
Description
Technical field
The present invention relates to the analytical chemistry field, relate in particular to a kind of lithium ion battery electrolyte salt LiBF
4the analytical approach of Free Fluoride content.
Background technology
Electrolytic solution plays a part to carry lithium ion between the both positive and negative polarity of lithium ion battery, and selecting suitable electrolytic solution is the key issue that obtains high-energy-density, long circulation life and high security lithium ion battery.
LiBF
4the better heat stability of base electrolyte, not too responsive to ambient moisture, be hopeful to develop into by civilian, military, three boat fields are miniature, the extensive outstanding electrolyte system of employing of energy storage and power lithium-ion battery.In battery industry, the content of free fluorine is weighed an important indicator of electrolyte quality often, for now, and also not about electrolytic salt LiBF
4analyze the national standard of measuring, some enterprises also never announced its industry assay method, and therefore, it is the task of top priority that its analytical approach is carried out to a series of exploration.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of simple to operate and lithium ion battery electrolyte salt LiBF fast and accurately
4the analytical approach of Free Fluoride content.
For addressing the above problem, a kind of lithium ion battery electrolyte salt LiBF of the present invention
4the analytical approach of Free Fluoride content comprises the following steps:
(1) the preparation of total ionic strength adjustment buffer (TISAB): add successively 57mL glacial acetic acid, 58.5gNaCl, 0.3g sodium citrate in the 500mL redistilled water, regulate pH value to 5.0 ~ 5.5 with 5mol/L NaOH solution after mixed dissolution, to be cooledly to diluting after room temperature, be settled to 1000mL and get final product;
(2) the preparation of fluorine ion standard serial solution: dissolve with redistilled water after 4.198g NaF (GR) is dried to constant weight under 105 ~ 106 ℃, and be settled to 1L with redistilled water, make 0.1mol/L NaF solution; Add the described total ionic strength adjustment buffer of 10 ~ 25mL (TISAB) in described 0.1mol/L NaF solution, and add redistilled water and be settled to 100mL, compound concentration is 1 * 10 respectively
-2~ 1 * 10
-6the serial fluorine ion standard solution of mol/L;
(3) treat the preparation of test sample solution: by LiBF
4put into redistilled water and dissolve, then add the described total ionic strength adjustment buffer of 10 ~ 25mL (TISAB), and add redistilled water and be settled to 100mL, compound concentration is 5 * 10
-2~ 5 * 10
-3the LiBF of mol/L
4solution;
(4) the making of typical curve: fluoride ion selective electrode and calomel reference electrode are formed to electrode pair, and this electrode pair and ionometer are connected, and start power supply, and preheating 20 ~ 40min, make potential value be stabilized in 0.1mV; Then by described step (2) the fluorine ion standard serial solution of gained at room temperature by order from thin to thick 5 potential values of replicate determination successively, record potential value and get its mean value, and mapping, the negative logarithm of concentration of take is set up equation of linear regression as horizontal ordinate, potential value as ordinate, when the coefficient R of this equation=0.9999, obtain typical curve, try to achieve this slope of a curve k=57.73 simultaneously;
(5) treat the test of test sample: described step (3) gained treat test sample solution 5 ~ 10mL in add 10 ~ 25mL total ionic strength adjustment buffer (TISAB), and add redistilled water and be settled to 50mL, then adopt the electrode pair activated to test it, obtain corresponding potential value
e f ; Calculate solution Free Fluoride content according to ion-selective electrode film potential computing formula; Wherein ion-selective electrode film potential computing formula is
, k is slope of standard curve;
rfor mol gas constant 8.314J
.mol
-1 .k
-1;
tfor measuring temperature;
ffor Faraday constant 96485.3383 ± 0.0083C/mol;
a f concentration for free fluorine content.
The present invention compared with prior art has the following advantages:
1, the present invention utilizes Fluoride ion selective electrode method to measure content of fluoride ion, and, by Precision Experiment and recovery experiment test, the present invention has higher preci-sion and accuracy.
(1) Precision Experiment:
Get the LiBF that the inventive method prepares
4liquid 5mL to be measured, in the 50mL volumetric flask, adds 12mLTISAB, adds water and is settled to 50mL, prepares 7 parts, and replicate determination 7 times (t=19.4 ℃), according to the gained potential value, is calculated as follows free fluorine percentage composition (referring to table 1):
In formula
w(F - )for the free fluorine percentage composition,
a(F - )for free fluorine concentration,
v(LiBF 4 )by being got liquid LiBF to be measured
4volume,
m (F)for the molal weight of fluorine,
m (LiBF 4 )for LiBF
4quality.
Table 1: the Precision Experiment of free fluorine to be measured
Then calculate standard deviation by following formula,
In formula, n is the mensuration number of times,
xfor free fluorine massfraction mean value,
x i for each free fluorine massfraction of measuring, S is standard deviation;
Standard deviation
; Relative standard deviation is
, precision is good.
(2) recovery experiment:
Get 7 parts of 5mL and treat test sample stoste (approximately 10
-3mol/L), in the 50mL volumetric flask, add respectively 10
-4mol/L standard F
-solution 2mL, 4mL, 6mL, 8mL, 10mL, 12mL, 14mL, respectively add 12.5mLTISAB, adds water and be settled to 50mL, and the sample number consecutively is 1,2,3,4,5,6,7.Fluoride ion selective electrode and mercurous chloride electrode are inserted in test solution, form electrode pair, connect good ionometer, switch on power, open magnetic stirring apparatus, middling speed stirs, and the results are shown in Table 2 to measure current potential (T=21 ℃), and be calculated as follows the recovery: P=(c
2-c
1)/c
3* 100%, in formula, P is recovery c
2for adding free fluorine concentration after standard specimen, c
1for adding mark liquid fluorine concentration, c
3for actual free fluorine dense.
Table 2: the recovery experiment of free fluorine to be measured
From table 2 data, can find out, the recovery, between 97.71% ~ 100%, meets the requirements.
2, because fluoride ion selective electrode is to use LaF
3the monocrystalline thin slice, selectivity is extremely strong, only has iron, aluminium ion to generate complex compound with fluorine, other ion does not affect, and in TISAB, adds sodium citrate can remove its impact.LiBF in measured system
4principal ingredient, and the equal iron-free of involved material and aluminium impurity, therefore only need consider that in body series, the impact of main content ion lithium ion and tetrafluoroborate ion gets final product.According to Li++F
-→ LiF (s) is known, Li in solution
+with F
-reaction generates the LiF white precipitate.Therefore in solution, free Li can not be arranged
+affect F
-mensuration, LiBF in body series
4be principal ingredient, may produce and disturb the mensuration of free fluorine.Take 10.9795gNaBF
4in a clean small beaker, by a small amount of water-soluble solution, proceed to the 100mL volumetric flask, add 25mLTISAB, water is settled to 100mL, this NaBF
4solution concentration is 1mol/L.Pipette 11 part 10
-2mol/L standard F
-each 5.00mL of solution, in the 50mL volumetric flask, adds the NaBF of 0mL, 0.1mL, 0.3mL, 0.5mL, 1mL, 3mL, 5mL, 10mL, 15mL, 20mL, 30mL1mol/L successively
4solution, add 12.5mLTISAB, and water is settled to 50mL.Sample number into spectrum is that 1,2,3,4,5,6,7,8,9,10,11 its potential values of survey are as table 3 (t=18.4 ℃).
Table 3: the impact that the fluoboric acid root is measured free fluorine
Simultaneously as seen from Figure 2, the fluoboric acid root not have interference substantially to the mensuration to free fluorine under the condition that concentration is less than 0.002mol/L that is determined at of free fluorine.Between 0.06mol/L ~ 0.60mol/L, all have a great impact, it between 0.02mol/L ~ 0.20mol/L, is the increase along with amount, potential value reduces, after along with the amount increase, potential value slightly increases, but also the standard electrode potential with this understanding far below fluorine ion reduces again after 0.50mol/L.
3, carry out the analysis of free fluorine content by setting up regression curve due to the present invention, therefore, simple to operate, quick.
The accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
The canonical plotting that Fig. 1 is fluorine mark liquid of the present invention.
Fig. 2 is affect the as a result figure of fluoboric acid root of the present invention on free fluorine mensuration.
Embodiment
A kind of lithium ion battery electrolyte salt LiBF
4the analytical approach of Free Fluoride content comprises the following steps:
(1) the preparation of total ionic strength adjustment buffer (TISAB): add successively 57mL glacial acetic acid, 58.5gNaCl, 0.3g sodium citrate in the 500mL redistilled water, regulate pH value to 5.0 ~ 5.5 with 5mol/L NaOH solution after mixed dissolution, to be cooledly to diluting after room temperature, be settled to 1000mL and get final product.
(2) the preparation of fluorine ion standard serial solution: dissolve with redistilled water after 4.198g NaF (GR) is dried to constant weight under 105 ~ 106 ℃, and be settled to 1L with redistilled water, make 0.1mol/L NaF solution; Add 10 ~ 25mL total ionic strength adjustment buffer (TISAB) in 0.1mol/L NaF solution, and add redistilled water and be settled to 100mL, compound concentration is 1 * 10 respectively
-2~ 1 * 10
-6the serial fluorine ion standard solution of mol/L.
(3) treat the preparation of test sample solution: by LiBF
4put into redistilled water and dissolve, then add 10 ~ 25mL total ionic strength adjustment buffer (TISAB), and add redistilled water and be settled to 100mL, compound concentration is 5 * 10
-2~ 5 * 10
-3the LiBF of mol/L
4solution.
(4) the making of typical curve: fluoride ion selective electrode and calomel reference electrode are formed to electrode pair, and this electrode pair and ionometer are connected, and start power supply, and preheating 20 ~ 40min, make potential value be stabilized in 0.1mV; Then by step (2) the fluorine ion standard serial solution of gained at room temperature by order from thin to thick 5 potential values of replicate determination successively, record potential value and get its mean value, and mapping, the negative logarithm of concentration of take is set up equation of linear regression as horizontal ordinate, potential value as ordinate, when the coefficient R of this equation=0.9999, obtain typical curve (referring to Fig. 1), try to achieve this slope of a curve k=57.73 simultaneously;
(5) treat the test of test sample: step (3) gained treat test sample solution 5 ~ 10mL in add 10 ~ 25mL total ionic strength adjustment buffer (TISAB), and add redistilled water and be settled to 50mL, then adopt the electrode pair activated to test it, obtain corresponding potential value
e f ; Calculate solution Free Fluoride content according to ion-selective electrode film potential computing formula; Wherein ion-selective electrode film potential computing formula is
, k is slope of standard curve;
rfor mol gas constant 8.314J
.mol
-1 .k
-1;
tfor measuring temperature;
ffor Faraday constant 96485.3383 ± 0.0083C/mol;
a f concentration for free fluorine content.
Wherein: ORION/901 type ionometer is provided by U.S. ORION company; PF-1 type fluoride ion selective electrode, 217 type biliquids connect mercurous chloride electrode and are provided by Shanghai Russell Science and Technology Ltd.; AL204-automatical analysis balance is provided by METTLER TOLEDO; Sodium citrate (A.R) is provided by Tianjin chemical reagent three factories; Glacial acetic acid (A.R) is provided by Beijing Chemical Plant; Sodium chloride (A.R) is provided by the Xi'an chemical reagent factory; Sodium fluoride (G.R) is provided by Tianjin Standard Science company limited; LiBF
4by Cathay's Huarong, provided.
Claims (1)
1. a lithium ion battery electrolyte salt LiBF
4the analytical approach of Free Fluoride content comprises the following steps:
(1) the preparation of total ionic strength adjustment buffer: add successively 57mL glacial acetic acid, 58.5gNaCl, 0.3g sodium citrate in the 500mL redistilled water, regulate pH value to 5.0 ~ 5.5 with 5mol/L NaOH solution after mixed dissolution, to be cooledly to diluting after room temperature, be settled to 1000mL and get final product;
(2) the preparation of fluorine ion standard serial solution: dissolve with redistilled water after 4.198g NaF is dried to constant weight under 105 ~ 106 ℃, and be settled to 1L with redistilled water, make 0.1mol/L NaF solution; Add the described total ionic strength adjustment buffer of 10 ~ 25mL in described 0.1mol/L NaF solution, and add redistilled water and be settled to 100mL, compound concentration is 1 * 10 respectively
-2~ 1 * 10
-6the serial fluorine ion standard solution of mol/L;
(3) treat the preparation of test sample solution: by LiBF
4put into redistilled water and dissolve, then add the described total ionic strength adjustment buffer of 10 ~ 25mL, and add redistilled water and be settled to 100mL, compound concentration is 5 * 10
-2~ 5 * 10
-3the LiBF of mol/L
4solution;
(4) the making of typical curve: fluoride ion selective electrode and calomel reference electrode are formed to electrode pair, and this electrode pair and ionometer are connected, and start power supply, and preheating 20 ~ 40min, make potential value be stabilized in 0.1mV; Then by described step (2) the fluorine ion standard serial solution of gained at room temperature by order from thin to thick 5 potential values of replicate determination successively, record potential value and get its mean value, and mapping, the negative logarithm of concentration of take is set up equation of linear regression as horizontal ordinate, potential value as ordinate, when the coefficient R of this equation=0.9999, obtain typical curve, try to achieve this slope of a curve k=57.73 simultaneously;
(5) treat the test of test sample: described step (3) gained treat add 10 ~ 25mL total ionic strength adjustment buffer in test sample solution 5 ~ 10mL, and add redistilled water and be settled to 50mL, then adopt the electrode pair activated to test it, obtain corresponding potential value
e f ; Calculate solution Free Fluoride content according to ion-selective electrode film potential computing formula; Wherein ion-selective electrode film potential computing formula is
, k is slope of standard curve;
rfor mol gas constant 8.314J
.mol
-1 .k
-1;
tfor measuring temperature;
ffor Faraday constant 96485.3383 ± 0.0083C/mol;
a f concentration for free fluorine content.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104569112A (en) * | 2015-01-06 | 2015-04-29 | 安徽科微智能科技有限公司 | Continuous on-line water ion concentration detection method based on ion selective electrode |
| CN107271530A (en) * | 2017-07-17 | 2017-10-20 | 云南云天化股份有限公司 | A kind of method of Oil repellent in fluorine-containing organic solvent of Accurate Determining |
| CN108469462A (en) * | 2018-01-22 | 2018-08-31 | 中国农业大学 | A kind of ion flow velocity and cell membrane potential synchronously obtaining device and method |
| CN111751243A (en) * | 2020-06-24 | 2020-10-09 | 东莞东阳光科研发有限公司 | Method for detecting content of fluorine ions in tetrafluoroborate |
| CN114280117A (en) * | 2021-12-29 | 2022-04-05 | 中美华世通生物医药科技(武汉)股份有限公司 | Method for measuring free fluorine content in 2-methyl fluoroacrylate-pentaerythritol triallyl ether copolymer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104569112A (en) * | 2015-01-06 | 2015-04-29 | 安徽科微智能科技有限公司 | Continuous on-line water ion concentration detection method based on ion selective electrode |
| CN107271530A (en) * | 2017-07-17 | 2017-10-20 | 云南云天化股份有限公司 | A kind of method of Oil repellent in fluorine-containing organic solvent of Accurate Determining |
| CN108469462A (en) * | 2018-01-22 | 2018-08-31 | 中国农业大学 | A kind of ion flow velocity and cell membrane potential synchronously obtaining device and method |
| CN111751243A (en) * | 2020-06-24 | 2020-10-09 | 东莞东阳光科研发有限公司 | Method for detecting content of fluorine ions in tetrafluoroborate |
| CN114280117A (en) * | 2021-12-29 | 2022-04-05 | 中美华世通生物医药科技(武汉)股份有限公司 | Method for measuring free fluorine content in 2-methyl fluoroacrylate-pentaerythritol triallyl ether copolymer |
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Application publication date: 20130220 |