CN116718692A - Method for measuring sulfate radical content by ion chromatography - Google Patents
Method for measuring sulfate radical content by ion chromatography Download PDFInfo
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- CN116718692A CN116718692A CN202310647677.3A CN202310647677A CN116718692A CN 116718692 A CN116718692 A CN 116718692A CN 202310647677 A CN202310647677 A CN 202310647677A CN 116718692 A CN116718692 A CN 116718692A
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004255 ion exchange chromatography Methods 0.000 title claims abstract description 28
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 42
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000010405 anode material Substances 0.000 claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 239000012086 standard solution Substances 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims abstract description 6
- 239000007924 injection Substances 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 26
- 238000001514 detection method Methods 0.000 abstract description 14
- 238000004458 analytical method Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- -1 sulfate radical Chemical class 0.000 description 26
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 12
- 239000012071 phase Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004879 turbidimetry Methods 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004848 nephelometry Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for measuring sulfate radical content by ion chromatography, which is mainly used for measuring the sulfate radical content in a lithium nickel manganese oxide anode material and comprises the following specific steps: 1) Preparing sulfate ion standard solution, detecting by using an ion chromatograph sample injection to obtain conductance-retention time chromatograms of sulfate content standard samples with different concentrations, and formulating a peak area-concentration standard curve of sulfate content; 2) Treating a lithium nickel manganese oxide positive electrode material solution; 3) And detecting the processed lithium nickel manganese oxide positive electrode material solution by adopting an ion chromatography method, and comparing a conductivity-retention time chromatogram of the lithium nickel manganese oxide positive electrode material solution with a peak area-concentration standard curve of sulfate radical content to obtain the content of the sulfate radical. The detection method provided by the invention has the advantages of higher precision, low detection limit, wide measurement range reaching 0.01-0.7%, higher precision, suitability for mass rapid sample analysis, and more effective detection means for the production process optimization and product quality analysis of the lithium nickel manganese oxide anode material.
Description
Technical Field
The invention belongs to the technical field of sulfate radical content determination, and particularly relates to a method for determining sulfate radical content by ion chromatography.
Background
The performance of the lithium battery depends on the anode material to a great extent, and the lithium nickel manganese oxide anode material has the advantages of abundant resources, low cost, environmental friendliness, high voltage, high energy density and the like, is widely applied in the high-power field, and becomes a research hot spot. In the process of preparing the lithium nickel manganese oxide, a certain amount of sulfate can be remained, so that the sulfate content is an important technical index of a finished product, and the rapid and accurate determination of the sulfate content in the lithium nickel manganese oxide anode material can provide convenience for production. At present, the method for measuring sulfate radical in the lithium nickel manganese oxide anode material mainly comprises a barium sulfate turbidimetry, but the measurement result of the barium sulfate turbidimetry is not ideal, the measurement range is only 0.1-0.7%, the detection cannot be performed when the sulfate radical content is lower than 0.1%, the precision is not enough, the condition and the consumption of the added barium nitrate are required to be high by the barium sulfate turbidimetry, the standing time before the measurement is also strict, the measurement needs to be completed within 15-30 minutes after the standing, and meanwhile, the operation method of experimenters is required to be strict, so that the method is not suitable for large-batch rapid measurement.
Disclosure of Invention
Aiming at the defects of the existing sulfate radical content detection technology, the invention provides a method for measuring the sulfate radical content by ion chromatography, which is mainly used for measuring the sulfate radical content in a lithium nickel manganese oxide positive electrode material, and compared with the method in the prior art, the method has the measurement range of 0.01-0.7% of sulfate radical ions in the positive electrode material; the measurement accuracy is higher, the sulfate radical content can be detected when the sulfate radical content is lower than 0.1%, and the measurement time is short.
The invention discloses a method for measuring sulfate radical content by ion chromatography, which is mainly used for measuring the sulfate radical content in a lithium nickel manganese oxide anode material and comprises the following specific steps:
1) Preparing sulfate ion standard solution, detecting by using an ion chromatograph sample injection to obtain conductance-retention time chromatograms of sulfate content standard samples with different concentrations, and formulating a peak area-concentration standard curve of sulfate content;
2) Treating a lithium nickel manganese oxide positive electrode material solution;
3) And detecting the processed lithium nickel manganese oxide positive electrode material solution by adopting an ion chromatography method, and comparing a conductivity-retention time chromatogram of the lithium nickel manganese oxide positive electrode material solution with a peak area-concentration standard curve of sulfate radical content to obtain the content of the sulfate radical.
Preferably, the method for treating the lithium nickel manganese oxide positive electrode material solution in the step 2) is as follows:
a. and (3) drying: drying the lithium nickel manganese oxide anode material in an oven, and then placing the dried lithium nickel manganese oxide anode material in a dryer, and cooling the dried lithium nickel manganese oxide anode material to room temperature;
b. preparing a solution: weighing the dried lithium nickel manganese oxide anode material, putting the dried lithium nickel manganese oxide anode material into a container, slowly adding hydrochloric acid, adding hydrogen peroxide, heating at a low temperature until the lithium nickel manganese oxide anode material is completely dissolved, continuously heating and evaporating until the state that only small dew is left at the bottom of the container, cooling, adding water for dissolving, transferring the solution into a volumetric flask, washing the container with water, transferring washing liquid into the volumetric flask, diluting with water, and shaking uniformly to obtain a lithium nickel manganese oxide anode material solution;
c. solution filtration: and (3) activating the H column and the Ag column by using water, standing for 10-15min, slowly passing the lithium nickel manganese oxide positive electrode material solution through the activated H column and the activated Ag column, discarding the first third filtrate, obtaining a sufficient amount of subsequent filtrate, and filtering the filtrate by a polyether sulfone syringe filter to obtain the treated lithium nickel manganese oxide positive electrode material solution.
Preferably, the drying temperature in the step a is 100-120 ℃ and the drying time is 2-3h.
Preferably, in the step b, the concentration of hydrochloric acid is 36.5%, and the concentration of hydrogen peroxide is 30%.
Preferably, 3ml of hydrochloric acid and 0.5ml of hydrogen peroxide are used for dissolving each 0.2g of lithium nickel manganese oxide positive electrode material solution in the preparation solution in the step b.
Preferably, the low temperature heating temperature in the step b is 100-150 ℃.
Preferably, the specification of the polyethersulfone syringe filter in the step c is 0.22 μm.
PreferablyIn the step 3), the ion chromatography condition is that a Metrosep ASuppp 5-250/4.0 chromatographic column is adopted as the chromatographic column, the flow rate of a mobile phase is 0.7-0.75mL/min, and the mmol/LNa of the mobile phase is 4.54mmol/LNa 2 CO 3 -0.8mmol/LNaHCO 3 The solution has a sample injection volume of 20-25 mu L.
Compared with the prior art, the invention has the following advantages:
the method reduces the interference of chloride ions on the measurement of sulfate radical by evaporating the solution at low temperature before constant volume, does not influence the peak time of sulfate radical ions, improves the detection precision, and samples and measures the sulfate radical by purifying through H-type and Ag-type solid phase extraction columns on an ion chromatograph. The ion chromatography has higher precision, low detection limit and wide measurement range, and can reach 0.01-0.7%, while the barium sulfate nephelometry in the prior art can only reach 0.1%; the method has higher precision, is suitable for mass rapid sample analysis, and provides a more effective detection means for the production process optimization and the product quality analysis of the lithium nickel manganese oxide anode material.
Drawings
FIG. 1 is an ion chromatogram of mobile phases of different concentrations in an embodiment of the invention;
FIG. 2 is a graph showing the drying by evaporation and non-drying by evaporation of a test sample before volume fixing in an embodiment of the invention;
FIG. 3 is a graph showing the detection patterns of chloride ions passing through H columns and Ag columns in the embodiment of the invention;
FIG. 4 is a graph showing the detection patterns of chloride ions passing through an Ag column and a H column and an Ag column in the embodiment of the invention;
description of the embodiments
The present invention will be described in further detail with reference to the following examples
Examples
A method for measuring sulfate radical content by ion chromatography comprises the following specific steps:
1) Preparing standard curve solution:
accurately transferring 10mL of sulfate ion standard solution into a 100mL volumetric flask by using a pipette, adding water to dilute to an end point scale, shaking uniformly, and placing in a refrigerator at 4 ℃ for storage to obtain stock solution; accurately transferring 0mL, 0.50mL, 1.25mL, 2.50mL, 5.0mL and 10.0mL stock solutions respectively by using a pipette, placing the stock solutions respectively in 50mL volumetric flasks, adding water to dilute to an end point scale, shaking uniformly, and standing for measurement;
2) Drying the lithium nickel manganese oxide anode material at 110 ℃ for 2.5 hours, then placing the lithium nickel manganese oxide anode material in a dryer, and cooling the lithium nickel manganese oxide anode material to room temperature;
3) Weighing 0.2g of dried lithium nickel manganese oxide anode material, putting the lithium nickel manganese oxide anode material into a 100mL beaker, slowly adding 3mL of hydrochloric acid, adding 0.5mL of hydrogen peroxide, heating to 120 ℃ at low temperature until the lithium nickel manganese oxide anode material is completely dissolved and evaporated to the bottom of the beaker, leaving only small dew, cooling, adding 5mL of water for dissolving, transferring the lithium nickel manganese oxide anode material into a 100mL volumetric flask, washing the beaker with water, transferring the washing solution into the volumetric flask, diluting the washing solution to 100mL with water, and shaking uniformly;
4) Activating the H column and the Ag column with 10mL of water, standing for 10min, slowly passing the solution prepared in the step 2) through the activated H column and the activated Ag column, discarding the previous 3mL of filtrate, obtaining the subsequent 2mL of filtrate, passing through a 0.22 mu m polyether sulfone syringe filter, and loading to be detected;
5) Analyzing the filtrate obtained in the step 3) by adopting an ion chromatography, wherein a chromatographic column adopts a Metrosep ASuppp 5-250/4.0 chromatographic column, the flow rate is 0.7mL/min, and the mobile phase is 4.54mmol/LNa 2 CO 3 -0.8mmol/LNaHCO 3 The solution was sampled to a volume of 20. Mu.L and the conductivity detector. Detecting conductivity-retention time chromatograms of sulfate radical content standard samples with different concentrations, and making a peak area-concentration standard curve of the sulfate radical content; detecting the conductivity-retention time chromatogram of the filtrate, and comparing with the peak area-concentration standard curve of sulfate radical content to obtain the sulfate radical content in the filtrate.
In order to examine the interference of other anions on sulfate ion peak integration, 7 anion mixed standard solutions are selected for separation, and three different concentration flows are used for eluting and separating relative to the standard solution to be detected respectively. The results are shown in FIG. 1, and the information such as specific concentration is shown in Table 1.
TABLE 1 Peak time of mobile phases at different concentrations
From FIGS. 1 and Table 1, it can be seen that the mobile phases of three concentrations are all good for separating 7 anions, but from the time, resource and environmental point of view 1 is selected to peak earlier # The mobile phase saves time and resources, and the fewer mobile phases reduce the treatment of waste liquid so as to be more environment-friendly.
The sample is dissolved by adding nitric acid and hydrochloric acid into hydrogen peroxide, and the test results when the sample amounts are 0.2g are shown in Table 2. As can be seen from Table 2, nitric acid is difficult to dissolve the sample, hydrochloric acid can dissolve the sample but the speed is slow, hydrochloric acid and hydrogen peroxide are added into the sample and mixed uniformly, and the sample can be completely dissolved by slightly heating the sample on a low-temperature electric hot plate for a few minutes.
TABLE 2 sample dissolution method
Since chloride ions also peak when measured by ion chromatography, too high a concentration can result in tailing and can severely affect the peak and integration of sulfate ions. Hydrochloric acid in the solution contains a large amount of chloride ions, and therefore, the amount of hydrochloric acid added should be as small as possible under conditions that ensure dissolution of the sample. Therefore, a series of tests of the addition amounts of hydrochloric acid and hydrogen peroxide were performed. Table 3 shows the test results of different amounts of hydrochloric acid and hydrogen peroxide added when the sample amount was 0.2 g. As shown in the results in Table 3, when the sample weighing amount is 0.2g, the hydrochloric acid consumption is 3mL, and the hydrogen peroxide consumption is 0.5mL, the sample can be just completely dissolved in a few minutes of micro heat on the low-temperature electric heating plate, and the measurement and analysis requirements are met. Therefore, when the sample amount is 0.2g, 3mL of hydrochloric acid and 0.5mL of hydrogen peroxide are selected as a sample dissolution system.
TABLE 3 hydrochloric acid+Hydrogen peroxide addition test
Since chloride ions have a certain interference with the measurement of sulfate, and a part of the added hydrochloric acid can be evaporated by heating, a comparative test of whether or not to evaporate before constant volume was performed, and the result is shown in fig. 2. As can be seen from FIG. 2, the chloride ion peak is wide and long without evaporation to dryness, which has affected the sulfate ion peak time, while the evaporated chloride ion peak is still wide but significantly smaller, and does not affect the sulfate ion peak time. Therefore, evaporation to dryness is advantageous for sulfate determination, and therefore, the solution is optionally heated to near dryness at low temperature prior to constant volume.
Because the solution contains metal ions such as lithium, sodium, potassium, calcium, iron, copper, chromium, cadmium and the like and residual chloride ions, the solution needs to be purified by a column before sample injection. The H column is selected to remove metal ions possibly existing in the solution and the Ag column is selected to remove chloride ions in the solution, and the results are shown in fig. 3 and 4. As can be seen from FIG. 3, the chloride ion peak is particularly high when the solution passes through the H column only, and the measurement of sulfate ions is seriously affected; while the chloride ion peak is greatly reduced when passing through the H column and the Ag column, the measurement of sulfate radical is facilitated, and as can be seen from FIG. 4, the interference peak is generated near the sulfate radical ion when only passing through the Ag column, but the interference peak is not generated when passing through the H column and the Ag column. Therefore, in summary, it is preferable to select H column+Ag column.
The mixed standard working solutions were separately measured. And drawing a calibration curve by taking the sulfate radical mass concentration (x) as an abscissa and the chromatographic peak area (y) as an ordinate. The result shows that the linear range of sulfate ions is 0-20.0 mug/L, and the linear equation is y= 8.54057 ×10 -3 +7.01333×10 -3 x, the correlation coefficient is 0.9998.
According to the measurement specification JJG823-2014, selecting corresponding 1.0 mug.L -1 The sulfate standard solution was subjected to 11 replicates and the limit of detection was calculated to be 0.01. Mu.g/L, with the 4-fold limit of detection concentration being used as the limit of quantification according to EPA SW-846 method specifications being 0.04. Mu.g/L.
And selecting 4 products with different grades, and respectively carrying out 11 times of parallel measurement on the sulfate radical content in the sample according to a set experimental method. 11 measured values were obtained, and the mean, standard deviation and relative standard deviation were calculated, the results are shown in Table 4, and the results prove that the precision meets the analysis requirements.
Table 4 results of the method precision experiments
Since no corresponding lithium nickel manganese oxide standard sample exists at present, the sample is subjected to standard adding recovery tests by adding sulfate ions with different contents into the sample, and sample treatment and measurement are carried out according to a test method, and the results are shown in Table 5. The method has the standard adding recovery rate of 96.1-106.3%, and can meet the measurement requirement.
Table 5 labeled recovery test
The results of the ion chromatography and the barium sulfate turbidimetry were respectively tested and are shown in table 6. As is clear from Table 6, the results of the two methods are not very different when the content is high, but the measurement result by the barium sulfate nephelometry is not ideal when the content is low. In addition, the barium sulfate nephelometry requires high conditions and usage of added barium nitrate, the standing time before measurement is also strict, measurement is required to be completed within a certain time, and the operation method of experimenters is strictly required, so that the method is not suitable for batch measurement. The pretreatment of the ion chromatography is simple and convenient, the stability of the sample after the treatment is good, and the method can be used for measuring a large number of samples.
Table 6 determination of sulfate content in lithium nickel manganate
In the experimental process, the ion chromatography and the barium sulfate turbidimetry are compared in terms of sample weighing, detection limit, pretreatment and the like, and the specific comparison results are shown in Table 7.
Table 7 comparison of the two methods
As is clear from Table 7, the ion chromatography method has a reliable measurement result, a low detection limit, and a good stability of the pretreated sample. Thus, ion chromatography is better than barium sulfate nephelometry, both in terms of accuracy of results and measurement range and in terms of efficiency.
The foregoing is merely exemplary embodiments of the present invention, and it should be noted that various changes, modifications, substitutions and alterations can be made herein by those skilled in the art without departing from the technical principles of the present invention, which are also intended to be regarded as the scope of the invention.
Claims (8)
1. The method for measuring the sulfate radical content by using the ion chromatography is mainly used for measuring the sulfate radical content in the lithium nickel manganese oxide anode material and is characterized by comprising the following specific steps of:
1) Preparing sulfate ion standard solution, detecting by using an ion chromatograph sample injection to obtain conductance-retention time chromatograms of sulfate content standard samples with different concentrations, and formulating a peak area-concentration standard curve of sulfate content;
2) Treating a lithium nickel manganese oxide positive electrode material solution;
3) And detecting the processed lithium nickel manganese oxide positive electrode material solution by adopting an ion chromatography method, and comparing a conductivity-retention time chromatogram of the lithium nickel manganese oxide positive electrode material solution with a peak area-concentration standard curve of sulfate radical content to obtain the content of the sulfate radical.
2. The method for measuring sulfate radical content by ion chromatography according to claim 1, wherein the method for treating the lithium nickel manganese oxide positive electrode material solution in the step 2) is as follows:
a. and (3) drying: drying the lithium nickel manganese oxide anode material in an oven, and then placing the dried lithium nickel manganese oxide anode material in a dryer, and cooling the dried lithium nickel manganese oxide anode material to room temperature;
b. preparing a solution: weighing the dried lithium nickel manganese oxide anode material, putting the dried lithium nickel manganese oxide anode material into a container, slowly adding hydrochloric acid, adding hydrogen peroxide, heating at a low temperature until the lithium nickel manganese oxide anode material is completely dissolved, continuously heating and evaporating until the state that only small dew is left at the bottom of the container, cooling, adding water for dissolving, transferring the solution into a volumetric flask, washing the container with water, transferring washing liquid into the volumetric flask, diluting with water, and shaking uniformly to obtain a lithium nickel manganese oxide anode material solution;
c. solution filtration: and (3) activating the H column and the Ag column by using water, standing for 10-15min, slowly passing the lithium nickel manganese oxide positive electrode material solution through the activated H column and the activated Ag column, discarding the first third filtrate, obtaining a sufficient amount of subsequent filtrate, and filtering the filtrate by a polyether sulfone syringe filter to obtain the treated lithium nickel manganese oxide positive electrode material solution.
3. The method for measuring sulfate content by ion chromatography according to claim 2, wherein the drying temperature in the step a is 100-120 ℃ and the drying time is 2-3h.
4. The method for measuring sulfate content by ion chromatography according to claim 2, wherein the hydrochloric acid concentration in the step b is 36.5% and the hydrogen peroxide concentration is 30%.
5. The method for measuring sulfate content by ion chromatography according to claim 2, wherein 3ml of hydrochloric acid and 0.5ml of hydrogen peroxide are used for dissolving each 0.2g of lithium nickel manganese oxide positive electrode material solution in the configuration solution in the step b.
6. The method for measuring sulfate content by ion chromatography according to claim 2, wherein the low temperature heating temperature in the step b is 100-150 ℃.
7. The method for measuring sulfate content by ion chromatography according to claim 2, wherein the specification of the polyethersulfone syringe filter in the step c is 0.22 μm.
8. The method for determining sulfate content by ion chromatography according to claim 1, wherein the ion chromatography in step 3) is performed byThe component is a chromatographic column selected from Metrosep ASupp5-250/4.0 chromatographic column, mobile phase flow rate of 0.7-0.75mL/min, mobile phase of 4.54mmol/LNa 2 CO 3 -0.8mmol/LNaHCO 3 The solution has a sample injection volume of 20-25 mu L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723476A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing lithium-ion battery anode material lithium nickel manganese dioxide (LiNiMnO2) |
| CN113008808A (en) * | 2019-12-19 | 2021-06-22 | 格林美（江苏）钴业股份有限公司 | Method for detecting nickel, cobalt, manganese and sulfate radicals in precursor of ternary cathode material |
| CN114270185A (en) * | 2019-08-29 | 2022-04-01 | 瑞士万通集团公司 | Method and device for determining at least one analyte substance in an analyte solution |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723476A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing lithium-ion battery anode material lithium nickel manganese dioxide (LiNiMnO2) |
| CN114270185A (en) * | 2019-08-29 | 2022-04-01 | 瑞士万通集团公司 | Method and device for determining at least one analyte substance in an analyte solution |
| CN113008808A (en) * | 2019-12-19 | 2021-06-22 | 格林美（江苏）钴业股份有限公司 | Method for detecting nickel, cobalt, manganese and sulfate radicals in precursor of ternary cathode material |
Non-Patent Citations (3)
| Title |
|---|
| MARCEL HEIDBÜCHEL 等: "Enabling Aqueous Processing of Ni-Rich Layered Oxide Cathode Materials by Addition of Lithium Sulfate", 《CHEMSUSCHEM》, pages 1 - 11 * |
| 李莎 等: "离子色谱法测定富锂锰基正极材料中的硫酸根", 《化学研究与应用》, vol. 33, no. 9, pages 1844 - 1848 * |
| 马兵兵 等: "超声提取-离子色谱法测定土壤中10 种水溶性阴离子", 《土壤》, vol. 51, no. 6, pages 1253 - 1256 * |
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