CN118671116B

CN118671116B - Method for determining element content using energy dispersive X-ray spectrometry

Info

Publication number: CN118671116B
Application number: CN202411062941.8A
Authority: CN
Inventors: 顾甜甜; 缪建存; 单兵兵; 赵云虎; 秦锦
Original assignee: Nantong Reshine New Material Co ltd
Current assignee: Nantong Reshine New Material Co ltd
Priority date: 2024-08-05
Filing date: 2024-08-05
Publication date: 2024-11-19
Anticipated expiration: 2044-08-05
Also published as: CN118671116A

Abstract

The present application discloses a method for determining the content of an element using an energy dispersive X-ray spectrometer, comprising the steps of: obtaining a first average response value of an element to be measured in a plurality of standard samples by an energy dispersive X-ray spectrometer, and obtaining a second average response value of an element to be measured in a plurality of standard samples by an inductively coupled plasma spectrometer; obtaining a calibration method of the energy dispersive X-ray spectrometer based on the first average response value and the second average response value; obtaining a first actual response value of the element to be measured in the sample to be measured by the energy dispersive X-ray spectrometer, and calibrating the first actual response value based on the calibration method to obtain the content value of the element to be measured in the sample to be measured. The method for determining the content of an element provided by the present application has the advantages of being simple and accurate.

Description

Method for measuring element content by using energy dispersion X-ray spectrometer

Technical Field

The application relates to the technical field of battery material detection, in particular to a method for measuring element content by using an energy dispersion X-ray spectrometer.

Background

In the current energy storage field, a lithium battery becomes one of the most widely used energy storage media due to the advantages of high energy density, long service life, stability and the like, and has huge market demand. The production of lithium ion batteries relies on a variety of raw materials, where the quality of the positive electrode material directly affects the performance and quality of the battery. The content of elements in the positive electrode material, such as nickel, cobalt, manganese, etc., is one of the key factors determining the performance of the battery. Therefore, accurate determination of the content of these elements in the positive electrode material is of great importance for ensuring the quality of lithium battery products.

Currently, methods for determining the content of elements in a positive electrode material mainly include conventional chemical analysis methods and instrumental analysis methods. The traditional chemical analysis method, such as using EDTA to titrate the total metal amount, and then respectively measuring the content of specific elements by a precipitation method and a redox method, has complex operation and long analysis time, and is difficult to meet the requirements of the rapidly-developed lithium battery industry. The instrument analysis method, such as inductively coupled plasma generation spectrometer analysis, can shorten the analysis time, but has poor testing accuracy and precision due to overlarge dilution factor and sensitivity of the instrument to environmental conditions, so that the wide application of the instrument in the lithium battery manufacturing industry is limited.

Disclosure of Invention

In view of the above, the present application provides a method for determining element content by using an energy dispersive X-ray spectrometer, so as to solve the above technical problems.

A method for determining elemental content using an energy-dispersive X-ray spectrometer, comprising the steps of: acquiring first average response values of elements to be detected in a plurality of standard samples through an energy dispersion X-ray spectrometer, and acquiring second average response values of the elements to be detected in the plurality of standard samples through an inductive coupling plasma generation spectrometer; obtaining a correction mode of the energy dispersion X-ray spectrometer according to the first average response value and the second average response value; the method comprises the steps of obtaining a first actual response value of an element to be detected in a sample to be detected through an energy dispersion X-ray spectrometer, and correcting the first actual response value according to a correction mode to obtain a content value of the element to be detected in the sample to be detected.

In some possible embodiments, the step of obtaining the first average response value of the element to be measured in the plurality of standard samples by the energy-dispersive X-ray spectrometer includes: providing a plurality of standard samples, wherein the content of the element to be detected in each standard sample is different; for each standard sample, a plurality of first response values of the element to be measured are obtained through multiple measurements of an energy dispersion X-ray spectrometer, and the plurality of first response values are averaged to obtain a first average response value.

In some possible embodiments, the step of obtaining, by the inductively coupled plasma-generating spectrometer, the second average response value of the element to be measured in the plurality of standard samples includes: providing a plurality of standard samples, wherein the content of the element to be detected in each standard sample is different; and carrying out multiple measurements on each standard sample through an inductively coupled plasma spectrometer to obtain a plurality of second response values of the element to be measured, and averaging the plurality of second response values to obtain a second average response value.

In some possible embodiments, the content of the element to be measured in the sample to be measured is within a preset range defined by the maximum content and the minimum content of the element to be measured in the plurality of standard samples.

In some possible embodiments, the number of measurements is 2-10.

In some possible embodiments, the step of "obtaining the correction mode of the energy-dispersive X-ray spectrometer according to the first average response value and the second average response value" includes: and taking the first average response value as an independent variable and the second average response value as a dependent variable, and performing linear fitting on the first average response value and the second average response value to obtain a linear regression equation.

In some possible embodiments, the step of "correcting the first actual response value according to the correction manner" includes: substituting the first actual response value into one side of an independent variable of the linear regression equation, and taking the calculation result as the content value of the element to be measured.

In some possible embodiments, the method further comprises the step of: acquiring a second actual response value of the element to be detected in the sample to be detected by using an inductive coupling plasma generation spectrometer as a verification value; and evaluating the accuracy of the content value by using the verification value.

In some possible embodiments, the number of standard samples is 3-8.

In some possible embodiments, the standard sample and the sample to be tested are nickel-cobalt-manganese ternary positive electrode materials, and the element to be tested is nickel, cobalt or manganese; or the standard sample and the sample to be detected are both lithium manganese iron phosphate anode materials, and the element to be detected is iron or manganese.

According to the method for measuring the element content by using the energy dispersion X-ray spectrometer, the energy dispersion X-ray spectrometer is used for obtaining the first average response value of the element to be measured in the plurality of standard samples, and the inductive coupling plasma generation spectrometer is used for obtaining the second average response value of the element to be measured in the plurality of standard samples. And obtaining a correction mode of the energy dispersion X-ray spectrometer according to the first average response value and the second average response value. The method comprises the steps of obtaining a first actual response value of an element to be detected in a sample to be detected through an energy dispersion X-ray spectrometer, and correcting the first actual response value according to a correction mode to obtain a content value of the element to be detected in the sample to be detected. Compared with the complex sample pretreatment and longer test period required by the inductively coupled plasma generation spectrometer, the energy dispersion X-ray spectrometer can provide a more rapid analysis result, thereby remarkably improving the test efficiency and reducing the burden of experimental operation.

Drawings

FIG. 1 is a flow chart of an embodiment of a method for determining elemental content using an energy dispersive X-ray spectrometer according to the present application.

Detailed Description

The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

Some embodiments of the present application are described in detail below with reference to the accompanying drawings. The following embodiments and features of the embodiments may be combined with each other without conflict.

In the present application, an Energy-dispersive X-ray spectrometer (EDX) is an important tool for analyzing surface elements of materials, and is often used in combination with a Scanning Electron Microscope (SEM) or a Transmission Electron Microscope (TEM) to obtain elemental composition and chemical information of a sample. The energy dispersive X-ray spectrometer is capable of rapidly and nondestructively performing qualitative and quantitative analysis of a sample.

In the present application, inductively coupled plasma emission spectrometry (Inductively Coupled Plasma Optical Emission Spectrometry, ICP-OES) is an analytical technique for measuring elemental concentrations. The method is particularly suitable for rapid analysis of various elements and simultaneous quantification, can process almost all types of aqueous solution samples, and is widely applied to the fields of environmental monitoring, food safety, medicine analysis, geological research and the like. The ICP-OES needs to perform pretreatment, such as digestion, dilution and the like, on the sample to be tested, and meanwhile, the test result of the ICP-OES is easily influenced by external environment.

Referring to fig. 1, fig. 1 is a flow chart of an embodiment of a method for determining element content using an energy-dispersive X-ray spectrometer according to the present application, which includes the following steps S11-S13.

S11, obtaining first average response values of elements to be detected in the plurality of standard samples through EDX, and obtaining second average response values of the elements to be detected in the plurality of standard samples through ICP-OES.

For the lithium battery anode material, the current standard method is to use ICP-OES to measure the element content, and although EDX can be used for quantitatively analyzing the element, due to the lack of a standard sample suitable for EDX, the method cannot be matched with the ICP-OES measurement result commonly used in the industry, and the test accuracy cannot be ensured.

The application provides a method for measuring the element content in a positive electrode material by using EDX, the measurement result can be matched with an ICP-OES measurement result which is common in the industry, firstly, the content analysis of the specified element to be measured is required to be carried out on a plurality of standard samples by using the EDX and the ICP-OES respectively, the plurality of standard samples are prepared according to a sample preparation standard GBT22554-2010 which is suitable for the ICP-OES, the element to be measured can be multiple, and the contents of multiple elements can be obtained simultaneously in one measurement by using the EDX and the ICP-OES. And (3) detecting the plurality of standard samples directly by using EDX to obtain the content of the element to be detected (such as cobalt, manganese and nickel), namely a first average response value F, and analyzing the element content of the plurality of standard samples by using ICP-OES to obtain a second average response value C of the same element to be detected in the plurality of standard samples.

S12, establishing an EDX correction mode according to the first average response value and the second average response value.

And the EDX and the ICP-OES respectively obtain the content of the element to be detected in the standard sample, namely, after the first average response value and the second average response value, an EDX correction mode is established by the plurality of first average response values and the plurality of second average response values, so that the EDX measuring result corresponding to the sample to be detected can be conveniently matched with the ICP-OES. For example, the two distributions may be plotted to obtain a point-to-point deviation value, and then averaged, or linear regression may be performed.

S13, obtaining a first actual response value of the element to be detected in the sample to be detected through EDX, and correcting the first actual response value according to a correction mode to obtain the content value of the element to be detected in the sample to be detected.

Further, analyzing the element content of the sample to be measured through EDX, obtaining a first actual response value of the element to be measured, correcting the first actual response value by using the correction mode, and taking the corrected result as the content value of the element to be measured in the sample to be measured. The content value is matched with the ICP-OES measurement result which is common in the industry standard, and is equivalent to replacing the ICP-OES measurement result after the EDX measurement result is simply converted by using a correction mode, and the correction mode can be implanted into an EDX processor for correction at the background, so that the content value of the element to be detected in the sample to be detected is directly obtained.

The method for determining the element content in the positive electrode material by using the EDX can directly obtain the detection result matched with the ICP-OES common in the industry, accords with the industry standard, and can directly detect the powdery positive electrode material by using the EDX relative to the ICP-OES in the detection method without pretreatment processes such as heating digestion, dilution and the like, and has the advantages of shorter test time, more stable test process, higher precision of test result and no damage to a sample.

In some embodiments, the "obtaining the first average response value of the element to be measured in the plurality of standard samples by EDX" in the step S11 specifically includes the following steps S21 to S22.

S21, providing a plurality of standard samples, wherein the content of the element to be detected in each standard sample is different.

The plurality of standard samples are lithium battery anode materials, and are prepared according to standard GBT22554-2010, the content of the element to be detected in each standard sample is different, the content of the element to be detected in the sample to be detected is within a preset range, and the preset range is defined by the maximum content and the minimum content of the element to be detected in the plurality of standard samples. When the standard sample is prepared, the standard sample with the element content coverage range to be measured as wide as possible can be selected, so that more applicable samples to be measured can be obtained.

For example, a ternary positive electrode material of a lithium battery is selected to prepare a plurality of standard samples, and elements to be detected include cobalt, manganese and nickel. The mass of cobalt accounts for 2% -23% of the total mass of the standard sample, the mass of manganese accounts for 12% -20% of the total mass of the standard sample, the mass of nickel accounts for 20% -47% of the total mass of the standard sample, and the content of elements to be detected in each standard sample is different. For example, a lithium iron manganese phosphate anode material is selected to prepare a plurality of standard samples, the elements to be detected comprise manganese and iron, the mass of manganese accounts for 13% -22% of the total mass of the standard samples, the mass of iron accounts for 13% -22% of the total mass of the standard samples, and the contents of the elements to be detected in the standard samples are different.

S22, for each standard sample, measuring a plurality of times by EDX to obtain a plurality of first response values of the element to be tested, and averaging the plurality of first response values to obtain a first average response value.

After preparing a plurality of standard samples, for each standard sample, measuring a plurality of times by EDX time sharing to obtain a plurality of first response values of the element to be measured therein, and averaging the plurality of first response values to obtain a first average response value, wherein the number of times of measuring the plurality of times is 2-10. For example, for a plurality of standard samples prepared by the ternary cathode material, each standard sample is measured by EDX time-sharing for a plurality of times, each measurement can obtain a first response value of the element cobalt, manganese and nickel to be measured, and after all the measurement is completed, the plurality of first response values are averaged to obtain first average response values of the element cobalt, manganese and nickel to be measured respectively.

Random errors and uncertainties in a single measurement can be reduced by time-sharing multiple measurements for each element to be measured and then taking the average as the first average response value. For example, there may be a situation that a certain measurement is interfered by the outside or the instrument is unstable instantaneously, and multiple measurements and averaging can effectively reduce the influence of these accidental factors, so that the measurement result is closer to the true value, and the measurement accuracy is improved.

In some embodiments, the "obtaining the second average response value of the element to be measured in the plurality of standard samples by ICP-OES" in the above step S11 specifically includes the following steps S31 to S32.

S31, providing a plurality of standard samples, wherein the content of the element to be detected in each standard sample is different. This step is the same as step S21 described above, and will not be described here again.

S32, for each standard sample, obtaining a plurality of second response values of the element to be detected through ICP-OES multiple times of measurement, and averaging the plurality of second response values to obtain a second average response value.

After preparing a plurality of standard samples, for each standard sample, measuring a plurality of times by ICP-OES to obtain a plurality of second response values of the element to be measured therein, and averaging the plurality of second response values to obtain a second average response value, wherein the number of times of measuring a plurality of times is 2-10. For example, for a plurality of standard samples prepared by the ternary positive electrode material, measuring each standard sample by ICP-OES time-sharing for a plurality of times, obtaining a second response value of the element cobalt, manganese and nickel to be measured by each measurement, and averaging the second response values after all the measurement to obtain second average response values of the element cobalt, manganese and nickel to be measured respectively.

Similarly, random errors and uncertainties in single measurement can be reduced by measuring each standard element to be measured in a time-sharing mode for multiple times, so that a measurement result is closer to a true value, and measurement accuracy is improved.

In some embodiments, the step S12 "establishes the EDX correction mode according to the first average response value and the second average response value" specifically includes:

And taking the first average response value as an independent variable and the second average response value as a dependent variable, and performing linear fitting on the first average response value and the second average response value to obtain a linear regression equation. Specifically, mintab software can be utilized to perform linear fitting, and a linear regression equation with high accuracy and reliability is obtained.

Further, the step S13 of correcting the first actual response value according to the correction mode to obtain the content value of the element to be measured in the sample to be measured specifically includes:

Substituting the first actual response value into one side of an independent variable of the linear regression equation, and taking the calculation result as the content value of the element to be measured.

According to the method, the first actual response value measured by EDX is corrected in a linear fitting mode, so that a detection result matched with the ICP-OES common in the industry is obtained, the method meets the industry standard, the test time is shorter, the test process is more stable, and the test result is more accurate.

In some embodiments, the method of the present application for determining the content of an element in a positive electrode material using an energy dispersive X-ray spectrometer further comprises the following steps S41 to S42.

S41, obtaining a second actual response value of the element to be detected in the sample to be detected through ICP-OES as a verification value.

In a similar manner to the above-described steps S31 to S32, a sample to be measured is prepared and a second actual response value of the element to be measured in the sample to be measured, which is also preferably an average value obtained by a plurality of measurements, is obtained by ICP-OES.

S42, evaluating the accuracy of the value to be contained by using the verification value.

And further taking the second actual response value as a verification value to evaluate the accuracy of the content value of the element to be measured in the sample to be measured, which is obtained before. The difference between the content value and the verification value may be used, for example, to evaluate its accuracy.

In the embodiment, after the content value of the element to be detected in the sample to be detected is obtained by using EDX, the verification value obtained by ICP-OES is used for carrying out accuracy assessment, so that the feasibility and the reliability of the method for measuring the content of the element by using the energy dispersion X-ray spectrometer are further verified.

The following describes the performance improvement brought by the technical scheme provided by the application in combination with specific examples and comparative examples.

Example 1

1) 8 Ternary lithium battery anode materials with 2% -23% of Co content, 12% -20% of Mn content and 20% -47% of Ni content are selected to prepare standard samples, the standard samples are prepared from nickel-cobalt-manganese ternary anode materials with different proportions, elements to be tested are Co, mn and Ni, and the standard for preparing the samples can be seen in GBT22554-2010.

2) And (3) taking part of the standard samples from each standard sample to a sample cup, manually compacting the standard samples by using a quartz glass rod to reach more than 2/3 of the volume of the sample cup, taking 30 seconds, setting the EDX test time to 200 seconds, testing on different days, repeatedly measuring for 2 times to obtain 2 first response values F of three elements to be tested in the standard samples, and obtaining a first average response value F after averaging. Wherein, for nickel, the first average response value is denoted as F1, for cobalt, the first average response value is denoted as F2, and for manganese, the first average response value is denoted as F3.

3) And weighing 1.25g of each standard sample, adding 20mL of 50% diluted hydrochloric acid, heating at the temperature of 250 ℃ for digestion, cooling the mixture to room temperature after digestion and clarification, transferring to a 250mL volumetric flask, metering the volume to scale with pure water, shaking uniformly, transferring to a 5 mL-100 mL volumetric flask, transferring to a 5 mL-50 mL volumetric flask, measuring on ICP-OES, preprocessing and testing once a day, repeating for 10 times to obtain 10 second response values C of each of three elements to be tested in the standard sample, and obtaining a second average response value C after averaging. Wherein, for nickel, the second average response value is denoted as C1, for cobalt, the second average response value is denoted as C2, and for manganese, the second average response value is denoted as C3.

4) And taking second average response values C corresponding to 8 standard samples as dependent variables, taking first average response values F as independent variables, and performing linear fitting by utilizing Mintab software to obtain a linear regression equation with better fitting goodness index and smaller error standard deviation. Wherein, for nickel, the linear regression equation is written as equation 1: c1 = -0.1481+1.008×f1 (R ² =0.9997); for cobalt, the linear regression equation is written as equation 2: c2 =0.07819+1.018×f2 (R ² =0.9989); for manganese, the linear regression equation is written as equation 3: c3 =0.0184+0.989×f3 (R ² = 0.9981). Wherein R ² is a decision coefficient for measuring the interpretation degree of the independent variable to the dependent variable, and the value ranges from 0 to 1. The closer the R value is to 1, the higher the interpretation of the independent variable to the dependent variable, and the better the model's goodness of fit. For example, an R value of 0.9997 means that the independent variable is able to interpret 98.97% variability of the dependent variable.

5) Preparing 2 samples to be tested according to the step 1), and respectively testing by using EDX according to the step 2) to obtain respective first actual response values f' of Ni, co and Mn in the 2 samples to be tested.

6) And obtaining the content values c 'of the three elements to be detected according to the first actual response values f' of Ni, co and Mn in the above formula 1, formula 2, formula 3 and 2 samples to be detected. The first actual response value f 'of each element to be detected is substituted into one side of the independent variable of the corresponding linear regression equation, and the calculated result is used as the content value c' of the element to be detected.

In this embodiment, EDX with higher testing efficiency is used to obtain the content value of the element to be tested in the sample to be tested, in order to verify the accuracy of the test result, 2 samples to be tested are further tested by ICP-OES according to the above step 3), and the verification values u of the three elements to be tested in the sample to be tested are obtained, and the specific results are shown in tables 1 and 2.

TABLE 1 comparative analysis of EDX-measured content value and ICP-OES-measured verification value of sample 1 to be tested

TABLE 2 comparative analysis of EDX-measured content value and ICP-OES-measured verification value of sample 2 to be tested

The results show that:

a) The difference between the average value of the content value c' measured by EDX and the average value of the verification value u measured by ICP-OES is very small for nickel (Ni), cobalt (Co) and manganese (Mn), which indicates that the content value of the element to be detected obtained by the method for measuring the element content in the positive electrode material by using EDX provided by the application is very close to the verification value obtained by using ICP-OES in the prior art, and the method provided by the application can be used for replacing the method in the prior art to obtain the same accurate test effect, and simultaneously, the test efficiency is remarkably improved and the burden of experimental operation is reduced.

B) The standard deviation of the content value c 'measured by EDX is much smaller than the standard deviation of the verification value u measured by ICP-OES, which shows that the content value c' is very consistent and accurate, i.e. the EDX test repeatability is better than ICP-OES and the test accuracy is higher.

Example 2

1) 3 Standard samples with Mn content of 13-22% and Fe content of 13-22% are selected, the standard samples are made of lithium manganese iron phosphate anode materials with different proportions, the elements to be detected are Fe and Mn, and the standard of sample preparation can be seen in GBT22554-2010.

2) And (3) for each standard sample, digging the standard sample into a sample cup, manually compacting the standard sample by using a quartz glass rod to reach more than 2/3 of the sample volume, taking 30 seconds, setting the EDX test time to 300 seconds, testing on different days, repeatedly measuring for 2 times to obtain 2 first response values F of two elements to be tested in the standard sample, and obtaining a first average response value F after averaging. Wherein, for iron, the first average response value is denoted as F4, and for manganese, the first average response value is denoted as F5.

3) For each standard sample, weighing 0.4g of standard sample, adding 5mL of 70% perchloric acid, shaking uniformly, heating on an electric furnace to dissolve until white smoke is exhausted, taking down and cooling to room temperature, transferring to a 100mL volumetric flask, fixing the volume to scale by pure water, shaking uniformly, taking a 1mL to 100mL volumetric flask, measuring on ICP-OES, preprocessing and testing once a day, repeating 10 times, measuring 10 second response values C, and obtaining a second average response value C after averaging. Wherein, for iron, the second average response value is denoted as C4 and for manganese, the second average response value is denoted as C5.

4) And taking second average response values C corresponding to the 3 standard samples as dependent variables, taking the first average response value F as independent variable, and performing linear fitting by utilizing Mintab software to obtain a linear regression equation with better fitting goodness index and smaller error standard deviation. Wherein, for iron, the linear regression equation is written as equation 4: c4 =0.0983+1.0001×f4 (R ² =0.998), and for manganese, the linear regression equation is written as formula 5, c5=0.6827+1.0172×f5 (r2=0.998).

5) Preparing 1 sample to be tested according to the step 1), testing the sample to be tested according to the step 2), and obtaining a first actual response value f' of Fe and Mn in the sample to be tested by EDX test.

6) Obtaining the content value c 'of each of the two elements to be measured, namely Fe and Mn, in the sample to be measured according to the above formulas 4 and 5 and the first actual response value f' of the sample to be measured. The first actual response value f 'of each element to be detected is substituted into one side of the independent variable of the corresponding linear regression equation, and the calculated result is used as the content value c' of the element to be detected.

In this embodiment, EDX with higher test efficiency is used to obtain the content value of the element to be tested in the sample to be tested, and in order to verify the accuracy of the test result, the sample to be tested is further tested according to step 3) by ICP-OES, and the verification values u' of the elements to be tested Fe and Mn are measured. See table 3 for specific results.

TABLE 3 comparative analysis of EDX-measured content value and ICP-OES-measured verification value of sample 3 to be tested

The results show that:

a) For iron (Fe) and manganese (Mn), the difference between the average value of the content value c ' ' measured by EDX and the average value of the verification value u ' measured by ICP-OES is very small, which indicates that the content value of the element to be detected obtained by using the method for measuring the element content in the positive electrode material by using EDX provided by the application is very close to the verification value obtained by using ICP-OES in the prior art, and the method provided by the application can be used for replacing the method in the prior art to obtain the same accurate test effect, and meanwhile, the test efficiency is remarkably improved and the burden of experimental operation is reduced.

B) The standard deviation of the content value c ' ' measured by EDX is smaller than the standard deviation of the verification value u ' measured by ICP-OES, which shows that the content value c ' ' is very consistent and accurate, i.e. the EDX test repeatability is better than ICP-OES and the test accuracy is higher.

The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the application, and all equivalent structural changes made by the present application in the specification and drawings, or direct/indirect application in other related technical fields are included in the scope of the present application.

Claims

1. A method for determining elemental content using an energy dispersive X-ray spectrometer, comprising the steps of:

providing a plurality of standard samples, wherein the content of an element to be detected in each standard sample is different;

obtaining a plurality of first response values of the element to be measured therein by measuring the energy-dispersive X-ray spectrometer a plurality of times for each of the standard samples, and averaging the plurality of first response values to obtain a first average response value, and

Measuring each standard sample for multiple times through an inductive coupling plasma generation spectrometer to obtain multiple second response values of the element to be measured, and averaging the multiple second response values to obtain a second average response value;

Taking the first average response value as an independent variable and the second average response value as a dependent variable, and performing linear fitting on the first average response value and the second average response value to obtain a linear regression equation;

And acquiring a first actual response value of the element to be detected in the sample to be detected through the energy dispersion X-ray spectrometer, substituting the first actual response value into one side of an independent variable of the linear regression equation, and taking a calculation result as a content value of the element to be detected to acquire the content value of the element to be detected in the sample to be detected.

2. The method of claim 1, wherein the content of the element to be measured in the sample to be measured is within a predetermined range defined by a maximum content and a minimum content of the element to be measured in the plurality of standard samples.

3. The method of claim 1, wherein the number of measurements is 2-10.

4. The method of claim 1, further comprising the step of:

acquiring a second actual response value of the element to be detected in the sample to be detected by the inductively coupled plasma generation spectrometer as a verification value;

And evaluating the accuracy of the content value by using the verification value.

5. The method of claim 1, wherein the number of standard samples is 3-8.

6. The method of claim 1, wherein the standard sample and the sample to be measured are nickel-cobalt-manganese ternary cathode materials, and the element to be measured is nickel, cobalt or manganese; or the standard sample and the sample to be detected are both lithium manganese iron phosphate anode materials, and the element to be detected is iron or manganese.