CN117169264A - Method for measuring content of lithium element in lithium-boron alloy - Google Patents
Method for measuring content of lithium element in lithium-boron alloy Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910000521 B alloy Inorganic materials 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- 238000005259 measurement Methods 0.000 claims abstract description 42
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 15
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 14
- 239000000523 sample Substances 0.000 claims description 98
- 238000001228 spectrum Methods 0.000 claims description 34
- 238000004458 analytical method Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 238000012937 correction Methods 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012488 sample solution Substances 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
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- 238000002360 preparation method Methods 0.000 abstract description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
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- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 239000011573 trace mineral Substances 0.000 description 1
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- 238000004846 x-ray emission Methods 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
Classifications
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- 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
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for measuring the content of lithium element in a lithium boron alloy, which comprises the following steps: s1) selecting a plurality of standard samples with different lithium contents to form a standard sample library; s2) firstly, placing a standard sample into an X-ray fluorescence spectrometer to measure and obtain a measured value of the concentration of the lithium element, and recording a first deviation value with the standard content; s3) continuously measuring the content of the lithium element in the standard sample by adopting an inductively coupled plasma emission spectrometer, and recording a second deviation value of the measured content of the lithium element and the standard content; s4) obtaining a first measured value of lithium content by adopting an X-ray fluorescence spectrometer to a sample to be analyzed; s5) taking the first deviation value corresponding to the first measured value as a comparison reference value, and if the comparison reference value exceeds a preset threshold value, continuously measuring the concentration of the lithium element in the sample to be analyzed by using an inductively coupled plasma emission spectrometer. The invention greatly improves the measurement precision; the method is suitable for measuring various lithium contents in the sample, has high sensitivity, and is simple and convenient for sample preparation and pretreatment.
Description
Technical Field
The invention relates to a method for measuring lithium, in particular to a method for measuring the content of lithium element in a lithium-boron alloy.
Background
The lithium content measuring method refers to measuring the content of lithium element in a sample by a series of chemical analysis methods. Lithium is an important chemical element and is widely used in the fields of manufacturing lithium batteries, alloy ceramics and the like. Therefore, accurate determination of lithium content is of great importance to the relevant industry.
Common lithium content measurement methods include flame atomic absorption spectrometry, inductively coupled plasma method, ion selective electrode method, and the like. The principle of flame atomic absorption spectrometry is that atoms in a sample are converted into gaseous atoms, the absorption light intensity is measured at a specific wavelength, and the lithium content in the sample is calculated by comparing the absorption light intensities of a standard solution and the sample. The ion selective electrode rule is a method based on electrochemical principle, which selectively adsorbs lithium ions on the surface of an electrode, and calculates the lithium content by measuring the change of the electrode potential. Has lower detection limit than the atomic absorption method, and is the most advanced method in the field of trace element analysis. However, the price is expensive and the pollution is easy to occur; the sample is generally digested to obtain a liquid sample, and components to be tested cannot be lost in the digestion process, so that interference substances cannot be introduced, and the method is safe and quick and does not cause difficulty in the subsequent operation steps; meanwhile, the use is complex and the cost is high.
From the above, the selection of the lithium content measurement method should be comprehensively considered according to the characteristics of the sample, the purpose of measurement, the availability of equipment and other factors.
The lithium-boron alloy is an anode material of a new generation of thermal battery, and has the characteristics of high lithium content, large specific capacity, electrochemical performance close to that of pure lithium and the like. The lithium-boron alloy is a composite material composed of a porous heat-resistant skeleton of a lithium-boron compound and metal lithium filled in pores, and mainly contains lithium, boron, magnesium, aluminum, calcium, iron, chromium and other elements. The components and the content of main elements and impurity elements in the lithium-boron alloy have direct influence on the performance of the thermal battery, and the accurate determination of the lithium content has important significance for the research and the production of the lithium-boron alloy material. However, the existing measuring methods have different advantages and disadvantages, and the measurement of lithium in the lithium-boron alloy is easily interfered by boron or elements such as magnesium, aluminum, calcium, iron, chromium and the like, so that the ideal test effect is difficult to obtain by a single testing method, and therefore, the existing testing method needs to be continuously improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for measuring the content of lithium element in lithium-boron alloy, which has high measurement precision, does not consume a sample to be measured, and has relatively low test cost.
The invention provides a method for measuring the content of lithium element in a lithium boron alloy, which aims to solve the technical problems and comprises the following steps: s1) selecting a plurality of standard samples with different lithium contents to form a standard sample library; s2) firstly, placing the standard sample subjected to surface treatment into an X-ray fluorescence spectrometer for full coverage scanning, measuring to obtain a measured value of lithium element concentration, recording a first deviation value with standard content, collecting a spectrum of the standard sample, and correcting the spectrum of the standard sample to obtain a standard working curve; s3) continuing to digest the standard sample to obtain a standard sample solution, measuring the content of lithium element by using an inductively coupled plasma emission spectrometer, and recording a second deviation value of the measured content of lithium element and the standard content; s4) carrying out surface treatment on the sample to be analyzed, calibrating the position of an analysis point in an observation area by adopting an X-ray fluorescence spectrometer, and processing analysis data in the observation area of the sample to be analyzed by utilizing a standard working curve to obtain a first measurement value of lithium content; s5) taking the first deviation value corresponding to the first measured value as a comparison reference value, if the comparison reference value exceeds a preset threshold value, continuously measuring a second measured value of the lithium element concentration of the sample to be analyzed by using the inductively coupled plasma emission spectrometer, correcting the second measured value by using the second deviation value as a final measured value, and otherwise, directly taking the first measured value as the final measured value.
Further, if the second deviation value corresponding to the second measured value of the lithium element concentration obtained in step S5 also exceeds the preset threshold value, and the second deviation value and the first deviation value are opposite in sign, taking the average value of the corrected second measured value and the first measured value as the final measured value.
Further, if the second deviation value corresponding to the second measured value of the lithium element concentration obtained in step S5 also exceeds the preset threshold, and the second deviation value is the same as the first deviation value in positive and negative, then the following is continuously determined: if the second deviation value and the first deviation value are both positive, indicating that the actual measured value is smaller, and taking the larger value of the first measured value and the second measured value as the final measured value; if the second deviation value and the first deviation value are both negative, this indicates that the actual measurement value is large, and therefore the smaller of the first measurement value and the second measurement value is taken as the final measurement value.
Further, the standard sample and the sample to be analyzed are subjected to surface grinding by using grinding equipment, and then cut, so that the diameters of the standard sample and the sample to be analyzed are within the range of 30-300 mm.
Further, in the step S1, standard samples with lithium content of 20.x%, 30.x%, 40.x%, 50.x%, 60.x%, 70.x%, 80.x% and 90.x% are selected to form a standard sample library, and in the step S2, first deviation values with corresponding content are obtained respectively, and in the step S5, the first deviation value with the closest lithium content is selected as a comparison reference value, or two adjacent first deviation values are adopted to be fitted through interpolation as the comparison reference value.
Further, the step S2 corrects the spectrum of the standard sample as follows: firstly, carrying out fitting background treatment on the obtained standard sample spectrum, and deducting background values of the characteristic spectrum and other spectrum peaks to obtain the net intensity of the characteristic spectrum; performing overlap correction on the interference spectrum line to obtain the net strength of the element to be detected; correcting the matrix effect by using the first deviation value to obtain a standard working curve; and the step S3 further comprises the step of measuring the content of boron element by adopting an inductively coupled plasma emission spectrometer, and the step S2 carries out overlap correction on interference spectral lines caused by the boron element.
Further, the X-ray fluorescence spectrometer comprises a high-voltage generator, an X-ray tube, a detector and a recording unit; the spectrum of the standard sample or the sample to be analyzed is collected, including analysis spectrum type, voltage and current of the X-ray tube, detector type, analysis time, region of interest calibration and correction curve type.
Further, the standard sample or the sample to be analyzed is added into a mixed solution of hydrofluoric acid and hydrogen peroxide for digestion.
Further, the digestion process of the standard sample or the sample to be analyzed is as follows: s31, taking a standard sample or a sample to be analyzed, placing the standard sample or the sample to be analyzed in a container, mixing the sample with nitric acid and hydrogen peroxide, and heating the mixture to boiling for reaction to obtain a reaction liquid A; s32, mixing the reaction solution A with hydrogen peroxide in a boiling state to perform oxidation reaction; s33, adding hydrochloric acid in a boiling state for continuous reaction; s34, flushing the wall of the container with water, continuing to react in a boiling state, and evaporating the concentrated solution; s35, flushing the wall of the container with water, cooling the solution to 55-60 ℃, maintaining the temperature, adding hydrofluoric acid, standing for reaction until the sample is completely digested, and clarifying the solution; s36, cooling and fixing the volume to obtain the standard sample solution.
Further, the analysis step in the step S4 is 1mm, 2mm, 5mm or 10mm, the scanning area is 100-1000 mm in length and 100-500 mm in width.
Compared with the prior art, the invention has the following beneficial effects: according to the method for measuring the content of the lithium element in the lithium-boron alloy, the X-ray fluorescence spectrum is adopted for measurement, a sample to be measured is not lost, and the test cost is relatively low; if the predicted precision does not meet the preset requirement, the inductively coupled plasma emission spectrometer is continuously adopted for measurement, so that the measurement precision is greatly improved; the method is suitable for measuring various lithium contents in the sample, has high sensitivity, is simple and convenient for sample preparation and pretreatment, can effectively avoid introducing impurity pollution, and reduces operation difficulty.
Drawings
FIG. 1 is a flow chart of the determination of lithium in a lithium boron alloy of the invention.
Detailed Description
The invention is further described below with reference to the drawings and examples.
X-ray fluorescence spectroscopy is a method that uses the change in absorption of X-rays by a sample as a function of the composition in the sample and how much it changes to determine the composition in the sample qualitatively or quantitatively. The X-ray fluorescence spectrum has the advantages of no damage to the surface of a sample, high analysis speed, high precision, simple sample preparation, simultaneous detection of multiple elements and the like, and can be used as a quantitative analysis method for representing the component distribution of the high-temperature alloy, but has the defect of easy interference when the spectrum is used for quantitative analysis. The applicant utilizes X-ray fluorescence spectrum to measure the content of lithium element in the lithium-boron alloy, and finds that the content is easy to be interfered by boron or elements such as magnesium, aluminum, calcium, iron, chromium and the like as impurities, and finally the measurement accuracy can be influenced. Although X-ray fluorescence measurements are typically calibrated, if the calibration value is too large to exceed a preset threshold, the accuracy of the calibrated measurement may not meet the final measurement requirements. In fact, the existing measurement methods have advantages and disadvantages, and a single measurement mode often cannot fully meet the measurement requirement of high-precision lithium element content. For this purpose, the applicant, when determining the standard sample and determining the standard curve, pre-records a first deviation value (i.e. correction value) from the standard content; if the correction value is too large, the estimated accuracy can not meet the measurement requirement, and the inductively coupled plasma emission spectrometer is continuously used for measurement, so that the measurement accuracy is greatly improved.
Referring to fig. 1, the method for determining the content of lithium element in the lithium boron alloy provided by the invention comprises the following steps:
s1) selecting a plurality of standard samples with different lithium contents to form a standard sample library;
s2) firstly, placing the standard sample subjected to surface treatment into an X-ray fluorescence spectrometer for full coverage scanning, measuring to obtain a measured value of lithium element concentration, recording a first deviation value with standard content, collecting a spectrum of the standard sample, and correcting the spectrum of the standard sample to obtain a standard working curve;
s3) continuing to digest the standard sample to obtain a standard sample solution, measuring the content of lithium element by using an inductively coupled plasma emission spectrometer, and recording a second deviation value of the measured content of lithium element and the standard content;
s4) carrying out surface treatment on the sample to be analyzed, calibrating the position of an analysis point in an observation area by adopting an X-ray fluorescence spectrometer, and processing analysis data in the observation area of the sample to be analyzed by utilizing a standard working curve to obtain a first measurement value of lithium content;
s5) taking the first deviation value corresponding to the first measured value as a comparison reference value, if the comparison reference value exceeds a preset threshold value, continuously measuring a second measured value of the lithium element concentration of the sample to be analyzed by using the inductively coupled plasma emission spectrometer, correcting the second measured value by using the second deviation value as a final measured value, and otherwise, directly taking the first measured value as the final measured value.
It is sometimes possible that the accuracy requirement cannot be met by using both the above-mentioned measurement methods, that is, the second deviation value corresponding to the second measurement value of the lithium element concentration obtained in step S5 also exceeds the preset threshold. In this case, the analysis can be further performed in the following two cases. The first case is that the second deviation value is opposite to the first deviation value in positive and negative, and one measured value is larger than the true value, and the other measured value is smaller than the true value, so that the average value of the corrected second measured value and the corrected first measured value is taken as a final measured value, and the measurement accuracy is improved by partial cancellation of measurement errors. In another case, if the second deviation value is the same as the first deviation value, the following is continued: if the second deviation value and the first deviation value are both positive, indicating that the actual measured value is smaller, and taking the larger value of the first measured value and the second measured value as the final measured value; if the second deviation value and the first deviation value are both negative, this indicates that the actual measurement value is large, and therefore the smaller of the first measurement value and the second measurement value is taken as the final measurement value.
The invention provides a method for measuring the content of lithium elements in a lithium-boron alloy, wherein the step S1 utilizes grinding equipment to grind the surface of a standard sample, and then cuts the sample to ensure that the diameter of the standard sample is within the range of 30-300 mm; so as to be directly used for the subsequent determination of an emission spectrometer. And step S4, polishing the surface of the sample to be analyzed by using a polishing device, and then cutting the sample to ensure that the diameter of the sample to be analyzed is in the range of 30-300 mm.
According to the method for measuring the content of the lithium element in the lithium-boron alloy, the standard samples with the lithium content of 20.X%, 30.X%, 40.X%, 50.X%, 60.X%, 70.X%, 80.X% and 90.X% are selected to form a standard sample library in the step S1, first deviation values with corresponding contents are obtained in the step S2 respectively, and the first deviation value with the closest lithium content is selected as a comparison reference value in the step S5 or is corrected through interpolation fitting through two adjacent first deviation values.
The invention provides a method for measuring the content of lithium elements in a lithium-boron alloy, which mainly comprises an excitation unit, a detector and a recording unit. The excitation unit consists of a high voltage generator and an X-ray tube, which function is to generate primary X-rays. The detector is used for converting the energy of X-ray photons into electric energy, and commonly used ones include a grid counter tube, a proportional counter tube, a scintillation counter tube, a semiconductor detector and the like. The recording unit consists of an amplifier, a pulse amplitude analyzer and a display part; the pulse analysis signal of the scaler can be directly input into a computer for online processing to obtain the content of the element to be measured.
The step S2 of the present invention includes: analysis line type, voltage and current of X-ray tube, filter type, detector type, analysis time, region of interest calibration, and correction curve type. The step S2 further comprises correcting the spectrum of the standard sample as follows: firstly, carrying out fitting background treatment on the obtained standard sample spectrum, and deducting background values of the characteristic spectrum and other spectrum peaks to obtain the net intensity of the characteristic spectrum; performing overlap correction on the interference spectrum line to obtain the net strength of the element to be detected; and correcting the matrix effect by using the first deviation value to obtain a standard working curve. For lithium boron alloys, the most predominant interfering element is boron. For this purpose, the step S3 further includes measuring the boron element content by using an inductively coupled plasma emission spectrometer, and the step S2 performs overlap correction on the interference spectrum caused by the boron element. The analysis step length in the step S4 is 1mm, 2mm, 5mm or 10mm, the scanning area length is 100-1000 mm, and the width is 100-500 mm.
The invention provides a method for measuring the content of lithium elements in a lithium-boron alloy, wherein in the step S3, a standard sample is added into mixed liquid of hydrofluoric acid and hydrogen peroxide for digestion; the method specifically comprises the following steps:
s31, placing the standard sample obtained in the step S2 in a container, mixing the standard sample with nitric acid and hydrogen peroxide, and heating to boiling for reaction to obtain a reaction solution A;
s32, mixing the reaction solution A with hydrogen peroxide in a boiling state to perform oxidation reaction;
s33, adding hydrochloric acid in a boiling state for continuous reaction;
s34, flushing the wall of the container with water, continuing to react in a boiling state, and evaporating the concentrated solution;
s35, flushing the wall of the container with water, cooling the solution to 55-60 ℃, maintaining the temperature, adding hydrofluoric acid, standing for reaction until the sample is completely digested, and clarifying the solution;
s36, cooling and fixing the volume to obtain the standard sample solution.
Taking the determination of the lithium content (50% -80% of mass fraction) in the lithium-boron alloy as an example, assuming that the preset threshold value is 0.2, adopting the determination method of the lithium element content in the lithium-boron alloy, aiming at 60.X% and 70.X% standard samples, the first measurement values are 60.28,70.21 respectively, and exceed the preset threshold value; the second measured values (after correction) were 59.5 and 69.45, respectively, the second deviation value was-0.5, -0.55, and the preset threshold was exceeded as well, and the average value of the second measured value and the first measured value was 59.89% and 69.83% respectively, due to the opposite positive and negative of the second deviation value and the first deviation value.
The comparative examples are combined with a lithium sulfate gravimetric method and an inductively coupled plasma atomic emission spectrometry to measure the mass of lithium sulfate, magnesium sulfate and boron oxide in the lithium-boron alloy, and then the difference is utilized to calculate the content of lithium, the two comparative examples are continuously measured for 11 times on a sample to be tested, and the content of lithium elements measured by the comparative examples is calculated as follows for a 60.X% standard sample:
for a standard sample of 70.X%, the content of lithium element measured in comparative example calculation is as follows:
therefore, according to the method for measuring the content of the lithium element in the lithium-boron alloy, the X-ray fluorescence spectrum is adopted for measurement, a sample to be measured is not lost, and the test cost is relatively low; if the predicted precision does not meet the measurement requirement, the inductively coupled plasma emission spectrometer is continuously adopted for measurement, so that the measurement precision is greatly improved; the method is suitable for measuring various lithium contents in the sample, has high sensitivity, is simple and convenient for sample preparation and pretreatment, can effectively avoid introducing impurity pollution, and reduces operation difficulty.
While the invention has been described with reference to the preferred embodiments, it is not intended to limit the invention thereto, and it is to be understood that other modifications and improvements may be made by those skilled in the art without departing from the spirit and scope of the invention, which is therefore defined by the appended claims.
Claims (10)
1. The method for measuring the content of the lithium element in the lithium boron alloy is characterized by comprising the following steps of:
s1) selecting a plurality of standard samples with different lithium contents to form a standard sample library;
s2) firstly, placing the standard sample subjected to surface treatment into an X-ray fluorescence spectrometer for full coverage scanning, measuring to obtain a measured value of lithium element concentration, recording a first deviation value with standard content, collecting a spectrum of the standard sample, and correcting the spectrum of the standard sample to obtain a standard working curve;
s3) continuing to digest the standard sample to obtain a standard sample solution, measuring the content of lithium element by using an inductively coupled plasma emission spectrometer, and recording a second deviation value of the measured content of lithium element and the standard content;
s4) carrying out surface treatment on the sample to be analyzed, calibrating the position of an analysis point in an observation area by adopting an X-ray fluorescence spectrometer, and processing analysis data in the observation area of the sample to be analyzed by utilizing a standard working curve to obtain a first measurement value of lithium content;
s5) taking the first deviation value corresponding to the first measured value as a comparison reference value, if the comparison reference value exceeds a preset threshold value, continuously measuring a second measured value of the lithium element concentration of the sample to be analyzed by using the inductively coupled plasma emission spectrometer, correcting the second measured value by using the second deviation value as a final measured value, and otherwise, directly taking the first measured value as the final measured value.
2. The method according to claim 1, wherein if the second deviation value corresponding to the second measurement value of the concentration of lithium element obtained in step S5 also exceeds the preset threshold value and the second deviation value is opposite to the first deviation value in sign, taking the average value of the corrected second measurement value and the first measurement value as the final measurement value.
3. The method for measuring the content of lithium element in a lithium-boron alloy according to claim 1, wherein if the second deviation value corresponding to the second measured value of the concentration of lithium element obtained in step S5 also exceeds the preset threshold value, and the second deviation value and the first deviation value are the same in positive and negative, continuing to determine as follows: if the second deviation value and the first deviation value are both positive, indicating that the actual measured value is smaller, and taking the larger value of the first measured value and the second measured value as the final measured value; if the second deviation value and the first deviation value are both negative, this indicates that the actual measurement value is large, and therefore the smaller of the first measurement value and the second measurement value is taken as the final measurement value.
4. The method for measuring the content of lithium elements in the lithium-boron alloy according to claim 1, wherein the standard sample and the sample to be analyzed are subjected to surface grinding by a grinding device and then subjected to cutting processing, so that the diameters of the standard sample and the sample to be analyzed are in the range of 30-300 mm.
5. The method for determining the content of lithium elements in a lithium-boron alloy according to claim 1, wherein the step S1 selects standard samples having lithium contents of 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90% to form a standard sample library, and the first deviation values at the respective contents are obtained in the step S2, respectively, and the step S5 selects the first deviation value having the closest lithium content as a comparison reference value, or uses two adjacent first deviation values as the comparison reference value by interpolation fitting.
6. The method for determining the content of lithium element in a lithium-boron alloy according to claim 1, wherein the step S2 corrects the spectrum of the standard sample as follows: firstly, carrying out fitting background treatment on the obtained standard sample spectrum, and deducting background values of the characteristic spectrum and other spectrum peaks to obtain the net intensity of the characteristic spectrum; performing overlap correction on the interference spectrum line to obtain the net strength of the element to be detected; correcting the matrix effect by using the first deviation value to obtain a standard working curve; and the step S3 further comprises the step of measuring the content of boron element by adopting an inductively coupled plasma emission spectrometer, and the step S2 carries out overlap correction on interference spectral lines caused by the boron element.
7. The method for measuring the content of lithium elements in the lithium-boron alloy according to claim 1, wherein the X-ray fluorescence spectrometer comprises a high-voltage generator, an X-ray tube, a detector and a recording unit; the spectrum of the standard sample or the sample to be analyzed is collected, including analysis spectrum type, voltage and current of the X-ray tube, detector type, analysis time, region of interest calibration and correction curve type.
8. The method for measuring the content of lithium element in the lithium-boron alloy according to claim 1, wherein the standard sample or the sample to be analyzed is added into a mixed solution of hydrofluoric acid and hydrogen peroxide for digestion.
9. The method for determining the content of lithium element in a lithium-boron alloy according to claim 8, wherein the digestion process of the standard sample or the sample to be analyzed is as follows:
s31, taking a standard sample or a sample to be analyzed, placing the standard sample or the sample to be analyzed in a container, mixing the sample with nitric acid and hydrogen peroxide, and heating the mixture to boiling for reaction to obtain a reaction liquid A;
s32, mixing the reaction solution A with hydrogen peroxide in a boiling state to perform oxidation reaction;
s33, adding hydrochloric acid in a boiling state for continuous reaction;
s34, flushing the wall of the container with water, continuing to react in a boiling state, and evaporating the concentrated solution;
s35, flushing the wall of the container with water, cooling the solution to 55-60 ℃, maintaining the temperature, adding hydrofluoric acid, standing for reaction until the sample is completely digested, and clarifying the solution;
s36, cooling and fixing the volume to obtain the standard sample solution.
10. The method for measuring the content of lithium elements in a lithium-boron alloy according to claim 1, wherein the analysis step in the step S4 is 1mm, 2mm, 5mm or 10mm, and the scanning area is 100-1000 mm in length and 100-500 mm in width.
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