CN106353383B - A kind of sensor detecting hexafluorophosphoricacid acid ions - Google Patents
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Abstract
The present invention provides a kind of methods for quantifying hexafluorophosphoric acid lithium content by detection hexafluoro-phosphate radical, i.e. using glass-carbon electrode as working electrode, it is to electrode with platinum filament, Ag/AgCl electrode is reference electrode, is respectively the pyrroles and 1.0x10 of 0.01~0.2mol/L in concentration using galvanostatic method‑310~60min of electropolymerization in the aqueous solution of the lithium hexafluoro phosphate of~0.1mol/L, 1~15mA/cm of current density2In range, there is the polypyrrole film (PF of hexafluorophosphoricacid acid ions in glassy carbon electrode surface doping6 ‑- PPy/GC), which is placed in the lithium hexafluoro phosphate aqueous solution of 0.1mol/L and impregnates 1h to get highly sensitive hexafluorophosphoricacid acid ions electrochemical sensor is arrived.By modified electrode (PF6 ‑- PPy/GC) it is placed in the aqueous solution of lithium hexafluoro phosphate as working electrode and Ag/AgCl electrode as reference electrode, modified electrode (PF6 ‑- PPy/GC) concentration be 1.0x10‑1~1.0x10‑5It is in good linear relationship, the nearly 59.4mV/PF of slope in the aqueous solution of mol/L lithium hexafluoro phosphate6 ‑。
Description
Technical field
The present invention relates to the detection methods of the raw material lithium hexafluoro phosphate purity of electrolyte for lithium ion battery, and in particular to one
Polypyrrole modifying glass-carbon electrode of the kind to adulterate hexafluorophosphoricacid acid ions passes through the measurement of current potential, detection six as working electrode
The electrochemical detection method of lithium fluophosphate.
Background technique
Lithium ion battery is the hot spot studied at present.It has obviously superior compared with traditional battery
Property.Since its voltage is high and negative electrode material is more active, so nonaqueous electrolyte must be used, but common organic solvent is led
It is electrically limited, it is not able to satisfy the needs of lithium ion battery, it is necessary to can be only achieved required conductivity in wherein dissolution lithium salts.It is logical
The lithium salts being often used mainly has LiPF6、LiAsF6、LiClO4、LiBF4And LiCF3SO3Deng.In these lithium salts, LiPF6Electricity
Conductance highest is avoided that it decomposes caused electrolyte polymerization by processing appropriate.So current lithium ion battery is substantially
It is using 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 is often difficult to separate survey with commonsense method
It is fixed, therefore the method in the case where three coexists while measuring its content is explored, for further studying lithium ion battery
Reaction mechanism and the performance for improving lithium-ions battery have great importance.The method of tradition measurement hexafluoro-phosphate radical is to adopt
With microtitrimetry, the chromatography of ions etc., but these methods are unable to satisfy the requirement of high-purity hexafluoro-phosphate radical analysis.
Summary of the invention
The purpose of the present invention is to solve the purity of current detection lithium hexafluoro phosphate or detection lithium-ion battery electrolytes
The problem of method of middle hexafluorophosphoric acid lithium content is complicated for operation, experimental operating conditions harshness and higher cost, provides a kind of inspection
The sensor of lithium hexafluoro phosphate is surveyed, lithium hexafluoro phosphate contains in the purity or lithium-ion battery electrolytes for detecting lithium hexafluoro phosphate
The electrochemical detection method of amount, this method have many advantages, such as that high sensitivity, easy to operate, analysis speed is fast, at low cost, can be realized
Simply and rapidly detect.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that: it is a kind of detect hexafluorophosphoric acid lithium content electrification
Method, feature the following steps are included:
(1) preparation of deposition solution
The pyrroles and 1.0x10 for being 0.01~0.2mol/L with deionized water compound concentration-3The hexafluorophosphoric acid of~0.1mol/L
The aqueous solution of lithium is as electric depositing solution of the invention.
(2) sensor (PF6 -- PPy/GC) preparation
It is to electrode with platinum filament, Ag/AgCl electrode is reference electrode, and processing is clean using glass-carbon electrode as working electrode
Glass-carbon electrode be respectively placed in the electric depositing solution of pyrroles described in step (1) and lithium hexafluoro phosphate aqueous solution, using permanent electricity
Stream method carries out electro-deposition, and current density is 1~15mA/cm2, the electropolymerization time is 10~60min, heavy in glassy carbon electrode surface electricity
Polypyrrole film (PF of the product doped with hexafluorophosphoricacid acid ions6 -- PPy/GC), it will be placed in by the electrode of electro-deposition modification
1h is impregnated in the lithium hexafluoro phosphate aqueous solution of 0.1mol/L to get highly sensitive hexafluorophosphoricacid acid ions electrochemical sensor is arrived
(PF6 --PPy/GC)。
(3) drafting of standard curve
By sensor (PF obtained in step (2)6 -- PPy/GC) it is used 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, using the negative logarithm of hexafluorophosphoricacid acid ions concentration as abscissa,
Standard curve, sensor (PF are drawn by ordinate of the corresponding potential value of concentration6 -- PPy/GC) the six of a series of various concentrations
With corresponding potential value in good linear relationship, the nearly 59.4mV/PF of slope in lithium fluophosphate aqueous solution6 -。
(4) measurement of sample
The testing sample solution handled well is taken, is tested according to the potential measurement method in step (3), the sound that will be obtained
It answers potential value to be brought into the corresponding abscissa of standard curve that step (3) obtains, the concentration of lithium hexafluoro phosphate can be obtained.
As limitation of the invention, the processing method of glass-carbon electrode described in step (2) are as follows: with diameter be the glass of 4mm
Carbon electrode is basal electrode, respectively in 0.5 μm and 0.3 μm of Al2O3After being polished into mirror surface on polishing powder, 1:1 nitric acid is successively used,
Ethyl alcohol and deionized water supersound washing 3min.
A series of various concentration 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 are as follows: reference electrode Ag/AgCl, in TISAB solution
It measuring, the preparation method of TISAB solution is that the glacial acetic acid for taking 57ml, 58g NaCl and 4g sodium citrate add water 500ml,
Adjusting pH with the NaOH of 5mol/L is 5~5.5 to get TISAB solution.
Sample to be tested described in step (4) is handled by the following method: being taken a certain amount of sample, is settled to 50ml, with 0.45 μ
M membrane filtration, filtrate is spare, and potential measurement value should be located at 1.0x10-1~1.0x10-5Between mol/L.
After adopting the above technical scheme, the invention has the following advantages that
(1) present invention select to be influenced lesser pyrroles by pH value as monomer, in electro-deposition polymerization process formation doped with
The polypyrrole film of hexafluorophosphoricacid acid ions, polypyrrole film carries out Selective recognition to hexafluorophosphoricacid acid ions, to form current potential
Response obtains the glass-carbon electrode of the polypyrrole film modification doped with hexafluorophosphoricacid acid ions, and the preparation process of the electrode is simple, will
The glass-carbon electrode of modification is stablized as working electrode, performance, and has good reproducibility.
It (2) can be to hexafluorophosphoricacid acid ions using the glass-carbon electrode of the polypyrrole film modification doped with hexafluorophosphoricacid acid ions
Direct Electrochemistry detection is carried out, the quick detection of lithium hexafluoro phosphate is realized, so that the detection process of each sample only needs rather
Clock can be completed, and testing cost is low.
(3) highly sensitive hexafluorophosphoricacid acid ions electrochemical sensor prepared by the present invention, modified electrode (PF6 --PPy/
GC) in 1.0x10-1~1.0x10-5It is in good linear relationship, the nearly 59.4mV/ of slope in the lithium hexafluoro phosphate aqueous solution of mol/L
PF6 -。
Detailed description of the invention
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 illustrate more clearly of the contents of the present invention, the present invention is made presently in connection with attached drawing and following embodiment further
Detailed description, but be noted that, these embodiments are only to illustrate to be used, and be not necessarily to be construed as implementing the present invention
Limitation.
(1) water used in experimentation is deionized water, and testing reagent used is that analysis is pure, is tested in room
Temperature is lower to be carried out.
(2) instrument and reagent used in the present embodiment:
Electrochemical workstation CHI660D (Shanghai Chen Hua instrument company) is used for the reality of constant current electro-deposition and potential measurement
It tests.Three-electrode system: working electrode is polypyrrole modifying glass-carbon electrode of the modification doped with hexafluorophosphoricacid acid ions, reference electrode
It is platinum electrode to electrode for Ag/AgCl electrode.
The hexafluorophosphoric acid lithium concentration in sample is measured according to the following steps:
(1) preparation of deposition solution
Use the aqueous solution of the lithium hexafluoro phosphate for the pyrroles and 0.01mol/L that deionized water compound concentration is 0.1mol/L as
Electric depositing solution of the invention.
(2) preparation of highly sensitive lithium hexafluoro phosphate sensor
Using diameter for 4mm glass-carbon electrode as basal electrode, respectively in 0.5 μm and 0.3 μm of Al2O3It polishes on polishing powder
After mirror surface, 1:1 nitric acid, ethyl alcohol and deionized water supersound washing 3min are successively used.
Uniformly by the deposition solution prepared in step 1 ultrasound, it is heavy that the above-mentioned glass-carbon electrode handled well is respectively placed in
In product solution, electro-deposition, current density 10mA/cm are carried out using galvanostatic method2, the electropolymerization time is 10min, in glass carbon electricity
Pole surface doping has the polypyrrole film (PF of hexafluorophosphoricacid acid ions6 -- PPy/GC), electro-deposition is placed on 0.1mol/L's
1h is impregnated in lithium hexafluoro phosphate aqueous solution to get modified electrode (PF6 -- PPy/GC), so that the electrification of the lithium hexafluoro phosphate be made
Learn sensor.
(3) test experience
Test experience is carried 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 are TISAB solution, measure different hexafluoro phosphorus respectively
Potential value under acid ion concentration, using the negative logarithm of hexafluorophosphoricacid acid ions concentration as abscissa, with the corresponding current potential of concentration
Value is ordinate, the standard curve of lithium hexafluoro phosphate can be obtained, 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) measurement of sample to be tested
10 samples of the μ L containing lithium hexafluoro phosphate are taken, in TISAB supporting electrolyte, are tested according to the detection in step (3)
Method and step carry out electro-chemical test, and to obtain current potential, gained potential value is calculated according to standard curve obtained by step (3)
The concentration of lithium hexafluoro phosphate in institute's sample.Mark-on reclaims are carried out to sample, calculate recovery of standard addition, the results are shown in Table 1.
Sample mark-on reclaims measurement result of the table 1 containing lithium hexafluoro phosphate
aFor the average value measured three times；RSD refers to: relative standard deviation
The relative standard deviation that each sample is measured in parallel 3 times is below 5%, illustrates essence when the method for the present invention practical measurement
Density is good；Recovery of standard addition illustrates that this method has good accuracy 96%~102%.
Based on above-mentioned test result, it can be seen that the method for Electrochemical Detection lithium hexafluoro phosphate of the present invention is easy to operate, side
Just quickly, testing cost is low, while realizing the electrochemical method directly detected to lithium hexafluoro phosphate.Above-described embodiment is only used for
Illustrate the contents of the present invention, but this is not a limitation of the present invention.
Claims (4)
1. a kind of method for detecting hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes, it is characterised in that: the detection
Method the following steps are included:
(1) preparation of deposition solution
The pyrroles and 1.0x10 for being 0.01~0.2mol/L with deionized water compound concentration-3The lithium hexafluoro phosphate of~0.1mol/L
Aqueous solution is as electric depositing solution；
(2) preparation of sensor PF6--PPy/GC
It is to electrode with platinum filament using glass-carbon electrode as working electrode, Ag/AgCl electrode is reference electrode, will handle clean glass
Carbon electrode is respectively placed in the electric depositing solution of pyrroles described in step (1) and lithium hexafluoro phosphate aqueous solution, using galvanostatic method
Electro-deposition is carried out, current density is 1~15mA/cm2, the electropolymerization time is 10~60min, is mixed in glassy carbon electrode surface electro-deposition
The miscellaneous polypyrrole film for having hexafluorophosphoricacid acid ions will be placed in the lithium hexafluoro phosphate water of 0.1mol/L by the electrode of electro-deposition modification
1h is impregnated in solution to get highly sensitive hexafluorophosphoricacid acid ions electrochemical sensor PF6--PPy/GC is arrived；
(3) drafting of standard curve
Using sensor PF6--PPy/GC obtained in step (2) as working electrode, Ag/AgCl electrode is set as reference electrode
In the aqueous solution of lithium hexafluoro phosphate, potential measurement is carried out, using the negative logarithm of hexafluorophosphoricacid acid ions concentration as abscissa, with dense
Spending corresponding potential value is ordinate, draws standard curve, a series of hexafluoro phosphorus of the sensor PF6--PPy/GC in various concentrations
It is in good linear relationship, slope 59.4mV/PF in sour lithium aqueous solution6 -；The potentiometric measurement, test condition are as follows:
Reference electrode is Ag/AgCl, is measured in TISAB solution, wherein the preparation method of TISAB solution is the ice for taking 57ml
Acetic acid, 58g NaCl and 4g sodium citrate add water 500ml, and adjusting pH with the NaOH of 5mol/L is 5~5.5 molten to get TISAB
Liquid；
(4) measurement of sample
The testing sample solution handled well is taken, is tested according to the potential measurement method in step (3), by obtained response electricity
Place value is brought into the corresponding abscissa of standard curve that step (3) obtains, and can obtain hexafluorophosphoric acid in lithium-ion battery electrolytes
Lithium content.
2. the method as described in claim 1 for detecting hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes, feature
Be: the processing method of step (2) described glass-carbon electrode are as follows: using diameter for 4mm glass-carbon electrode as basal electrode, exist respectively
0.5 μm and 0.3 μm of Al2O3After being polished into mirror surface on polishing powder, 1:1 nitric acid, ethyl alcohol and deionized water supersound washing are successively used
3min。
3. the method as described in claim 1 for detecting hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes, feature
Be: a series of concentration of the lithium hexafluoro phosphate aqueous solution of various concentrations described in step (3) 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. the method as described in claim 1 for detecting hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes, feature
Be: sample to be tested described in step (4) is handled by the following method: taking sample to be settled to 50ml, with 0.45 μm of membrane filtration, filter
Liquid is spare, and potential measurement value should be located at 1.0x10-1~1.0x10-5Between mol/L.
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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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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 |