CN110161133A - A kind of method that external standard method tests and analyzes component in lithium ion function electrolyte - Google Patents
A kind of method that external standard method tests and analyzes component in lithium ion function electrolyte Download PDFInfo
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Abstract
The invention belongs to a kind of methods that external standard method tests and analyzes component in lithium ion function electrolyte；Include the following steps: the drafting of each material standard curve in lithium ion function electrolyte: choosing at least three kinds of electrolyte solvent samples for needing to detect；Mixed liquor is configured to by least two or more additives are added in above-mentioned at least three kinds of electrolyte solvent samples, it tries to please measuring bottle, analysis level adiponitrile is added into volumetric flask respectively as diluent, is diluted to 100ML graduation mark, gas chromatograph detection is carried out, response is obtained；The measurement of each material content in lithium ion function electrolyte；The drafting of lithium salts standard curve in lithium ion function electrolyte；The measurement of lithium salt content in solvent；Have the advantages that method is simple, testing cost is low, the period is short and precision is high.
Description
Technical field
The invention belongs to compound mensuration technical fields in lithium ion function electrolyte, and in particular to a kind of external standard method detection point
The method for analysing component in lithium ion function electrolyte.
Background technique
Currently, the research to lithium-ion battery electrolytes organic component test method, sends out from initial qualitative analysis
Open up the accurate quantitative analysis stage.Battery producer is increasingly stringenter the monitoring requirement of electrolyte manufacturer processing procedure,
Whether the material and ratio to addition are within the scope of allowable error；Appearance of the material additional amount of solvent and additive to further battery
It is larger therefore particularly important to the analysis detection of electrolyte component to measure circulating effect.
Summary of the invention
The purpose of the present invention is to overcome the defects in the prior art, and provides that a kind of method is simple, testing cost is low, all
The method that the external standard method that phase is short and precision is high tests and analyzes component in lithium ion function electrolyte.
The object of the present invention is achieved like this: this method comprises the following steps:
1.1: the drafting of each material standard curve in lithium ion function electrolyte: choosing at least three kinds electrolysis for needing to detect
Liquid solvent samples；It is configured to mixed liquor by least two or more additives are added in above-mentioned at least three kinds of electrolyte solvent samples,
Take 6 100ML volumetric flasks respectively, be separately added into respectively into volumetric flask 4.43g, 8.86g, 17.72g, 26.58g, 35.44g and
Then 44.3g is added analysis level adiponitrile as diluent into volumetric flask respectively, is diluted to 100ML graduation mark, carries out gas phase
Chromatograph detection obtains response, and draws standard curve according to the response of the content of each solvent or additive；The gas phase
Chromatographic testing conditions are as follows: use Shimadzu GC-2014 gas chromatograph, chromatographic column: rtx-5 30*0.25*0.25 low pole
Chromatographic column, by the way of make-up gas, nitrogen pressure 75Kpa, Hydrogen Vapor Pressure 50Kpa, air pressure 50Kpa, column temperature
Case takes temperature programming mode: keeping 3min, heating rate in the environment of 45 DEG C are as follows: 10 DEG C/min, is warming up to 250 DEG C and protects
Hold 3min；Column flow 0.5ml/min, shunt mode, segregation ratio 50, injector temperature are 250 DEG C, and detector temperature is 300 DEG C；
The electrolyte solvent include ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl ester, diethyl carbonate,
Ethyl acetate, ethyl propionate, methyl acetate；The additive includes vinylene carbonate, toluene, cyclohexylbenzene, 1,3 propane sulphurs
Acid lactone, fluorinated ethylene carbonate and phosphite ester；
1.2: 11g analysis to be detected the measurement of each material content in lithium ion function electrolyte: being added in separatory funnel
Then electrolyte 44g saturated brine is added into separatory funnel and mixed liquor is made, above-mentioned mixed liquor concussion 3-5min is removed lithium
Salt takes upper layer organic solution or lower layer's organic solution, and filters out organic solvent 10ML using the syringe filters of 0.2um, will
Above-mentioned organic solvent is placed on 100ML volumetric flask, and analysis level adiponitrile is added as diluent, is diluted to 100ML graduation mark, obtains
To response, the content of each component in analysis electrolyte to be detected is obtained by standard curve；
2.1: the drafting of lithium salts standard curve in lithium ion function electrolyte: taking the lithium standard solution of 1000mg/L, respectively
1mg, 5mg, 10mg are taken, the lithium standard solution of 20mg is placed in the volumetric flask of 4 different 1000ML, is dilute with deionized water
Agent is released, is diluted to 1000ML graduation mark respectively, concentration is respectively 1mg/L, 5mg/L, 10mg/L, the standard solution of 20mg/L, so
The standard solution after above-mentioned dilution is measured respectively with plasma emission spectrometry (ICP) afterwards, and each according to them
From concentration value C and corresponding absorbance intensity value A make canonical plotting；And equation of linear regression is found out, equation are as follows: y
=2563.9x-1269.6, coefficient R2=1；
2.2: the measurement of lithium salt content in solvent: taking concentration is 37% concentrated hydrochloric acid 100mL, and 100mL deionized water is added
Dilution is stand-by, and hydrochloric acid solution is made；Using pipette or liquid-transfering gun accurately take lithium ion function electrolyte 20mL to be detected in
In the separatory funnel of 125mL, the concussion of 30mL hydrochloric acid solution is added, stands 10min, water phase extracts gained lithium salt solution, is used in combination
After hydrochloric acid is stripped organic phase 2 times, extraction gained water phase lithium salt solution mixed collection three times, 10mL water phase lithium salts is taken after collection
Solution, while it being settled to 100mL with deionized water, which is diluted to 500 times, electrolyte to be detected is made；Use plasma
Body emission spectrometric analyzer carries out plasma emission spectrometry to electrolyte to be detected, obtains their absorbance value A, root
The lithium salt C of the electrolyte to be measured after dilution is acquired according to absorbance value A and standard curve0, further according to formula calculate to
Survey the lithium salt C of electrolyte；The calculation formula are as follows: C=C0× P/ (6.941 × 1000), in above-mentioned formula: C0: diluted sample
Lithium salt value (mg/L) in product, P: being deionized water to the diluted multiple of water phase lithium salt solution, 6.941 be the atom matter of lithium
Amount.
The present invention has the advantages that method is simple, testing cost is low, the period is short and precision is high.
Detailed description of the invention
Fig. 1 is the solvent canonical plotting of dimethyl carbonate in experimental example two of the present invention.
Fig. 2 is the solvent canonical plotting of methyl ethyl ester in experimental example one of the present invention.
Fig. 3 is the solvent canonical plotting of diethyl carbonate in experimental example one of the present invention.
Fig. 4 is the solvent canonical plotting of ethylene carbonate in experimental example one of the present invention.
Fig. 5 is the additive canonical plotting of vinylene carbonate in experimental example one of the present invention.
Fig. 6 is the additive canonical plotting of 1,3 propane sulfonic acid lactones in experimental example one of the present invention.
Fig. 7 is the solvent canonical plotting of propene carbonate in experimental example two of the present invention.
Fig. 8 is the solvent canonical plotting of ethyl acetate in experimental example two of the present invention.
Fig. 9 is the solvent canonical plotting of ethyl propionate in experimental example two of the present invention.
Figure 10 is the solvent canonical plotting of methyl acetate in experimental example two of the present invention.
Figure 11 is the additive canonical plotting of toluene in experimental example two of the present invention.
Figure 12 is the additive canonical plotting of cyclohexylbenzene in experimental example two of the present invention.
Figure 13 is the additive canonical plotting of two phosphorous acid ester of experimental example of the present invention.
Figure 14 is the additive canonical plotting of fluorinated ethylene carbonate in experimental example two of the present invention.
Figure 15 is the lithium salts canonical plotting in experimental example one of the present invention.
Specific embodiment
The present invention is a kind of method that external standard method tests and analyzes component in lithium ion function electrolyte, and this method includes as follows
Step:
1.1: the drafting of each material standard curve in lithium ion function electrolyte: choosing at least three kinds electrolysis for needing to detect
Liquid solvent samples；It is configured to mixed liquor by least two or more additives are added in above-mentioned at least three kinds of electrolyte solvent samples,
Take 6 100ML volumetric flasks respectively, be separately added into respectively into volumetric flask 4.43g, 8.86g, 17.72g, 26.58g, 35.44g and
Then 44.3g is added analysis level adiponitrile as diluent into volumetric flask respectively, is diluted to 100ML graduation mark, carries out gas phase
Chromatograph detection obtains response, and draws standard curve according to the response of the content of each solvent or additive；The gas phase
Chromatographic testing conditions are as follows: use Shimadzu GC-2014 gas chromatograph, chromatographic column: rtx-5 30*0.25*0.25 low pole
Chromatographic column, by the way of make-up gas, nitrogen pressure 75Kpa, Hydrogen Vapor Pressure 50Kpa, air pressure 50Kpa, column temperature
Case takes temperature programming mode: keeping 3min, heating rate in the environment of 45 DEG C are as follows: 10 DEG C/min, is warming up to 250 DEG C and protects
Hold 3min；Column flow 0.5ml/min, shunt mode, segregation ratio 50, injector temperature are 250 DEG C, and detector temperature is 300 DEG C；
The electrolyte solvent include ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl ester, diethyl carbonate,
Ethyl acetate, ethyl propionate, methyl acetate；The additive includes vinylene carbonate, toluene, cyclohexylbenzene, 1,3 propane sulphurs
Acid lactone, fluorinated ethylene carbonate and phosphite ester；
1.2: 11g analysis to be detected the measurement of each material content in lithium ion function electrolyte: being added in separatory funnel
Then electrolyte 44g saturated brine is added into separatory funnel and mixed liquor is made, above-mentioned mixed liquor concussion 3-5min is removed lithium
Salt takes upper layer organic solution or lower layer's organic solution, and filters out organic solvent 10ML using the syringe filters of 0.2um, will
Above-mentioned organic solvent is placed on 100ML volumetric flask, and analysis level adiponitrile is added as diluent, is diluted to 100ML graduation mark, obtains
To response, the content of each component in analysis electrolyte to be detected is obtained by standard curve；
2.1: the drafting of lithium salts standard curve in lithium ion function electrolyte: taking the lithium standard solution of 1000mg/L, respectively
1mg, 5mg, 10mg are taken, the lithium standard solution of 20mg is placed in the volumetric flask of 4 different 1000ML, to be diluted to respectively
1000ML graduation mark, concentration are respectively 1mg/L, 5mg/L, 10mg/L, then the standard solution of 20mg/L uses plasma emission
Spectrum analysis (ICP) is respectively measured the standard solution after above-mentioned dilution, and according to their own concentration value C and correspondence
Absorbance intensity value A make canonical plotting；And equation of linear regression is found out, and equation are as follows: y=2563.9x-1269.6,
Coefficient R2=1；
2.2: the measurement of lithium salt content in solvent: taking concentration is 37% concentrated hydrochloric acid 100mL, and 100mL deionized water is added
Dilution is stand-by, and hydrochloric acid solution is made；Using pipette or liquid-transfering gun accurately take lithium ion function electrolyte 20mL to be detected in
In the separatory funnel of 125mL, the concussion of 30mL hydrochloric acid solution is added, stands 10min, water phase extracts gained lithium salt solution, is used in combination
After hydrochloric acid is stripped organic phase 2 times, extraction gained water phase lithium salt solution mixed collection three times, 10mL water phase lithium salts is taken after collection
Solution, while it being settled to 100mL with deionized water, which is diluted to 500 times, electrolyte to be detected is made；Use plasma
Body emission spectrometric analyzer carries out plasma emission spectrometry to electrolyte to be detected, obtains their absorbance value A, root
The lithium salt C of the electrolyte to be measured after dilution is acquired according to absorbance value A and standard curve0, further according to formula calculate to
Survey the lithium salt C of electrolyte；The calculation formula are as follows: C=C0× P/ (6.941 × 1000), in above-mentioned formula: C0: diluted sample
Lithium salt value (mg/L) in product, P: being deionized water to the diluted multiple of water phase lithium salt solution, 6.941 be the atom matter of lithium
Amount.
For the more detailed explanation present invention, the present invention is further elaborated now in conjunction with embodiment.Specific embodiment
It is as follows:
Embodiment one:
A kind of method that external standard method tests and analyzes component in lithium ion function electrolyte, this method comprises the following steps:
The drafting of each material standard curve in 1.1 lithium ion function electrolytes: solvent chooses ethylene carbonate, methyl
As analysis object, additive chooses vinylene carbonate and 1 for ethyl ester and diethyl carbonate, and 3 propane sulfonic acid lactones are made
It is configured to mixed liquor for analysis object, additive will be added in electrolyte solvent sample and be configured to mixed liquor and take 6 100ML respectively
Volumetric flask takes 6 100ML volumetric flasks respectively, be separately added into respectively into volumetric flask 4.43g, 8.86g, 17.72g, 26.58g,
Then 35.44g and 44.3g is added analysis level adiponitrile as diluent into volumetric flask respectively, is diluted to 100ML graduation mark,
Gas chromatograph detection is carried out, obtains response, and standard curve is drawn according to the response of the content of each solvent or additive；
The testing conditions of the gas chromatograph are as follows: use Shimadzu GC-2014 gas chromatograph, chromatographic column: rtx-530*0.25*0.25
Low pole chromatographic column, by the way of make-up gas, nitrogen pressure 75Kpa, Hydrogen Vapor Pressure 50Kpa, air pressure is
50Kpa, column oven take temperature programming mode: keeping 3min, heating rate in the environment of 45 DEG C are as follows: and 10 DEG C/min, heating
To 250 DEG C and keep 3min；Column flow 0.5ml/min, shunt mode, segregation ratio 50, injector temperature are 250 DEG C, detector
Temperature is 300 DEG C；Coefficient R >=0.9999；It is formulated as follows the different mixed standard solution concentration of table and pipettes exact mass:
The solvent of drafting and the canonical plotting of additive are referring specifically to as shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
1.2: it is to be detected that 11g the measurement of each material content in lithium ion function electrolyte: is separately added into separatory funnel
Electrolyte is analyzed, 44g saturated brine is then added into separatory funnel, mixed liquor is made, above-mentioned mixed liquor concussion 3-5min is removed
Lithium salts is removed, takes upper layer organic solution or lower layer's organic solution, and filter out the organic molten of 10ML using the syringe filters of 0.2um
The organic solvent of 10ML is placed on 100ML volumetric flask by agent, and analysis level adiponitrile is added as diluent, is diluted to 100ML quarter
Line is spent, the organic solvent in electrolyte to be tested is detected with the gas chromatograph testing conditions in above-mentioned 1.1, is responded
Value obtains the content of each solvent component in analysis electrolyte to be detected by standard curve；Survey is repeated twice by the above method
Determine each solvent component in electrolyte content itself the result is as follows:
2.1: the drafting of lithium salts standard curve in lithium ion function electrolyte: taking the lithium standard solution of 1000mg/L, respectively
1mg, 5mg, 10mg are taken, the lithium standard solution of 20mg is placed in the volumetric flask of 4 different 1000ML, is dilute with deionized water
Agent is released, is diluted to 1000ML graduation mark respectively, concentration is respectively 1mg/L, 5mg/L, 10mg/L, the standard solution of 20mg/L, so
The standard solution after above-mentioned dilution is measured respectively with plasma emission spectrometry (ICP) afterwards, and each according to them
From concentration value C and corresponding absorbance intensity value A make canonical plotting；And equation of linear regression is found out, equation are as follows: y
=2563.9x-1269.6, coefficient R2=1；The lithium salts canonical plotting of drafting is referring specifically to Figure 15.
2.2: the measurement of lithium salt content in solvent: taking concentration is 37% concentrated hydrochloric acid 100mL, and 100mL deionized water is added
Dilution is stand-by, and hydrochloric acid solution is made；Using pipette or liquid-transfering gun accurately take lithium ion function electrolyte 20mL to be detected in
In the separatory funnel of 125mL, the concussion of 30mL hydrochloric acid solution is added, stands 10min, water phase extracts gained lithium salt solution, is used in combination
After hydrochloric acid is stripped organic phase 2 times, extraction gained water phase lithium salt solution mixed collection three times, 10mL water phase lithium salts is taken after collection
Solution, while it being settled to 100mL with deionized water, which is diluted to 500 times, electrolyte to be detected is made；Use plasma
Body emission spectrometric analyzer carries out plasma emission spectrometry to electrolyte to be detected, obtains their absorbance value A, root
The lithium salt C of the electrolyte to be measured after dilution is acquired according to absorbance value A and standard curve0, further according to formula calculate to
Survey the lithium salt C of electrolyte；The calculation formula are as follows: C=C0× P/ (6.941 × 1000), in above-mentioned formula: C0: diluted sample
Lithium salt value (mg/L) in product, P: being deionized water to the diluted multiple of water phase lithium salt solution, 6.941 be the atom matter of lithium
Amount.By the above method be repeated twice measurement lithium ion function electrolyte in lithium salts content itself the result is as follows:
| Sample ID | Lithium salt MOL/L |
| Test value 1 | 1.00 |
| Test value 2 | 0.98 |
| Average value | 0.99 |
| Actual value | 1.00 |
| Relative error | - 1% |
Embodiment two
A kind of method that external standard method tests and analyzes component in lithium ion function electrolyte, this method comprises the following steps:
1.1: the drafting of each material standard curve in lithium ion function electrolyte: choosing the electrolyte solvent sample for needing to detect
Product are as follows: propene carbonate, dimethyl carbonate, ethyl acetate, ethyl propionate and methyl acetate；By above-mentioned electrolyte solvent sample
Interior addition toluene, cyclohexylbenzene, fluorinated ethylene carbonate and phosphite ester are configured to mixed liquor as additive, take 6 respectively
100ML volumetric flask is separately added into 4.43g, 8.86g, 17.72g, 26.58g, 35.44g and 44.3g, so into volumetric flask respectively
Analysis level adiponitrile is added into volumetric flask respectively afterwards as diluent, is diluted to 100ML graduation mark, carries out gas chromatograph inspection
It surveys, obtains response, and standard curve is drawn according to the response of the content of each solvent or additive；The gas chromatograph
Testing conditions are as follows: use Shimadzu GC-2014 gas chromatograph, chromatographic column: rtx-5 30*0.25*0.25 low pole chromatographic column is adopted
With the mode of make-up gas, nitrogen pressure 75Kpa, Hydrogen Vapor Pressure 50Kpa, air pressure 50Kpa, column oven takes program
Heating mode: 3min, heating rate are kept in the environment of 45 DEG C are as follows: 10 DEG C/min, be warming up to 250 DEG C and keep 3min；Column
Flow 0.5ml/min, shunt mode, segregation ratio 50, injector temperature are 250 DEG C, and detector temperature is 300 DEG C；Coefficient R
≥0.9999；It is formulated as follows the different mixed standard solution concentration of table and pipettes exact mass:
The canonical plotting of the solvent of drafting and additive referring specifically to such as Fig. 1, Fig. 7, Fig. 8, Fig. 9, Figure 10, Figure 11,
Shown in Figure 12, Figure 13 and Figure 14.
1.2: it is to be detected that 11g the measurement of each material content in lithium ion function electrolyte: is separately added into separatory funnel
Electrolyte is analyzed, 44g saturated brine is then added into separatory funnel, mixed liquor is made, above-mentioned mixed liquor concussion 3-5min is removed
Lithium salts is removed, takes upper layer organic solution or lower layer's organic solution, and filter out the organic molten of 10ML using the syringe filters of 0.2um
The organic solvent of 10ML is placed on 100ML volumetric flask by agent, and analysis level adiponitrile is added as diluent, is diluted to 100ML quarter
Line is spent, the organic solvent in electrolyte to be tested is detected with the gas chromatograph testing conditions in above-mentioned 1.1, is responded
Value obtains the content of each solvent component in analysis electrolyte to be detected by standard curve；Survey is repeated twice by the above method
Determine each solvent component in electrolyte content itself the result is as follows:
2.1: the drafting of lithium salts standard curve in lithium ion function electrolyte: taking the lithium standard solution of 1000mg/L, respectively
1mg, 5mg, 10mg are taken, the lithium standard solution of 20mg is placed in the volumetric flask of 4 different 1000ML, is dilute with deionized water
Agent is released, is diluted to 1000ML graduation mark respectively, concentration is respectively 1mg/L, 5mg/L, 10mg/L, the standard solution of 20mg/L, so
The standard solution after above-mentioned dilution is measured respectively with plasma emission spectrometry (ICP) afterwards, and each according to them
From concentration value C and corresponding absorbance intensity value A make canonical plotting；And equation of linear regression is found out, equation are as follows: y
=2563.9x-1269.6, coefficient R2=1；
2.2: the measurement of lithium salt content in solvent: taking concentration is 37% concentrated hydrochloric acid 100mL, and 100mL deionized water is added
Dilution is stand-by, and hydrochloric acid solution is made；Using pipette or liquid-transfering gun accurately take lithium ion function electrolyte 20mL to be detected in
In the separatory funnel of 125mL, the concussion of 30mL hydrochloric acid solution is added, stands 10min, water phase extracts gained lithium salt solution, is used in combination
After hydrochloric acid is stripped organic phase 2 times, extraction gained water phase lithium salt solution mixed collection three times, 10mL water phase lithium salts is taken after collection
Solution, while it being settled to 100mL with deionized water, which is diluted to 500 times, electrolyte to be detected is made；Use plasma
Body emission spectrometric analyzer carries out plasma emission spectrometry to electrolyte to be detected, obtains their absorbance value A, root
The lithium salt C of the electrolyte to be measured after dilution is acquired according to absorbance value A and standard curve0, further according to formula calculate to
Survey the lithium salt C of electrolyte；The calculation formula are as follows: C=C0× P/ (6.941 × 1000), in above-mentioned formula: C0: diluted sample
Lithium salt value (mg/L) in product, P: being deionized water to the diluted multiple of water phase lithium salt solution, 6.941 be the atom matter of lithium
Amount.By the above method be repeated twice measurement lithium ion function electrolyte in lithium salts content itself the result is as follows:
| Sample ID | Lithium salt MOL/L |
| Test value 1 | 1.00 |
| Test value 2 | 0.99 |
| Average value | 0.995 |
| Actual value | 1.00 |
| Relative error | - 0.50% |
Experimental example
A kind of method that external standard method tests and analyzes component in lithium ion function electrolyte, this method comprises the following steps:
1.1: the drafting of each material standard curve in lithium ion function electrolyte: choosing the electrolyte solvent sample for needing to detect
Product are ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl ester, diethyl carbonate, ethyl acetate, propionic acid
Ethyl ester, methyl acetate；The additive that will be added in above-mentioned electrolyte solvent sample are as follows: vinylene carbonate, toluene, cyclohexyl
Benzene, 1,3 propane sultones, fluorinated ethylene carbonate and phosphite ester are configured to mixed liquor, take 6 100ML capacity respectively
Bottle, is separately added into 4.43g, 8.86g, 17.72g, 26.58g, 35.44g and 44.3g, then respectively to appearance into volumetric flask respectively
Analysis level adiponitrile is added in measuring bottle as diluent, is diluted to 100ML graduation mark, carries out gas chromatograph detection, rung
It should be worth, and standard curve is drawn according to the response of the content of each solvent or additive；The testing conditions of the gas chromatograph
Are as follows: Shimadzu GC-2014 gas chromatograph is used, chromatographic column: rtx-5 30*0.25*0.25 low pole chromatographic column, using make-up gas
Mode, nitrogen pressure 75Kpa, Hydrogen Vapor Pressure 50Kpa, air pressure 50Kpa, column oven takes temperature programming mould
3min, heating rate are kept in the environment of 45 DEG C are as follows: 10 DEG C/min, be warming up to 250 DEG C and keep 3min likes:；Column flow
0.5ml/min, shunt mode, segregation ratio 50, injector temperature are 250 DEG C, and detector temperature is 300 DEG C；
1.2: 11g analysis to be detected the measurement of each material content in lithium ion function electrolyte: being added in separatory funnel
Then electrolyte 44g saturated brine is added into separatory funnel and mixed liquor is made, above-mentioned mixed liquor concussion 3-5min is removed lithium
Salt takes upper layer organic solution or lower layer's organic solution, and filters out organic solvent 10ML using the syringe filters of 0.2um, will
Above-mentioned organic solvent is placed on 100ML volumetric flask, and analysis level adiponitrile is added as diluent, is diluted to 100ML graduation mark, obtains
To response, the content of each component in analysis electrolyte to be detected is obtained by standard curve, as shown in Figure 1；Pass through above-mentioned side
Method be repeated twice measurement electrolyte in each solvent component content itself the result is as follows:
2.1: the drafting of lithium salts standard curve in lithium ion function electrolyte: taking the lithium standard solution of 1000mg/L, respectively
1mg, 5mg, 10mg are taken, the lithium standard solution of 20mg is placed in the volumetric flask of 4 different 1000ML, is dilute with deionized water
Agent is released, is diluted to 1000ML graduation mark respectively, concentration is respectively 1mg/L, 5mg/L, 10mg/L, the standard solution of 20mg/L, so
The standard solution after above-mentioned dilution is measured respectively with plasma emission spectrometry (ICP) afterwards, and each according to them
From concentration value C and corresponding absorbance intensity value A make canonical plotting, as shown in Figure 2；And equation of linear regression is found out,
Equation are as follows: y=2563.9x-1269.6, coefficient R2=1；
2.2: the measurement of lithium salt content in solvent: taking concentration is 37% concentrated hydrochloric acid 100mL, and 100mL deionized water is added
Dilution is stand-by, and hydrochloric acid solution is made；Using pipette or liquid-transfering gun accurately take lithium ion function electrolyte 20mL to be detected in
In the separatory funnel of 125mL, the concussion of 30mL hydrochloric acid solution is added, stands 10min, water phase extracts gained lithium salt solution, is used in combination
After hydrochloric acid is stripped organic phase 2 times, extraction gained water phase lithium salt solution mixed collection three times, 10mL water phase lithium salts is taken after collection
Solution, while it being settled to 100mL with deionized water, which is diluted to 500 times, electrolyte to be detected is made；Use plasma
Body emission spectrometric analyzer carries out plasma emission spectrometry to electrolyte to be detected, obtains their absorbance value A, root
The lithium salt C of the electrolyte to be measured after dilution is acquired according to absorbance value A and standard curve0, further according to formula calculate to
Survey the lithium salt C of electrolyte；The calculation formula are as follows: C=C0× P/ (6.941 × 1000), in above-mentioned formula: C0: diluted sample
Lithium salt value (mg/L) in product, P: being deionized water to the diluted multiple of water phase lithium salt solution, 6.941 be the atom matter of lithium
Amount.
By the above method be repeated twice measurement lithium ion function electrolyte in lithium salts content itself the result is as follows:
| Sample ID | Lithium salt MOL/L |
| Test value 1 | 1.00 |
| Test value 2 | 0.98 |
| Average value | 0.99 |
| Actual value | 1.25 |
| Relative error | - 1.00% |
From the table of experimental example data comparison can be seen that electrolyte sample solvent to be tested test value and actual value it
Between test error within 1.5%, very close test value, the relative error mean value of test exist partial data
0.37%, additive vinylene carbonate lower for content, 1,3 propane sulfonic acid lactones ingredients, according to the difference of its function
Corresponding reaction occurs in the different phase of battery work, as film for additive (vinylene carbonate, 1.3 propane sulfonic acid lactones,
Toluene, cyclohexyl benzene etc.) in the first charge and discharge process of battery i.e. participation film formation reaction, therefore waste is larger, and test is caused to tie
The relative error of fruit and original formulation is larger, and the test between the test value and actual value of electrolyte sample lithium salt content to be tested misses
Difference is within -1%, and very close test value, the relative error mean value of test use external standard method -0.5% to partial data
Detection lithium-ion electrolyte component completes the quantitative analysis of electrolyte, in actual test, it is also necessary to prepare based on the analysis results
A series of difference standard liquids, make corresponding standard curve, test sample, the method in specific test method and project
It is completely the same.
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically
Protection scope bright, that they are not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention
Or change should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of method that external standard method tests and analyzes component in lithium ion function electrolyte, it is characterised in that: this method includes such as
Lower step:
1.1: it is molten the drafting of each material standard curve in lithium ion function electrolyte: to choose at least three kinds of electrolyte for needing to detect
Agent sample；It is configured to mixed liquor by least two or more additives are added in above-mentioned at least three kinds of electrolyte solvent samples, respectively
Take 6 100ML volumetric flasks, be separately added into respectively into volumetric flask 4.43g, 8.86g, 17.72g, 26.58g, 35.44g and
Then 44.3g is added analysis level adiponitrile as diluent into volumetric flask respectively, is diluted to 100ML graduation mark, carries out gas phase
Chromatograph detection obtains response, and draws standard curve according to the response of the content of each solvent or additive；The gas phase
Chromatographic testing conditions are as follows: use Shimadzu GC-2014 gas chromatograph, chromatographic column: rtx-5 30*0.25*0.25 low pole
Chromatographic column, by the way of make-up gas, nitrogen pressure is 75 Kpa, and Hydrogen Vapor Pressure is 50 Kpa, and air pressure is 50 Kpa, column
Incubator takes temperature programming mode: keeping 3min, heating rate in the environment of 45 DEG C are as follows: 10 DEG C/min, is warming up to 250 DEG C
And keep 3min；Column flow 0.5ml/min, shunt mode, segregation ratio 50, injector temperature are 250 DEG C, and detector temperature is
300℃；The electrolyte solvent includes ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl ester, carbonic acid
Diethylester, ethyl acetate, ethyl propionate, methyl acetate；The additive includes vinylene carbonate, toluene, cyclohexylbenzene, 1,
3 propane sultones, fluorinated ethylene carbonate and phosphite ester；
1.2: 11g analysis electrolysis to be detected the measurement of each material content in lithium ion function electrolyte: being added in separatory funnel
Then liquid 44g saturated brine is added into separatory funnel and mixed liquor is made, above-mentioned mixed liquor concussion 3-5min is removed lithium salts,
Upper layer organic solution or lower layer's organic solution are taken, and filters out organic solvent 10ML using the syringe filters of 0.2um, it will be above-mentioned
Organic solvent is placed on 100ML volumetric flask, and analysis level adiponitrile is added as diluent, is diluted to 100ML graduation mark, is rung
It should be worth, the content of each component in analysis electrolyte to be detected is obtained by standard curve；
2.1: the drafting of lithium salts standard curve in lithium ion function electrolyte: taking the lithium standard solution of 1000mg/L, take respectively
The lithium standard solution of 1mg, 5mg, 10mg, 20mg are placed in the volumetric flask of 4 1000 different ML, are dilute with deionized water
Agent is released, is diluted to 1000ML graduation mark respectively, concentration is respectively 1 mg/L, 5mg/L, 10 mg/L, and the standard of 20 mg/L is molten
Then liquid is respectively measured the standard solution after above-mentioned dilution with plasma emission spectrometry (ICP), and according to it
Respective concentration value C and corresponding absorbance intensity value A make canonical plotting；And equation of linear regression is found out, equation
Are as follows: y=2563.9x-1269.6, coefficient R2=1；
2.2: the measurement of lithium salt content in solvent: taking concentration is 37% concentrated hydrochloric acid 100mL, and the dilution of 100 mL deionized waters is added
For use, hydrochloric acid solution is made；Accurately take lithium ion function electrolyte 20mL to be detected in 125mL using pipette or liquid-transfering gun
Separatory funnel in, the concussion of 30mL hydrochloric acid solution is added, stands 10min, water phase extracts gained lithium salt solution, and anti-with hydrochloric acid
After extraction organic phase 2 times, extraction gained water phase lithium salt solution mixed collection three times, 10mL water phase lithium salt solution is taken after collection,
It is settled to 100mL with deionized water simultaneously, which is diluted to 500 times, electrolyte to be detected is made；Use plasma emission
Spectroanalysis instrument carries out plasma emission spectrometry to electrolyte to be detected, their absorbance value A is obtained, according to extinction
Angle value A and standard curve acquire the lithium salt C of the electrolyte to be measured after dilution0, electrolysis to be measured is calculated further according to formula
The lithium salt C of liquid；The calculation formula are as follows: C=C0× P/(6.941 × 1000), in above-mentioned formula: C0: in dilute sample
Lithium salt value (mg/L), P: being deionized water to the diluted multiple of water phase lithium salt solution, 6.941 be the atomic mass of lithium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111257470A (en) * | 2020-03-03 | 2020-06-09 | 广州天赐高新材料股份有限公司 | Pretreatment method for detecting organic solvent in electrolyte and detection method |
| CN111474165A (en) * | 2020-04-03 | 2020-07-31 | 河南华瑞高新材料有限公司 | Method for testing concentration content of lithium hexafluorophosphate in lithium ion functional electrolyte by using ICP (inductively coupled plasma) |
| CN111474251A (en) * | 2020-04-08 | 2020-07-31 | 河南华瑞高新材料有限公司 | Method for monitoring organic components in electrolyte production process by using area correction normalization method |
| CN111999417A (en) * | 2020-09-03 | 2020-11-27 | 江苏华盛锂电材料股份有限公司 | Method for measuring residual solvent in solid electrolyte lithium salt |
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2018
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111257470A (en) * | 2020-03-03 | 2020-06-09 | 广州天赐高新材料股份有限公司 | Pretreatment method for detecting organic solvent in electrolyte and detection method |
| CN111474165A (en) * | 2020-04-03 | 2020-07-31 | 河南华瑞高新材料有限公司 | Method for testing concentration content of lithium hexafluorophosphate in lithium ion functional electrolyte by using ICP (inductively coupled plasma) |
| CN111474251A (en) * | 2020-04-08 | 2020-07-31 | 河南华瑞高新材料有限公司 | Method for monitoring organic components in electrolyte production process by using area correction normalization method |
| CN111999417A (en) * | 2020-09-03 | 2020-11-27 | 江苏华盛锂电材料股份有限公司 | Method for measuring residual solvent in solid electrolyte lithium salt |
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