CN106353383A - Sensor for detecting hexafluorophosphate ions - Google Patents
Sensor for detecting hexafluorophosphate ions Download PDFInfo
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- CN106353383A CN106353383A CN201610884861.XA CN201610884861A CN106353383A CN 106353383 A CN106353383 A CN 106353383A CN 201610884861 A CN201610884861 A CN 201610884861A CN 106353383 A CN106353383 A CN 106353383A
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- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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Abstract
The invention provides a method for quantitating content of lithium hexafluorophosphate by detecting hexafluorophosphate radicals. The method is characterized in that a glassy carbon electrode serves as a working electrode, a platinum filament serves as a counter electrode, an Ag/AgCl electrode serves as a reference electrode, electrochemical polymerization is performed in aqueous solutions of 0.01-0.2mol/L pyrrole and 1.0*10<3>-0.1mol/L lithium hexafluorophosphate for 10-60 minutes, a polypyrrole film (PF6<->-PPY/GC) doped with hexafluorophosphate ions is electrically deposited on a surface of the glassy carbon electrode in a current density range of 1-15mA/cm<2>, and the modified electrode is put in 0.1mol/L lithium hexafluorophosphate aqueous solution for immersion for 1 hour to obtain a high-sensitive electrochemical sensor for detecting the hexafluorophosphate ions. The modified electrode (PF6<->-PPy/GC) serving as the working electrode and the Ag/AgCl electrode serving as the reference electrode are put in the lithium hexafluorophosphate aqueous solution, the modified electrode (PF6<->-PPy/GC) exhibits a good linear relationship in 1.0*10<-1>-1.0*10<-5>mol/L lithium hexafluorophosphate aqueous solution, and the slope rate is close to 59.4mV/PF6<->.
Description
Technical field
The present invention relates to the detection method of the raw material lithium hexafluoro phosphate purity of electrolyte for lithium ion battery is and in particular to one
Plant using the polypyrrole modifying glass-carbon electrode of hexafluorophosphoricacid acid ions of adulterating as working electrode, by the measurement of current potential, detect six
The electrochemical detection method of lithium fluophosphate.
Background technology
Lithium ion battery is a focus of current research.It has obviously superior compared with traditional battery
Property.Because its voltage is high and negative material is more active, so nonaqueous electrolyte must be used, but the leading of common organic solvent
Electrically limited it is impossible to meet lithium ion battery needs it is necessary to wherein dissolving lithium salts can be only achieved required electrical conductivity.Logical
The lithium salts often using mainly has lipf6、liasf6、liclo4、libf4And licf3so3Deng.In these lithium salts, lipf6Electricity
Conductance highest, by suitable process, is avoided that it decomposes the electrolyte polymerization causing.So current lithium ion battery is substantially
It is to use lipf6For electrolyte.In common lithium ion battery, hexafluoro-phosphate radical is the main component in its electrolyte, fluorine
Ion, phosphate anion are then wherein main foreign ions.And three's hybrid ionic commonsense method is often difficult to separate survey
Fixed, therefore explore the method simultaneously measuring its content in the case that three coexists, for studying lithium ion battery further
The performance of reaction mechanism and improvement lithium-ions battery has great importance.The method that tradition measures hexafluoro-phosphate radical is to adopt
With microtitrimetry, chromatography of ions etc., but these methods cannot meet the requirement of high-purity hexafluoro-phosphate radical analysis.
Content of the invention
The invention aims to solving to detect the purity of lithium hexafluoro phosphate or detection lithium-ion battery electrolytes at present
The method complex operation of middle hexafluorophosphoric acid lithium content, the harsh and relatively costly problem of experimental operating conditions, there is provided Yi Zhongjian
Survey the sensor of lithium hexafluoro phosphate, for detecting that in the purity of lithium hexafluoro phosphate or lithium-ion battery electrolytes, lithium hexafluoro phosphate contains
The electrochemical detection method of amount, the method has that sensitivity is high, easy to operate, analyze speed fast, low cost and other advantages, is capable of
Simply and rapidly detect.
In order to solve the above problems, the technical solution used in the present invention is: a kind of electrification of detection hexafluorophosphoric acid lithium content
Method, its feature comprises the following steps:
(1) preparation of deposition solution
Deionized water compound concentration is pyrroles and the 1.0x10 of 0.01～0.2mol/l-3The hexafluorophosphoric acid of～0.1mol/l
The aqueous solution of lithium is as the electric depositing solution of the present invention.
(2) sensor (pf6 -- ppy/gc) preparation
With glass-carbon electrode as working electrode, it is to electrode with platinum filament, ag/agcl electrode is reference electrode, will process clean
Glass-carbon electrode be respectively placed in pyrroles described in step (1) and the electric depositing solution of lithium hexafluoro phosphate aqueous solution, using permanent electricity
Stream method carries out electro-deposition, and electric current density is 1～15ma/cm2, the electropolymerization time is 10～60min, heavy in glassy carbon electrode surface electricity
Long-pending polypyrrole film (the pf doped with hexafluorophosphoricacid acid ions6 -- ppy/gc), the electrode modified through electro-deposition is placed in
Soak 1h in the lithium hexafluoro phosphate aqueous solution of 0.1mol/l, that is, obtain highly sensitive hexafluorophosphoricacid acid ions electrochemical sensor
(pf6 --ppy/gc).
(3) drafting of standard curve
Sensor (the pf being obtained in step (2)6 -- ppy/gc) as working electrode, ag/agcl electrode is as reference electricity
Pole is placed in the aqueous solution of lithium hexafluoro phosphate, carries out potential measurement, with the negative logarithm of hexafluorophosphoricacid acid ions concentration as abscissa,
Standard curve, sensor (pf are drawn for vertical coordinate with the corresponding potential value of concentration6 -- ppy/gc) the six of a series of variable concentrations
With corresponding potential value in good linear relationship, the nearly 59.4mv/pf of slope in lithium fluophosphate aqueous solution6 -.
(4) mensure of sample
Take the testing sample solution handled well, tested according to the potential measurement method in step (3), by the sound obtaining
Potential value is answered to be brought into the corresponding abscissa of standard curve that step (3) obtains, you can to obtain the concentration of lithium hexafluoro phosphate.
As limitation of the invention, the processing method of the glass-carbon electrode described in step (2) is: with the glass of a diameter of 4mm
Carbon electrode is basal electrode, respectively in the al of 0.5 μm and 0.3 μm2o3After being polished into minute surface on polishing powder, use 1:1 nitric acid successively,
Ethanol and deionized water supersound washing 3min.
A series of variable concentrations standard solution described in step (3) refer to that concentration is 1.0x10-1～1.0x10-5mol/l
Lithium hexafluoro phosphate aqueous solution, respectively 1.0x10-5mol/l、1.0×10-4mol/l、1.0×10-3mol/l、1.0×10- 2Mol/l and 1.0 × 10-1mol/l.
Potentiometric measurement described in step (3), test condition is as follows: reference electrode is ag/agcl, in tisab solution
Measure, the compound method of tisab solution is, take glacial acetic acid, 58g nacl and the 4g sodium citrate of 57ml to add water 500ml,
Adjusting ph with the naoh of 5mol/l is 5～5.5, obtains final product tisab solution.
Testing sample described in step (4) is processed by the following method: takes a certain amount of sample, is settled to 50ml, uses 0.45 μ
M membrane filtration, filtrate is standby, and potential measurement value should be located at 1.0x10-1～1.0x10-5Between mol/l.
After technique scheme, the invention has the advantages that
(1) present invention selects to be affected less pyrroles for monomer by ph value, formed in electro-deposition polymerization process doped with
The polypyrrole film of hexafluorophosphoricacid acid ions, polypyrrole film carries out Selective recognition to hexafluorophosphoricacid acid ions, thus forming current potential
Response, obtains the glass-carbon electrode modified doped with the polypyrrole film of hexafluorophosphoricacid acid ions, and the preparation process of this electrode is simple, will
The glass-carbon electrode modified as working electrode, its stable performance, and there is good repeatability.
(2) glass-carbon electrode modified using the polypyrrole film doped with hexafluorophosphoricacid acid ions can be to hexafluorophosphoricacid acid ions
Carry out Direct Electrochemistry detection it is achieved that the quick detection of lithium hexafluoro phosphate is so that the detection process of each sample only needs rather
Clock can complete, and testing cost is low.
(3) the high sensitivity hexafluorophosphoricacid acid ions electrochemical sensor of present invention preparation, modified electrode (pf6 --ppy/
Gc) in 1.0x10-1～1.0x10-5It is in good linear relationship in the lithium hexafluoro phosphate aqueous solution of mol/l, the nearly 59.4mv/ of slope
pf6 -.
Brief description
Fig. 1 modified electrode (pf6 -- ppy/gc) potential response under different hexafluorophosphoric acid lithium concentrations.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
In order to be illustrated more clearly that present disclosure, presently in connection with accompanying drawing and following examples, the present invention is made further
Detailed description, but it is noted that, these embodiments only illustrate and are used, and are not necessarily to be construed as the present invention is implemented
Restriction.
(1) used in experimentation, water is deionized water, and experiment reagent used is that analysis is pure, and experiment is all in room
Carry out under temperature.
(2) the present embodiment is used instrument and reagent:
Electrochemical workstation chi660d (Shanghai Chen Hua instrument company) is used for the reality of constant current electro-deposition and potential measurement
Test.Three-electrode system: working electrode is the polypyrrole modifying glass-carbon electrode modified doped with hexafluorophosphoricacid acid ions, reference electrode
For ag/agcl electrode, it is platinum electrode to electrode.
Hexafluorophosphoric acid lithium concentration according in following steps determination sample:
(1) preparation of deposition solution
Deionized water compound concentration is the aqueous solution conduct of the lithium hexafluoro phosphate of the pyrroles of 0.1mol/l and 0.01mol/l
The electric depositing solution of the present invention.
(2) preparation of high sensitivity lithium hexafluoro phosphate sensor
With the glass-carbon electrode of a diameter of 4mm as basal electrode, respectively in the al of 0.5 μm and 0.3 μm2o3Polish on polishing powder
After becoming minute surface, use 1:1 nitric acid, ethanol and deionized water supersound washing 3min successively.
Will be ultrasonic for the deposition solution of preparation in step 1 uniform, it is heavy that the above-mentioned glass-carbon electrode handled well is respectively placed in
In long-pending solution, electro-deposition is carried out using galvanostatic method, electric current density is 10ma/cm2, the electropolymerization time is 10min, in glass carbon electricity
Pole surface doping has the polypyrrole film (pf of hexafluorophosphoricacid acid ions6 -- ppy/gc), it is placed in 0.1mol/l's after electro-deposition
Soak 1h in lithium hexafluoro phosphate aqueous solution, obtain final product modified electrode (pf6 -- ppy/gc), thus the electrification of this lithium hexafluoro phosphate is obtained
Learn sensor.
(3) test experience
Test experience is to carry out on chi660d electrochemical workstation, and reference electrode is ag/agcl electrode, working electrode
The modified glassy carbon electrode prepared using step of the present invention (2), supporting electrolyte is tisab solution, measures different hexafluoro phosphorus respectively
Potential value under acid ion concentration, with the negative logarithm of hexafluorophosphoricacid acid ions concentration as abscissa, with the corresponding current potential of concentration
It is worth for vertical coordinate, you can obtain the standard curve of lithium hexafluoro phosphate, as shown in figure 1, wherein, the concentration of lithium hexafluoro phosphate is respectively
1.0x10-5mol/l、1.0×10-4mol/l、1.0×10-3mol/l、1.0×10-2Mol/l and 1.0 × 10-1mol/l.This six
The range of linearity of lithium fluophosphate electrochemical sensor is 1.0x10-1～1.0x10-5Mol/l mol/l, the nearly 59.4mv/ of slope
pf6 -.
(4) mensure of testing sample
10 μ l are taken to contain the sample of lithium hexafluoro phosphate, in tisab supporting electrolyte, according to the detection test in step (3)
Method and step carry out electro-chemical test, and to obtain current potential, gained potential value, according to step (3) gained standard curve, calculates
The concentration of lithium hexafluoro phosphate in institute's test sample product.Sample is carried out with mark-on reclaims, calculates recovery of standard addition, its result is as shown in table 1.
Table 1 contains the sample mark-on reclaims measurement result of lithium hexafluoro phosphate
aMeansigma methodss for three mensure；Rsd refers to: relative standard deviation
The relative standard deviation that each sample parallel assay is 3 times is below 5%, and essence during the inventive method practical measurement is described
Density is good；Recovery of standard addition 96%～102%, illustrates that the method has good accuracy.
Based on above-mentioned test result it can be seen that the method for Electrochemical Detection lithium hexafluoro phosphate of the present invention is simple to operate, side
Just quick, testing cost is low, is simultaneously achieved the electrochemical method to lithium hexafluoro phosphate direct detection.Above-described embodiment is only used for
Present disclosure is described, but this is not limitation of the present invention.
Claims (5)
1. a kind of detection lithium hexafluoro phosphate electrochemical method it is characterised in that: described detection method comprises the following steps:
(1) preparation of deposition solution
Deionized water compound concentration is pyrroles and the 1.0x10 of 0.01～0.2mol/l-3The lithium hexafluoro phosphate of～0.1mol/l
Aqueous solution is as electric depositing solution；
(2) sensor (pf6 -- ppy/gc) preparation
With glass-carbon electrode as working electrode, it is to electrode with platinum filament, ag/agcl electrode is reference electrode, clean glass will be processed
Carbon electrode is respectively placed in pyrroles described in step (1) and the electric depositing solution of lithium hexafluoro phosphate aqueous solution, using galvanostatic method
Carry out electro-deposition, electric current density is 1～15ma/cm2, the electropolymerization time is 10～60min, mixes in glassy carbon electrode surface electro-deposition
Miscellaneous polypyrrole film (the pf having hexafluorophosphoricacid acid ions6 -- ppy/gc), the electrode modified through electro-deposition is placed in 0.1mol/l's
Soak 1h in lithium hexafluoro phosphate aqueous solution, that is, obtain highly sensitive hexafluorophosphoricacid acid ions electrochemical sensor (pf6 --ppy/
gc)；
(3) drafting of standard curve
Sensor (the pf being obtained in step (2)6 -- ppy/gc) as working electrode, ag/agcl electrode is put as reference electrode
In the aqueous solution of lithium hexafluoro phosphate, carry out potential measurement, with the negative logarithm of hexafluorophosphoricacid acid ions concentration as abscissa, with dense
Spending corresponding potential value is vertical coordinate, draws standard curve, sensor (pf6 -- ppy/gc) a series of variable concentrations hexafluoro
It is in good linear relationship in lithium phosphate aqueous solution, slope is 59.4mv/pf6 -；
(4) mensure of sample
Take the testing sample solution handled well, tested according to the potential measurement method in step (3), by the response obtaining electricity
Place value is brought into the corresponding abscissa of standard curve that step (3) obtains, you can obtain the concentration of lithium hexafluoro phosphate.
2. as claimed in claim 1 detection lithium hexafluoro phosphate electrochemical method it is characterised in that: the described glass carbon of step (2)
The processing method of electrode is: with the glass-carbon electrode of a diameter of 4mm as basal electrode, respectively in the al of 0.5 μm and 0.3 μm2o3Polishing
After being polished into minute surface on powder, use 1:1 nitric acid, ethanol and deionized water supersound washing 3min successively.
3. as claimed in claim 1 detection lithium hexafluoro phosphate electrochemical method it is characterised in that: described in step (3)
The concentration of the lithium hexafluoro phosphate aqueous solution of serial variable concentrations is respectively 1.0x10-5mol/l、1.0×10-4mol/l、1.0×10-3mol/l、1.0×10-2Mol/l and 1.0 × 10-1mol/l.
4. as claimed in claim 1 detection lithium hexafluoro phosphate electrochemical method it is characterised in that: the electricity described in step (3)
Position measurement method, test condition is as follows: reference electrode is ag/agcl, measures in tisab solution, wherein, tisab solution
Compound method be to take glacial acetic acid, 58g nacl and the 4g sodium citrate of 57ml to add water 500ml, adjusted with the naoh of 5mol/l
Ph is 5～5.5, obtains final product tisab solution.
5. as claimed in claim 1 detection lithium hexafluoro phosphate electrochemical method it is characterised in that: treating described in step (4)
Test sample product are processed by the following method: take sample to be settled to 50ml, with 0.45 μm of membrane filtration, filtrate is standby, and potential measurement value
1.0x10 should be located at-1～1.0x10-5Between mol/l.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349047A (en) * | 2020-03-03 | 2020-06-30 | 扬州大学 | Carbon paste ion selective electrode and preparation method and application thereof |
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2016
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| CN101858882A (en) * | 2010-03-17 | 2010-10-13 | 江南大学 | Nitrate ion selective electrode based on polypyrrole film and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349047A (en) * | 2020-03-03 | 2020-06-30 | 扬州大学 | Carbon paste ion selective electrode and preparation method and application thereof |
| CN111349047B (en) * | 2020-03-03 | 2022-06-14 | 扬州大学 | Carbon paste ion selective electrode and preparation method and application thereof |
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Address after: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Co-patentee after: Jiangsu Xintai Material Technology Co., Ltd. Patentee after: Changzhou University Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Co-patentee before: JIANGSU XINTAI MATERIALS TECHNOLOGY CO., LTD. Patentee before: Changzhou University |
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