CN106248609A - A kind of ultraviolet spectrophotometer measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes - Google Patents
A kind of ultraviolet spectrophotometer measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes Download PDFInfo
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- CN106248609A CN106248609A CN201610893378.8A CN201610893378A CN106248609A CN 106248609 A CN106248609 A CN 106248609A CN 201610893378 A CN201610893378 A CN 201610893378A CN 106248609 A CN106248609 A CN 106248609A
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- lithium
- ion battery
- battery electrolytes
- ultraviolet spectrophotometer
- hexafluorophosphoric acid
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003792 electrolyte Substances 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 52
- -1 hexafluorophosphoric acid lithium Chemical compound 0.000 title claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 63
- 239000010452 phosphate Substances 0.000 claims abstract description 63
- 238000004737 colorimetric analysis Methods 0.000 claims abstract description 17
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 32
- 229910017604 nitric acid Inorganic materials 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 32
- 238000002835 absorbance Methods 0.000 claims description 21
- 229940010552 ammonium molybdate Drugs 0.000 claims description 21
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 21
- 239000011609 ammonium molybdate Substances 0.000 claims description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 230000029087 digestion Effects 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 9
- 229940005654 nitrite ion Drugs 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 5
- 229950000845 politef Drugs 0.000 claims description 4
- OTGFEQJKSRFOED-UHFFFAOYSA-N [P].[V].[Mo] Chemical compound [P].[V].[Mo] OTGFEQJKSRFOED-UHFFFAOYSA-N 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 21
- 238000012360 testing method Methods 0.000 abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 28
- 229910052744 lithium Inorganic materials 0.000 description 28
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 26
- 239000007788 liquid Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a kind of ultraviolet spectrophotometer and measure the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes, described method is particularly as follows: carry out phosphorus vanadium molybdate yellow colorimetric method with ultraviolet spectrophotometer after being cleared up by lithium-ion battery electrolytes and detect the sample after clearing up, measure the mass concentration of the phosphate radical of the sample after clearing up and then obtain hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes, it is an object of the invention to provide the convenient detection method of hexafluorophosphoric acid lithium content in a kind of lithium-ion battery electrolytes, the method is without expensive instrument and equipment, testing cost is cheap and accuracy of detection is high, repeatability is excellent.
Description
Technical field
The present invention relates to technical field of analysis and detection, particularly relate to a kind of ultraviolet spectrophotometer and measure lithium ion battery
The method of hexafluorophosphoric acid lithium content in electrolyte.
Background technology
Lithium ion battery is widely used because having the advantages such as energy density height, good cycle.Lithium ion battery battery
Solve the liquid key component as lithium battery, very big to the performance impact of battery.Lithium hexafluoro phosphate is as lithium ion battery battery
Solving the electrolyte of liquid, its content directly can affect the electrical conductivity of lithium-ion battery electrolytes, finally affects the property of lithium ion battery
Can, therefore in Accurate Determining lithium-ion battery electrolytes, the content of lithium hexafluoro phosphate is particularly significant.
The means such as patent CN1621808A ion chromatograph, atomic absorption spectrophotometer measure lithium ion battery electrolysis
The method of lithium salt in liquid, its relative error is bigger.PF6-is changed into PO43-and contains to measure lithium salts by patent CN1888893A
Amount, pre-treatment required time is longer, and testing conditions requires that higher process is complicated, it is more difficult to promote, the most rare employing.Patent
CN 102323184 A uses the sedimentation method, but the reagent toxicity more complicated side of bigger whole operating process used in its experiment
Method accuracy is low.Patent 201610294724.0 uses ion chromatograph to detect containing of PF6-in lithium-ion battery electrolytes to be measured
Amount, uses potentiometric titrimeter to detect the content of F-in lithium-ion battery electrolytes to be measured, and some fluorinated additive may shadow
Ringing the content of F-, result cannot test out.
In order to improve the problems referred to above, Chinese patent application CN201510907291.7 discloses a kind of employing resolution method to electricity
Solve after liquid processes and be then passed through the method that lithium hexafluoro phosphate therein measured by plasma photo-electric direct reading spectrometer.The method
Can effectively solve above-mentioned problem, but its equipment cost is up to hundreds of thousands to the most up to a million, testing cost is high, and for entirely
The degree of accuracy of the lithium hexafluoro phosphate in the electrolyte of the variable concentrations of series need to improve.
Summary of the invention
Based on this, it is an object of the invention to provide the easy inspection of hexafluorophosphoric acid lithium content in a kind of lithium-ion battery electrolytes
Survey method, the method is without expensive instrument and equipment, and testing cost is cheap and accuracy of detection is high, and repeatability is excellent.
Concrete technical scheme is as follows: a kind of ultraviolet spectrophotometer measures lithium hexafluoro phosphate in lithium-ion battery electrolytes
The method of content, it is characterised in that described method is particularly as follows: use uv-spectrophotometric after being cleared up by lithium-ion battery electrolytes
Meter carries out phosphorus vanadium molybdate yellow colorimetric method and detects the sample after clearing up, and measures the mass concentration of the phosphate radical of the sample after clearing up
And then obtain hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content, institute
That states carries out what the sample after clearing up was detected by phosphorus vanadium molybdate yellow colorimetric method with ultraviolet spectrophotometer method particularly includes:
Sample is moved into and adds the salpeter solution and vanadium ammonium molybdate colour developing that volume ratio is 1:1 in color comparison tube by step (11)
Liquid, is diluted with water to scale, shakes up, and places a period of time；
Step (12) uses ultraviolet spectrophotometer absorbance of sample in determination step (11) at 420nm；
The curve of the standard phosphate root solution that the absorbance that step (12) is obtained by step (13) is good with measured in advance is carried out
Contrast, the concentration of the phosphate radical solution obtained in step (11) in sample.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content, institute
In the step (11) stated, amount of samples is 1ml, and salpeter solution is 4ml, and vanadium ammonium molybdate nitrite ion is 5mL.
Case study on implementation adds the salpeter solution of 4mL, and the vanadium ammonium molybdate nitrite ion of 5mL so that the absorbance of solution is fitted
In, color speed is fast, favorable reproducibility, and sensitivity is best.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content, institute
What the lithium-ion battery electrolytes stated was cleared up concretely comprises the following steps:
Step (21) weighs in the counteracting tank that 3-5g lithium-ion battery electrolytes is placed in politef material, adds 5-
After the ultra-pure water of 15mL, heat treated；
The step (22) solution in step (21) adds 5-15mL strong reagents, then by politef material
Counteracting tank is put into and is cleared up instrument and clear up；
Step (23) solution in step (22) is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content,
In described step (21), described heat treated condition is that temperature is 135-145 DEG C, and heat time heating time is 4h.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content,
In described step (22), described strong reagents is concentrated nitric acid, and its mass fraction is about 60-70%.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content,
In described step (22), described digestion condition is 200 DEG C, and clearing up pressure is 1.5～3.5MPa, and digestion time is 20min.
In above-mentioned ultraviolet spectrophotometer measures lithium-ion battery electrolytes in the method for hexafluorophosphoric acid lithium content, root
According to the mass concentration of phosphate radical and then obtain the circular of hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes and be: root
According to chemical equationThe mass concentration utilizing phosphate radical calculates
The content of lithium hexafluoro phosphate in lithium-ion battery electrolytes, wherein computing formula is as follows:
In formula, W is hexafluorophosphoric acid lithium content, wt%；W1 is the mass concentration of phosphate radical, mg/mL；M is lithium hexafluoro phosphate
Relative molecular mass, 151.9g/mol；M1 is phosphate radical relative molecular mass, 31g/mol；M is lithium-ion battery electrolytes matter
Amount, g；V is color comparison tube volume, 50mL；P is extension rate, 200.
The organic principle volatilization as far as possible that the purpose that step (21) heats is so that in lithium-ion battery electrolytes is gone out, in case
Residual organic principle has the functional group such as double bond and conjugated bonds to affect later stage solution colourity, thus causes bigger error.Meanwhile, add
Hot temperature can not be the highest, and this is owing in lithium-ion battery electrolytes, hexafluoro-phosphate radical, during being changed into phosphate radical, first turns
Become trifluoro oxygen phosphorus.If heating-up temperature too Gao Zehui causes trifluoro oxygen phosphorus to have certain volatilization, thus causes phosphorus loss, finally
Make test result less than normal.The present invention is by considering heating and temperature control at 135-145 DEG C, and thinks that this temperature is
Optimal treatment temperature.
In described step (22), described strong reagents is concentrated nitric acid, and its mass fraction is about 60-70% so that below
Digestion process reaction the most abundant, digestion process is best.In the present invention, do not repel and use hydrochloric acid or sulphuric acid, but use
It is error lower for concentrated nitric acid.
In described step (22), described digestion condition is 200 DEG C, and clearing up pressure is 1.5～3.5MPa, and digestion time is
20min。
The purpose cleared up in this programme is destroy in lithium-ion battery electrolytes in the material of the organic principle of residual double
The structure such as key or conjugated bonds and be completely dissolved above heating a period of time after all lithium-ion battery electrolytes.Meanwhile,
Hexafluoro-phosphate radical in lithium-ion battery electrolytes can be completely transformed into phosphate radical by clearing up.Therefore, clear up and can enter one
Step reduces organic principle and remains the Chroma Error caused, and is prevented from hexafluoro-phosphate radical simultaneously and changes the error not exclusively caused.
Principle and the advantage of the present invention are as follows:
The present invention uses phosphorus vanadium molybdate yellow colorimetric method to utilize ultraviolet spectrophotometer to measure the phosphate radical in the solution after clearing up
Content, and then reach to detect the purpose of the content of lithium hexafluoro phosphate in electrolyte.
Being in place of its excellence, phosphorus vanadium molybdate yellow colorimetric method is measured more convenient, and the price of ultraviolet spectrophotometer is low, has
Effect reduces measures cost, it is even more important that use phosphorus vanadium molybdate yellow colorimetric method to replace plasma photo-electric direct reading spectrometer to survey
Amount its accuracy of detection of phosphate radical is the highest, and error is little, requires that the detection of high electrolyte is to have very much for high accuracy, repeatability
Benefit.
Accompanying drawing explanation
Fig. 1 is phosphate content and the canonical plotting of absorbance thereof of embodiment；
Detailed description of the invention
By the following examples the application is further elaborated.
First, phosphorus vanadium molybdate yellow colorimetric method standard curve making method is as follows:
1, preparation vanadium ammonium molybdate nitrite ion: be dissolved in water 100mL by 40g ammonium molybdate (analytical pure), moves into 500mL volumetric flask
In, it is diluted with water to scale；3g ammonium vanadate (analytical pure) is dissolved in 100mL water, adds 200mL concentrated nitric acid (65%), stirring
After dissolving, move in 500mL volumetric flask, be diluted with water to scale.During use into, ammonium molybdate solution is slowly poured Ammonium Vanadate Solution
In, and mix according to volume ratio 1:1, stir, can use.
2, preparation standard phosphate root solution: weigh 105～110 DEG C of dried potassium dihydrogen phosphate (analytical pure) 0.4394g
(being accurate to 0.0001g), with after 100mL water dissolution, moves in 1000mL volumetric flask, is diluted with water to scale, phosphoric acid in this solution
The mass concentration of root is 0.148mg/mL.
3, draw phosphate radical mass concentration and the standard curve of absorbance thereof: take 1,2,3,4,5,6,7mL standard phosphorus solution
Move in 50mL color comparison tube respectively, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate nitrite ion 5mL, be diluted with water to scale, shake
Even, after placing 30min, use Evolution 300 type dual-beam ultraviolet spectrophotometer (Thermo company of the U.S.) at 420nm
Place, for comparison its absorbance of measurement (such as table 1) and draws standard curve (such as accompanying drawing 1) with reagent blank with the cuvette of 3cm.
It should be understood that (1+1) as herein described nitric acid refers to 1 volume commercially available concentrated nitric acid (65wt%)+1 volume
Water, mixing.
65% nitric acid as herein described refers to the salpeter solution that mass percent is 65%.
Table 1 standard phosphate root solution and absorbance thereof
| Phosphate radical mass concentration (× 10-3mg/mL) | 2.968 | 5.936 | 8.903 | 11.871 | 14.839 | 17.807 | 20.775 |
| Absorbance | 0.112 | 0.211 | 0.335 | 0.436 | 0.541 | 0.658 | 0.764 |
Embodiment 1
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 5%, 4.99g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 5mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 2
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 9.5%, 4.87g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 5mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 3
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 12.5%, 3.50g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 5mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 4
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 15%, 3.50g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 5mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 5
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 20%, 3.42g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 5mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 6
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 24%, 3.62g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 5mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 7
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 15%, 3.68g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 2mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Embodiment 8
A kind of ultraviolet spectrophotometer of the present embodiment measures the method for hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes,
Comprise the steps:
1, taking the lithium-ion battery electrolytes of known lithium hexafluoro phosphate mass percentage content 15%, 3.54g (is accurate to
0.01), in counteracting tank, after adding the ultra-pure water of 10mL, then put 140 DEG C of heating 4h on the heaters, stop heating, cooling
To room temperature.
2, in counteracting tank, add 15mL concentrated nitric acid (65%), put into counteracting tank to clear up to carry out on instrument clearing up and in temperature be
200 DEG C, pressure is under 3.0MPa, keeps 20min.After having cleared up, treat that instrument temperature is down to 50 DEG C, pressure be down to 0.2MPa with
Under, open instrument, take out counteracting tank；Digestion solution is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
3, moving in 50mL color comparison tube with pipette, extract 1mL sample, add colourless (1+1) nitric acid 4mL, vanadium ammonium molybdate shows
Color liquid 8mL, is diluted with water to scale, shakes up, and after placing 30min, uses Evolution300 type dual-beam uv-spectrophotometric
Meter (Thermo company of the U.S.), 420nm at, with the cuvette of 3cm with reagent blank for comparison its absorbance of measurement, goes forward side by side one
Step calculates the mass concentration of phosphate radical in solution.
4, utilize the mass concentration of phosphorus vanadium molybdate yellow colorimetric method repeated measure detection phosphate radical, calculate containing of lithium hexafluoro phosphate
Amount, averages, such as table 2.
Experimental result is as shown in table 2:
Table 2 sample tests and error
It should be understood that content measured in table 2 is the content of lithium hexafluoro phosphate.
As shown in Table 2, using the method for testing of the present invention, its testing cost is lower, detects the simplest.
It is especially noted that when the consumption of vanadium ammonium molybdate nitrite ion controls at 5ml, test lithium ion battery lithium from
In sub-battery electrolyte, hexafluorophosphoric acid lithium content error is within 1%.
It should be noted that in the present invention, (1+1) nitric acid used in phosphorus vanadium molybdate yellow colorimetric method is particularly important, its
Purposes is, by solution degree of colour developing regulation to an optimal point, to improve the repeatability of absorbance detection.
In the present invention, the consumption of vanadium ammonium molybdate nitrite ion also accurately to control, the least then extinction of vanadium ammonium molybdate usage amount
Spending little, detection error is big；And usage amount is too big, absorbance is very strong, causes sensitivity low, it is impossible to the trace of reflection phosphate concentration
Change.
The proportioning of the vanadium ammonium molybdate nitrite ion of the present invention and (1+1) nitric acid is appropriate, can ensure its accuracy of detection and inspection
Surveying in the case of sensitivity, improve the repeatability of detection, be effectively improved in traditional scheme, accuracy of detection, repeatability, detection are sensitive
Spend the problem that three can not be unified.
Additionally, in the present invention, double bond and conjugated bonds are significant on the impact of absorbance, need if to eliminate this impact
It is noted that following item: the nitric acid using 60-70% in step (22) is the most superior compared to hydrochloric acid or sulphuric acid, and its reason is
In solution preocess, using the nitric acid of 60-70% to clear up the most complete, this is owing to the oxidisability of nitric acid is most appropriate to process in electrolyte
Organic substance, effectively reducing the functional groups such as double bond and conjugated bonds that wherein Organic substance comprised affects later stage solution colourity.
Meanwhile, thoroughly eliminating double bond and conjugated bonds not merely just can be completed by the nitric acid of 60-70%, it also needs to
In the requirement of 135-145 DEG C of long-time heating in matching step (21), first pass through 135-145 DEG C and eliminate most organic
Thing, in the process, temperature is too low, and Organic substance cannot fully volatilize, and temperature is too high, then easily cause the loss of trifluoro oxygen phosphorus,
Error is made to occur.Secondly, by the nitric acid of 60-70% in the case of High Temperature High Pressure, improve double bond and the decomposition of conjugated bonds, carry
High measurement accuracy.It should be noted that double bond and conjugated bonds are in plasma photo-electric direct reading spectrometer will not be to testing result
Cause significantly impact, but the impact in spectrophotometer is significant.
Therefore, the present invention, while effectively reducing testing cost, simplifying characterization processes, coordinates above-mentioned operation, permissible
Reach to significantly improve accuracy of detection, sensitivity and reproducible purpose.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore it is construed as limiting the scope of the patent.It should be pointed out that, for the person of ordinary skill of the art,
On the premise of present inventive concept, it is also possible to make some deformation and improvement, these broadly fall into protection scope of the present invention.
Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1. a method for hexafluorophosphoric acid lithium content during ultraviolet spectrophotometer measures lithium-ion battery electrolytes, its feature exists
In, described method is particularly as follows: carry out phosphorus vanadium molybdenum Huang colorimetric with ultraviolet spectrophotometer after being cleared up by lithium-ion battery electrolytes
Sample after clearing up is detected by method, measures the mass concentration of the phosphate radical of the sample after clearing up and then obtains lithium ion battery
Hexafluorophosphoric acid lithium content in electrolyte.
Ultraviolet spectrophotometer the most according to claim 1 measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes
Method, it is characterised in that described carry out phosphorus vanadium molybdate yellow colorimetric method with ultraviolet spectrophotometer the sample after clearing up is examined
Survey method particularly includes:
Sample is moved into and adds salpeter solution and the vanadium ammonium molybdate nitrite ion that volume ratio is 1:1 in color comparison tube by step (11), uses
Water is diluted to scale, shakes up, and places a period of time；
Step (12) uses ultraviolet spectrophotometer absorbance of sample in determination step (11) at 420nm；
The curve of the standard phosphate root solution that the absorbance that step (12) is obtained by step (13) is good with measured in advance contrasts,
The concentration of the phosphate radical solution obtained in step (11) in sample.
Ultraviolet spectrophotometer the most according to claim 2 measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes
Method, it is characterised in that in described step (11), amount of samples is 1ml, and salpeter solution is 4ml, and vanadium ammonium molybdate nitrite ion is
5mL。
Ultraviolet spectrophotometer the most according to claim 1 measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes
Method, it is characterised in that what described lithium-ion battery electrolytes was cleared up concretely comprises the following steps:
Step (21) weighs in the counteracting tank that 3-5g lithium-ion battery electrolytes is placed in politef material, adds 5-15mL's
After ultra-pure water, heat treated；
The step (22) solution in step (21) adds 5-15mL strong reagents, then clearing up politef material
Tank is put into and is cleared up instrument and clear up；
Step (23) solution in step (22) is first gone in 50mL volumetric flask dilute constant volume, then take 25mL diluent in
100mL volumetric flask dilutes constant volume.
Ultraviolet spectrophotometer the most according to claim 4 measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes
Method, it is characterised in that in described step (21), described heat treated condition is that temperature is 135-145 DEG C, and heat time heating time is
4h。
Ultraviolet spectrophotometer the most according to claim 5 measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes
Method, it is characterised in that in described step (22), described strong reagents is concentrated nitric acid, and its mass fraction is about 60-70%.
Ultraviolet spectrophotometer the most according to claim 6 measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes
Method, it is characterised in that in described step (22), described digestion condition is 200 DEG C, clearing up pressure is 1.5～3.5MPa, disappears
The solution time is 20min.
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| CN109211885A (en) * | 2017-06-29 | 2019-01-15 | 宁夏软件工程院有限公司 | A kind of electrolytic process manganese ion concentration measuring device and measurement method |
| CN110243775A (en) * | 2019-06-20 | 2019-09-17 | 江西理工大学 | The analyzing detecting method and preparation method thereof of polyethyleneglycol content in a kind of electrolyte of copper foil |
| CN110873694A (en) * | 2018-08-31 | 2020-03-10 | 中国科学院物理研究所 | Device and method for detecting ion content in secondary battery electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107422267A (en) * | 2017-04-10 | 2017-12-01 | 上海电气集团股份有限公司 | The SOC detection means and method of all-vanadium flow battery |
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