CN113311015A - Method for analyzing content of main elements in nickel cobalt lithium manganate positive electrode material - Google Patents

Method for analyzing content of main elements in nickel cobalt lithium manganate positive electrode material Download PDF

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CN113311015A
CN113311015A CN202110653733.5A CN202110653733A CN113311015A CN 113311015 A CN113311015 A CN 113311015A CN 202110653733 A CN202110653733 A CN 202110653733A CN 113311015 A CN113311015 A CN 113311015A
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张敏
梁鲁西
耿帅
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Hubei Eve Power Co Ltd
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    • G01—MEASURING; TESTING
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    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract

The invention provides a method for analyzing the content of a main element in a nickel cobalt lithium manganate positive electrode material. The analysis method comprises the following steps: (1) performing tabletting treatment on a standard sample, then testing the tabletting sample by using an X-ray fluorescence spectrometer, selecting a model correction curve spectrogram, preprocessing the curve spectrogram, and establishing to obtain a corresponding standard curve; (2) and (3) tabletting the sample to be detected, testing the tabletted sample by using an X-ray fluorescence spectrometer, and obtaining the content of the main element in the sample to be detected according to the corresponding standard curve in the step (1). The method adopts the X-ray fluorescence spectrometer to analyze multiple elements such as Ni, Co, Mn and the like in NCM at one time, has the advantages of simple operation, high analysis speed, safety, rapidness, low cost, high accuracy, good stability, high detection efficiency and high practicability, and is suitable for practical production.

Description

Method for analyzing content of main elements in nickel cobalt lithium manganate positive electrode material
Technical Field
The invention belongs to the technical field of chemical element component analysis in lithium ion batteries, and relates to the technical field of a method for analyzing the content of a main element in a nickel cobalt lithium manganate positive electrode material.
Background
The lithium nickel cobalt manganese oxide (NCM) of the ternary cathode material of the lithium ion battery has the advantages of high specific capacity, wide discharge voltage range, stable electrochemical performance, good safety performance and the like, and has wide application rangeHas good market prospect. NCM binding LiCoO2、LiNiO2、LiMnO2The characteristics of the three components have obvious synergistic effect. The main elements of NCM are Ni, Co and Mn, and the addition of Co can reduce the occurrence of cation mixed discharge and effectively stabilize the structure of the material; the capacity of the material can be improved by adding Ni; by adding Mn, the cost of the material can be reduced, and the stability and safety of the material can be improved. The accurate determination of Ni, Co and Mn in NCM and its precursor is the difficult point and key of preparing NCM.
Currently, instrument analysis methods such as plasma emission spectrometry (ICP-AES) and Atomic Absorption Spectrometry (AAS) are mostly used to measure the nickel, cobalt and manganese contents in NCM and its precursors. However, since the measurement objects of ICP-AES and AAS are mainly trace components, and the nickel-cobalt-manganese content in NCM is a constant level, the sample needs to be diluted by several thousand times or more, and the larger the dilution, the larger the error. The chemical analysis method is also adopted to determine the nickel, cobalt and manganese contents of NCM, if the chemical titration method is mostly a single element analysis method, the detection process is complicated, the analysis speed is slow, the analysis period is long, more manpower is required to be invested, the consumption of chemical reagents is high, the detection cost is high, and in addition, a large amount of chemical waste liquid causes pollution to the environment, so that the requirement of fast-paced production cannot be completely met. Meanwhile, the 3 elements belong to the same transition metal and have similar properties, so that the elements are easy to interfere with each other, and the difficulty is increased for selecting the method. The X-ray fluorescence spectrometry has a very good development space due to the unique advantages of relatively simple pretreatment, no damage to a sample, simultaneous determination of multiple elements, no harsh requirements on laboratory conditions, simple operation technology, low price and the like. With the continuous progress and popularization of scientific technology, the X-ray fluorescence spectrum analysis technology is applied to wider departments and fields.
Principle of X-ray fluorescence spectroscopy: the X-ray tube emits X-rays (high energy) once, and when the sample is irradiated, an inner electron is expelled to generate a hole, so that the whole atomic system is in an unstable excited state. When the energy released by the electrons in the outer layer jumping into the holes in the inner layer is not absorbed in the atoms but emitted in the form of radiation, X-ray fluorescence is generated, the energy of which is equal to the energy difference between the two energy levels. Thus, the energy or wavelength of X-ray fluorescence is characteristic, with a one-to-one correspondence to the element. The kind and content of the element can be known by measuring the wavelength and intensity of the fluorescent X-ray.
CN111735903A discloses a method for detecting the content of nickel, cobalt and manganese by mass method complexometric titration, which comprises the following steps: step 1: digesting and diluting the battery material containing nickel, cobalt and manganese to a set mass and constant volume, titrating with EDTA standard solution, and calculating the total content of nickel, cobalt and manganese by the consumption of the EDTA standard titration solution; step 2: after the battery material containing nickel, cobalt and manganese is dissolved by acid, the proportion of nickel, cobalt and manganese is detected by inductively coupled plasma emission spectroscopy (ICP); and step 3: and (4) calculating the contents of nickel, cobalt and manganese according to the result of the step (1) and the result of the step (2).
CN109884037A discloses a method for determining the proportion of nickel, cobalt and manganese in a ternary material NCM. In the literature, an ICP instrument is adopted to measure the proportion of nickel, cobalt and manganese in a solution to be measured, and the method comprises the following steps: preparing a standard solution, namely preparing three standard points; the first standard point is a standard solution STD1, and the total concentration of metal ions is controlled to be 120-200 mg/L; the total concentration of metal ions of the second standard point standard solution STD2 is controlled to be 230-320 mg/L, and the total concentration of metal ions of the third standard point standard solution STD3 is controlled to be 330-390 mg/L; the metal ions are metal ions of nickel, cobalt and manganese.
The conventional ICP elemental measurement method is adopted in the two documents, the pretreatment of a sample is inevitably involved, the detection process is complicated, the analysis speed is low, the analysis period is long, more manpower is required to be invested, the consumption of chemical reagents is high, the detection cost is high, the pollution to the environment is caused by a large amount of chemical waste liquid, the measured sample cannot be reused, and the requirement of fast-paced production cannot be completely met.
Therefore, how to rapidly, efficiently, inexpensively and safely analyze the content of the main element in the nickel cobalt lithium manganate cathode material is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide the technical field of analysis methods of main element contents in a nickel cobalt lithium manganate positive electrode material. The method adopts an X-ray fluorescence spectrometer to respectively measure the contents of Ni, Co and Mn elements in the nickel cobalt lithium manganate positive electrode material (NCM), quickly measures the contents of Ni, Co and Mn in the NCM, is safe, quick, low in cost, high in accuracy, good in stability, high in detection efficiency and extremely practical, and is suitable for practical production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an analysis method of main element content in a nickel cobalt lithium manganate positive electrode material, which comprises the following steps:
(1) performing tabletting treatment on a standard sample, then testing the tabletting sample by using an X-ray fluorescence spectrometer, selecting a model correction curve spectrogram, preprocessing the curve spectrogram, and establishing to obtain a corresponding standard curve;
(2) and (3) tabletting the sample to be detected, testing the tabletted sample by using an X-ray fluorescence spectrometer, and obtaining the content of the main element in the sample to be detected according to the corresponding standard curve in the step (1).
In the invention, the lithium nickel cobalt manganese oxide positive electrode material can be selected from LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.6Co0.1Mn0.3O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Mn0.05O2And the like.
In the present invention, it is confirmed by related studies that the atomic numbers of three elements of nickel, cobalt and manganese are close to each other according to the common general knowledge of those skilled in the art, so that the response sensitivities of the spectra to the three elements are substantially consistent during ICP-OES measurement, and therefore, the molar ratio measured by the ICP-OES method is used as an agreed true value to evaluate the accuracy of the spectral measurement.
In the present invention, the X-ray fluorescence spectrometer type may be an energy dispersive type.
In the invention, the standard sample in the step (1) refers to a nickel cobalt lithium manganate positive electrode material with known main element content, and the sample to be detected in the step (2) refers to a nickel cobalt lithium manganate positive electrode material with main element content to be verified or determined.
According to the method, the conventional ICP method is not adopted to measure the contents of Ni, Co and Mn elements in the nickel cobalt lithium manganate positive electrode material, an NCM sample with known and accurate content is used as a standard sample, an X-ray fluorescence spectrometer is adopted for testing, a standard curve of the content of main elements in the standard sample is established by obtaining a spectrogram of the standard sample, then the sample to be tested is tested, a spectrogram of the sample to be tested is obtained, the spectrogram of the sample to be tested is compared with the standard curve obtained by the spectrogram of the standard sample with known content, and the content of the main elements in the sample to be tested can be obtained.
The analysis method provided by the invention has the following advantages:
the sample to be detected does not need any pretreatment process, and the preparation is simple; the sample is tabletted, so that the compactness of the sample is ensured, the matrix effect of the sample is reduced to the greatest extent, and the stability and the repeatability of the tabletted sample are better than those of a loose powder sample; during the tabletting and sample preparation period, no other reagent is added, and the sample preparation is directly carried out by tabletting, so that the tabletting and sample preparation cost is greatly saved; the tablet press is only used for preparing samples, chemical reagents are not used, the risk coefficient is small, the safety risk basically does not exist in the sample treatment process, and the number of times of post personnel contacting with a hazard source is reduced; the established standard sample curve can be used for a long time, and the detection period of the measurement sample is short; the detection method has the advantages of high accuracy, good stability, high detection efficiency and high practicability, and is worthy of popularization and application.
Preferably, the main elements in the standard sample in the step (1) are nickel element, cobalt element and manganese element.
Preferably, the main elements in the sample to be detected in the step (2) are nickel element, cobalt element and manganese element.
Preferably, the pressure in the tabletting process in the step (1) and the pressure in the tabletting process in the step (2) are respectively and independently 30-50 t, such as 30t, 35t, 40t, 45t or 50 t.
Preferably, the dwell time in the tabletting process in step (1) and the dwell time in the tabletting process in step (2) are each independently 60 to 100s, for example 60s, 70s, 80s, 90s, 100s or the like.
Preferably, during the test in step (1), the Ka spectral line of the main element in the standard sample is taken as an analysis line, and the 2 θ angle corresponding to the spectral line is selected.
Preferably, in the testing process in the step (1), the voltage of the light pipe is 30-45 KV, such as 30KV, 35KV, 40KV or 45 KV.
Preferably, in the testing process in step (1), the light pipe current is 800-1000 μ A, such as 800 μ A, 850 μ A, 900 μ A, 950 μ A or 1000 μ A.
Preferably, the Ka spectral line of the main element in the sample to be tested is taken as an analysis line, and the 2 θ angle corresponding to the spectral line is selected at the same time.
Preferably, in the testing process in the step (2), the voltage of the light pipe is 30-45 KV, such as 30KV, 35KV, 40KV or 45 KV.
Preferably, in the testing process in step (2), the light pipe current is 800-1000 μ A, such as 800 μ A, 850 μ A, 900 μ A, 950 μ A or 1000 μ A.
Preferably, the test time in the step (1) and the test time in the step (2) are respectively and independently 50-100 s, such as 50s, 60s, 70s, 80s, 90s or 100 s.
Preferably, the selected model calibration curve spectrogram in step (1) comprises:
and (2) testing the main elements in the standard sample in the step (1), testing the X-ray fluorescence intensity of the main elements, referring to the standard value, and correcting the measured X-ray fluorescence intensity value by using the model matrix to obtain a corrected curve map.
In the invention, the determination of the standard value is carried out by taking an NCM sample with known accurate content as a standard sample, analyzing and determining the content of the main element in the NCM sample by adopting a chemical method, an ICP-OES method and other testing means, and taking the test data as the element standard value.
Preferably, the model base includes any one of extended compton, base parameter thin, base parameter thick no-standard, lucas-blueprint base, spectrum Procedure, plating thickness and composition analysis, influence factor, Multilayer.
As a preferred technical solution, the analysis method comprises the steps of:
(1) tabletting a standard sample for 60-100 s under the pressure of 30-50 t, taking a Ka spectral line of main elements in the standard sample as an analysis line, selecting a 2 theta angle corresponding to the spectral line, setting the voltage of a light pipe to be 30-45 KV, setting the current of the light pipe to be 800-1000 muA, testing the tabletting sample by using an X-ray fluorescence spectrometer for 50-100 s, testing the X-ray fluorescence intensity of the main elements, correcting the measured X-ray fluorescence intensity value by using a model matrix according to a standard value to obtain a corrected curve map, and establishing to obtain a corresponding standard curve;
(2) tabletting a sample to be detected for 60-100 s under the pressure of 30-50 t, taking the Ka spectral line of main elements in the sample to be detected as an analysis line, simultaneously selecting a 2 theta angle corresponding to the spectral line, setting the voltage of a light pipe to be 30-45 KV, setting the current of the light pipe to be 800-1000 muA, testing the tabletting sample by using an X-ray fluorescence spectrometer for 50-100 s, testing the X-ray fluorescence intensity of the main elements, and obtaining the content of the main elements in the sample to be detected according to the corresponding standard curve in the step (1);
the method comprises the following steps of (1) obtaining standard samples, wherein main elements in the standard samples in the step (1) are nickel elements, cobalt elements and manganese elements, the main elements in the samples to be detected in the step (2) are nickel elements, cobalt elements and manganese elements, and the model base body in the step (1) comprises any one of expanded Compton, thin basic parameters, thick basic parameters, no standard sample, Lucas-diagram base body, Spectro Procedure, coating thickness and component analysis, influence coefficients and Multilayer.
The invention provides a method for determining contents of Ni, Co and Mn elements in a nickel cobalt lithium manganate positive electrode material by a conventional ICP method, which comprises the following steps:
(1) the sample was passed through a 50 μm sieve, dried at 110 ℃. + -. 5 ℃ for 2h and placed in a desiccator to cool to room temperature. 0.20g of sample is weighed to the nearest 0.0001 g.
(2) Sample pretreatment: putting the sample into a 100mL beaker, adding 20mL hydrochloric acid (1+1), putting the beaker on a low-temperature electric hot plate for heating and dissolving, cooling, transferring the sample into a 200mL volumetric flask, and adding 2.00mL internal standard solution (2.5400 g of yttrium oxide [ w ] is weighed)(Y2O3)≥99.99％]Adding 30mL of hydrochloric acid into a beaker, heating to dissolve, taking down, cooling, washing a surface dish and the wall of the beaker with water, transferring the beaker into a 1000mL volumetric flask, diluting the beaker with water to a scale, mixing the beaker and the wall of the beaker uniformly, wherein 1mL of the solution contains 2mg of yttrium), diluting the beaker and the wall of the beaker with water to a scale, and mixing the beaker and the wall of the beaker uniformly.
(3) Preparation of a standard solution:
nickel standard storage solution: weighing 2.0000g pure nickel [ w ](Ni)≥99.99％]Placing in a beaker, adding 50mL hydrochloric acid (1+1), heating to dissolve, taking off, cooling, washing the surface dish and the wall of the cup with water, transferring into a 500mL volumetric flask, diluting with water to the scale, and mixing uniformly, wherein 1mL of the solution contains 4.0mg of nickel.
Cobalt standard storage solution: weighing 1.0000g pure cobalt [ w ](Co)≥99.99％]Placing in a beaker, adding 50mL hydrochloric acid (1+1), heating to dissolve, taking off, cooling, washing the surface dish and the wall of the cup with water, transferring into a 500mL volumetric flask, diluting with water to the scale, and mixing uniformly, wherein 1mL of the solution contains 2.0mg of cobalt.
Manganese standard storage solution: weighing 1.0000g pure manganese [ w ](Mn)≥99.99％]Placing in a beaker, adding 50mL hydrochloric acid (1+1), heating to dissolve, taking off, cooling, washing the surface dish and the wall of the cup with water, transferring into a 500mL volumetric flask, diluting with water to the scale, and mixing uniformly, wherein 1mL of the solution contains 2.0mg of manganese.
(4) Preparation of a series of standard solutions: accurately transferring 0mL, 10.00mL, 15.00mL and 20.00mL of lithium standard storage solution, 0mL, 7.00mL, 12.00mL and 18.00mL of nickel standard storage solution, 0mL, 5.00mL, 15.00mL and 30.00mL of cobalt standard storage solution and 0mL, 10.00mL, 20.00mL and 30.00mL of manganese standard storage solution into a group of 200mL volumetric flasks, respectively adding 2.00mL of internal standard solution, diluting to a scale with water, and uniformly mixing.
(5) Measurement: after the instrument runs stably, the emission light intensities of nickel, cobalt and manganese are measured by using a series of standard solutions according to the optimized working conditions of the instrument and the recommended wavelength of an analysis spectral line, the emission light intensities of the elements to be measured in the standard series solutions are measured from low to high, the mass concentration of the elements to be measured is taken as an abscissa, the emission light intensities are taken as ordinates, and a working curve is automatically drawn by a computer. The computer automatically calculates the mass concentration of the element to be measured from the working curve by measuring the intensity of the emitted light of the sample solution and the element to be measured in the blank solution along with the sample.
Compared with the prior art, the invention has the following beneficial effects:
the sample nickel cobalt lithium manganate positive electrode material to be detected does not need any pretreatment process, and the preparation is simple; only simple tabletting treatment is needed, the damage to the sample to be detected is small, the cost is saved, no chemical reagent is used, the risk coefficient is small, the safety risk does not exist basically in the treatment process of the sample to be detected, and the number of times of post personnel contacting with a hazard source is reduced; the established standard curve can be used for a long time, and the detection period of a measurement sample is short; therefore, the method for analyzing the main elements in the nickel cobalt lithium manganate cathode material provided by the invention has the advantages of high accuracy, good stability, high detection efficiency and high practicability, and is worthy of popularization and application.
Drawings
FIG. 1 is a graph comparing the mass percentages of Ni elements obtained by XRF and ICP respectively for the standard samples provided in examples 1-5.
FIG. 2 is a graph comparing the mass percentages of Co elements obtained by XRF and ICP for the standard samples provided in examples 1-5.
FIG. 3 is a graph showing a comparison of Mn element mass percentages obtained by XRF method and ICP method for standard samples provided in examples 1-5.
FIG. 4 is a graph showing the XRF method for standard Ni elements of the standard samples provided in examples 1 to 5.
FIG. 5 is a standard XRF plot of elemental Co for the standard samples provided in examples 1-5.
FIG. 6 is a graph showing XRF method calibration curves of Mn element for the standard samples provided in examples 1 to 5.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In one aspect, the present invention provides a specific embodiment, and in the specific embodiment, a method for establishing a standard curve in a lithium nickel cobalt manganese oxide positive electrode material is provided, as follows:
performing tabletting treatment on a standard sample with known content for 60-100 s under the pressure of 30-50 t, taking a Ka spectral line of a main element in a nickel-cobalt lithium manganate positive electrode material as an analysis line, simultaneously selecting a 2 theta angle corresponding to the spectral line, setting the voltage of a light pipe to be 30-45 KV, setting the current of the light pipe to be 800-1000 muA, performing content test on the tabletting sample by adopting a German Sespectrocube polarization energy dispersion X fluorescence analyzer, testing the X-ray fluorescence intensity of the main element, referring to a standard value, correcting the measured X-ray fluorescence intensity value by using a model substrate to obtain a corrected curve map, establishing a corresponding standard curve, determining the standard value by analyzing and determining the content of nickel, cobalt and manganese in the sample by adopting an ICP-OES test means, and taking test data as an element standard value.
First, a standard sample of a known content, each of which has a chemical formula of LiNi, is provided0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.6Co0.1Mn0.3O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Mn0.05O2。
On the basis of the standard curve, the content of the main elements in the sample to be tested is tested and analyzed, and the specific method comprises the following steps:
tabletting a sample to be detected for 60-100 s under the pressure of 30-50 t, taking the Ka spectral line of main elements in the sample to be detected as an analysis line, simultaneously selecting a 2 theta angle corresponding to the spectral line, setting the voltage of a light pipe to be 30-45 KV, setting the current of the light pipe to be 800-1000 muA, testing the tabletting sample by using an X-ray fluorescence spectrometer for 50-100 s, testing the X-ray fluorescence intensity of the main elements, and obtaining the content of the main elements in the sample to be detected according to the corresponding standard curve in the step (1).
Example 1
The embodiment provides a method for establishing a standard curve in a lithium nickel cobalt manganese oxide positive electrode material, which is performed based on the specific embodiment:
wherein the chemical formula of the standard sample is LiNi0.5Co0.2Mn0.3O2The main elements in the standard sample are Ni, Co and Mn, the pressure is 40t, the tabletting time is 80s, the light pipe voltage is 40KV, the light pipe current is 900 muA, and the testing time is 70 s.
Example 2
The embodiment provides a method for establishing a standard curve in a lithium nickel cobalt manganese oxide positive electrode material, which is performed based on the specific embodiment:
wherein the chemical formula of the standard sample is LiNi0.6Co0.1Mn0.3O2The main elements in the standard sample are Ni, Co and Mn, the pressure is 30t, the tabletting time is 100s, the light pipe voltage is 30KV, the light pipe current is 850 muA, and the testing time is 80 s.
Example 3
The embodiment provides a method for establishing a standard curve in a lithium nickel cobalt manganese oxide positive electrode material, which is performed based on the specific embodiment:
wherein the chemical formula of the standard sample is LiNi0.8Co0.1Mn0.1O2The main elements in the standard sample are Ni, Co and Mn, the pressure is 35t, the tabletting time is 90s, the light tube voltage is 45KV, the light tube current is 1000 muA, and the testing time is 55 s.
Example 4
The embodiment provides a method for establishing a standard curve in a lithium nickel cobalt manganese oxide positive electrode material, which is performed based on the specific embodiment:
wherein the chemical formula of the standard sample is LiNi0.6Co0.2Mn0.2O2In the standard sampleThe main elements are Ni, Co and Mn, the pressure is 50t, the tabletting time is 60s, the light tube voltage is 45KV, the light tube current is 1000 muA, and the testing time is 55 s.
Example 5
The embodiment provides a method for establishing a standard curve in a lithium nickel cobalt manganese oxide positive electrode material, which is performed based on the specific embodiment:
wherein the chemical formula of the standard sample is LiNi0.85Co0.1Mn0.05O2The main elements in the standard sample are Ni, Co and Mn, the pressure is 35t, the tabletting time is 90s, the light tube voltage is 45KV, the light tube current is 1000 muA, and the testing time is 55 s.
The mass percentages of Ni, Co and Mn after the test on the standard samples of examples 1-5 are shown in table 1.
TABLE 1
Figure BDA0003112912230000111
Based on the data of the mass percentages of nickel, cobalt and manganese provided in examples 1 to 5 in table 1, and the analysis comparison of the standard values of the elements obtained by ICP analysis of the standard samples in examples 1 to 5, the results are shown in fig. 1 to 3 (fig. 1 to 3, sample 1 to example 1, sample 2 to example 2-1, sample 3 to example 3-1, sample 4 to example 4, sample 5 to example 2-2, sample 6 to example 3-2, and sample 7 to example 5), and the fitting degree of the concentration curve to the standard curve is: r2Ni＝0.996196，R2Co＝0.996259，R2The Mn is 0.998046, which is more than 0.99, the linear relation is good, the accuracy of the result obtained by the analysis method provided by the invention can be verified, and the established standard curve can be used as a benchmark.
Based on the mass percentages and the element standard values of Ni, Co and Mn in examples 1-5, a Lucas Tooth model is adopted to correct the influence of fluorescence absorption among elements, and the Lucas Tooth model is a self-contained calibration model of the instrument. Measuring the intensity of the sample by X-ray fluorescence spectrometer to obtain the standard sample chemistryThe value is an abscissa, the fluorescence intensity of each element measured by a fluorometer is used as an ordinate to draw a working curve of each element, namely a standard curve, and the fitting degrees of the standard curve after correction are respectively as follows: r2Ni＝0.994，R2Co＝0.9919，R2Mn is 0.9968, all > 0.99, and the linear relation is good, as shown in the attached figures 4-6.
Two samples to be tested are selected and respectively correspond to application example 1 and application example 2.
Application example 1
The application example provides an analysis method for the content of a main element in a sample to be tested, which is performed based on a test analysis method in a specific implementation mode and specifically comprises the following steps:
the pressure is 30t, the time of tabletting treatment is 100s, the light tube voltage is 30KV, the light tube current is 850 muA, and the test time is 80 s.
The test was repeated 10 times for the test sample of example 1, and the results are shown in table 2.
TABLE 2
Figure BDA0003112912230000121
Figure BDA0003112912230000131
From the data results in table 2, it can be seen that the sample to be measured in application example 1 is LiNi from the data results of the contents of the main elements in the sample to be measured in application example 10.6Co0.1Mn0.3O2。
Application example 2
The application example provides an analysis method for the content of a main element in a sample to be tested, which is performed based on a test analysis method in a specific implementation mode and specifically comprises the following steps:
the pressure was 35t, the duration of the sheeting treatment was 90s, the tunnel voltage was 45KV, the tunnel current was 1000 muA, and the test duration was 55 s.
The test was repeated 10 times for the test sample of application example 2, and the results are shown in table 3.
TABLE 3
Ni/wt％ Co/wt％ Mn/wt％
Application example 2-1 49.9313 7.3939 2.7136
Application examples 2-2 50.0322 7.3716 2.7249
Application examples 2 to 3 50.1443 7.4293 2.7230
Application examples 2 to 4 50.2446 7.4139 2.7154
Application examples 2 to 5 49.9261 7.4191 2.7212
Application examples 2 to 6 49.9490 7.3929 2.7042
Application examples 2 to 7 50.0493 7.4010 2.7147
Application examples 2 to 8 49.9973 7.3923 2.6999
Application examples 2 to 9 49.9801 7.3706 2.6923
Application examples 2 to 10 50.2063 7.3859 2.7183
Mean value of 50.0061 7.401 2.7058
Standard deviation of 0.115 0.0193 0.0107
CV value 0.23 0.26 0.39
From the data results in table 3, it can be seen that the sample to be measured in application example 2 is LiNi, from the data results of the contents of the main elements in the sample to be measured in application example 20.8Co0.1Mn0.1O2。
The data results in tables 2 and 3 show that the analysis method provided by the invention can still maintain the accuracy of the data after a plurality of tests.
And selecting 3 samples to be tested, carrying out XRF test, analyzing the contents of nickel, cobalt and manganese in the samples, measuring the results every day, and respectively corresponding to application examples 3-5.
Application example 3
The application example provides an analysis method for the content of a main element in a sample to be tested, which is performed based on a test analysis method in a specific implementation mode and specifically comprises the following steps:
the pressure was 50t, the duration of the sheeting treatment was 60s, the tunnel voltage was 45KV, the tunnel current was 1000 muA, and the test duration was 55 s.
Application example 4
The application example provides an analysis method for the content of a main element in a sample to be tested, which is performed based on a test analysis method in a specific implementation mode and specifically comprises the following steps:
the pressure was 35t, the duration of the sheeting treatment was 90s, the tunnel voltage was 45KV, the tunnel current was 1000 muA, and the test duration was 55 s.
Application example 5
The application example provides an analysis method for the content of a main element in a sample to be tested, which is performed based on a test analysis method in a specific implementation mode and specifically comprises the following steps:
the pressure was 40t, the duration of the sheeting treatment was 80s, the tunnel voltage was 40KV, the tunnel current was 900 μ A, and the test duration was 70 s.
The samples to be tested in application examples 3-5 were tested each time for 5 days, wherein the mass percentage (wt%) of nickel is shown in table 4.
TABLE 4
Figure BDA0003112912230000151
Figure BDA0003112912230000161
Synchronously applying the samples to be tested provided by the examples 3-5 to test by an ICP method to obtain the mass percentage ratio of the main elements of nickel, cobalt and manganese;
the average mass percentage of the main elements nickel, cobalt and manganese in the sample to be tested in application examples 3 to 5 in 5 days was collated with the result obtained by performing the ICP test on the sample to be tested, and the result is shown in table 5.
TABLE 5
Figure BDA0003112912230000162
Figure BDA0003112912230000171
From the data results in tables 4 and 5, it can be seen that the sample to be measured in application example 3 is LiNi, from the data results of the contents of the main elements in the sample to be measured in application example 30.6Co0.2Mn0.2O2(ii) a From the data result of the main element content in the sample to be measured in application example 4, it can be known that the sample to be measured in application example 4 is LiNi0.85Co0.1Mn0.05O2(ii) a From the data result of the main element content in the sample to be measured in application example 5, it can be known that the sample to be measured in application example 5 is LiNi0.5Co0.2Mn0.3O2。
From the data results in table 4, it can be known that the method for analyzing the content of the main element in the nickel cobalt lithium manganate positive electrode material provided by the invention has long-term stability, high accuracy and extremely small error range.
From the data results in table 5, it can be seen that the analysis method for the content of the main element in the nickel cobalt lithium manganate positive electrode material provided by the present invention is consistent with the result obtained by the ICP method known to those skilled in the art, which proves the accuracy of the analysis method provided by the present application.
In conclusion, the invention adopts the X-ray fluorescence spectrometer to respectively measure the contents of Ni, Co and Mn elements in the nickel-cobalt-manganese positive electrode material (NCM), quickly measures the contents of Ni, Co and Mn in the NCM, is safe, quick, low in cost, high in accuracy, good in stability, high in detection efficiency and extremely practical, and is suitable for practical production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The method for analyzing the content of the main element in the nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps of:
(1) performing tabletting treatment on a standard sample, then testing the tabletting sample by using an X-ray fluorescence spectrometer, selecting a model correction curve spectrogram, preprocessing the curve spectrogram, and establishing to obtain a corresponding standard curve;
(2) and (3) tabletting the sample to be detected, testing the tabletted sample by using an X-ray fluorescence spectrometer, and obtaining the content of the main element in the sample to be detected according to the corresponding standard curve in the step (1).
2. The method for analyzing the content of the main elements in the nickel cobalt lithium manganate positive electrode material of claim 1, wherein the main elements in the standard sample of step (1) are nickel element, cobalt element and manganese element;
preferably, the main elements in the sample to be detected in the step (2) are nickel element, cobalt element and manganese element.
3. The method for analyzing the content of the main element in the nickel cobalt lithium manganate positive electrode material according to claim 1 or 2, wherein the pressure in the tabletting process in step (1) and the pressure in the tabletting process in step (2) are each independently 30 to 50 t.
4. The method for analyzing the content of the main element in the nickel cobalt lithium manganate positive electrode material according to any one of claims 1 to 3, wherein the dwell time in the tabletting process in step (1) and the dwell time in the tabletting process in step (2) are each independently 60 to 100 seconds.
5. The method for analyzing the content of main elements in a nickel cobalt lithium manganate positive electrode material as set forth in any of claims 1-4, characterized in that, in the testing process of step (1), Ka spectral line of main elements in the standard sample is taken as an analysis line, and 2 theta angle corresponding to the spectral line is selected;
preferably, in the test process in the step (1), the voltage of the light pipe is 30-45 KV;
preferably, in the testing process in the step (1), the light pipe current is 800-1000 muA.
6. The method for analyzing the content of the main elements in the nickel cobalt lithium manganate positive electrode material according to any one of claims 1 to 5, wherein a Ka spectral line of the main elements in the sample to be tested is taken as an analysis line, and a 2 theta angle corresponding to the spectral line is selected;
preferably, in the test process in the step (2), the voltage of the light pipe is 30-45 KV;
preferably, in the testing process in the step (2), the light pipe current is 800-1000 muA.
7. The method for analyzing the content of the main element in the nickel cobalt lithium manganate positive electrode material of any one of claims 1 to 6, wherein the time of the test in step (1) and the time of the test in step (2) are each independently 50 to 100 s.
8. The method for analyzing the content of main elements in the nickel cobalt lithium manganate positive electrode material of any one of claims 1 to 7, wherein the selected model calibration curve spectrogram in step (1) comprises:
and (2) testing the main elements in the standard sample in the step (1), testing the X-ray fluorescence intensity of the main elements, referring to the standard value, and correcting the measured X-ray fluorescence intensity value by using the model matrix to obtain a corrected curve map.
9. The method of claim 8, wherein the model matrix comprises any one of Compton extension, thin basic parameter, thick basic parameter without standard sample, Lucas-diagram matrix, Spectro Procedure, coating thickness and composition analysis, influence coefficient, and Multilayer.
10. The method for analyzing the content of the main element in the lithium nickel cobalt manganese oxide positive electrode material according to any one of claims 1 to 9, wherein the method comprises the following steps:
(1) tabletting a standard sample for 60-100 s under the pressure of 30-50 t, taking a Ka spectral line of main elements in the standard sample as an analysis line, selecting a 2 theta angle corresponding to the spectral line, setting the voltage of a light pipe to be 30-45 KV, setting the current of the light pipe to be 800-1000 muA, testing the tabletting sample by using an X-ray fluorescence spectrometer for 50-100 s, testing the X-ray fluorescence intensity of the main elements, correcting the measured X-ray fluorescence intensity value by using a model matrix according to a standard value to obtain a corrected curve map, and establishing to obtain a corresponding standard curve;
(2) tabletting a sample to be detected for 60-100 s under the pressure of 30-50 t, taking the Ka spectral line of main elements in the sample to be detected as an analysis line, simultaneously selecting a 2 theta angle corresponding to the spectral line, setting the voltage of a light pipe to be 30-45 KV, setting the current of the light pipe to be 800-1000 muA, testing the tabletting sample by using an X-ray fluorescence spectrometer for 50-100 s, testing the X-ray fluorescence intensity of the main elements, and obtaining the content of the main elements in the sample to be detected according to the corresponding standard curve in the step (1);
the method comprises the following steps of (1) obtaining standard samples, wherein main elements in the standard samples in the step (1) are nickel elements, cobalt elements and manganese elements, the main elements in the samples to be detected in the step (2) are nickel elements, cobalt elements and manganese elements, and the model base body in the step (1) comprises any one of expanded Compton, thin basic parameters, thick basic parameters, no standard sample, Lucas-diagram base body, Spectro Procedure, coating thickness and component analysis, influence coefficients and Multilayer.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113702410A (en) * 2021-09-15 2021-11-26 宁波大地化工环保有限公司 Analysis method for rapidly testing elements in nickel-containing waste residue
CN114113184A (en) * 2021-11-29 2022-03-01 南京航空航天大学 Scattering correction method for X-ray fluorescence thin layer analysis of tailing slurry
CN115629057A (en) * 2022-10-19 2023-01-20 杭州谱育科技发展有限公司 Lithium battery positive electrode material analysis method based on LIBS technology
CN115639231A (en) * 2022-08-31 2023-01-24 茂名阪田油墨有限公司 Quantitative detection method for Co element in printing ink
CN118671116A (en) * 2024-08-05 2024-09-20 南通瑞翔新材料有限公司 Method for measuring element content by using energy dispersion X-ray spectrometer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104880477A (en) * 2015-06-19 2015-09-02 金川集团股份有限公司 X-fluorescence joint-measurement analysis method for elements of mixed copper concentrate
CN106769335A (en) * 2017-02-26 2017-05-31 合肥国轩高科动力能源有限公司 Fuse piece for drift correction of X-ray fluorescence spectrometer and preparation method and application thereof
CN109557118A (en) * 2018-12-10 2019-04-02 武钢集团昆明钢铁股份有限公司 A kind of method of each component content in x-ray fluorescence spectrometry ferro-titanium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104880477A (en) * 2015-06-19 2015-09-02 金川集团股份有限公司 X-fluorescence joint-measurement analysis method for elements of mixed copper concentrate
CN106769335A (en) * 2017-02-26 2017-05-31 合肥国轩高科动力能源有限公司 Fuse piece for drift correction of X-ray fluorescence spectrometer and preparation method and application thereof
CN109557118A (en) * 2018-12-10 2019-04-02 武钢集团昆明钢铁股份有限公司 A kind of method of each component content in x-ray fluorescence spectrometry ferro-titanium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113702410A (en) * 2021-09-15 2021-11-26 宁波大地化工环保有限公司 Analysis method for rapidly testing elements in nickel-containing waste residue
CN114113184A (en) * 2021-11-29 2022-03-01 南京航空航天大学 Scattering correction method for X-ray fluorescence thin layer analysis of tailing slurry
CN114113184B (en) * 2021-11-29 2023-11-03 南京航空航天大学 Scattering correction method for X fluorescence thin layer analysis of tailing pulp
CN115639231A (en) * 2022-08-31 2023-01-24 茂名阪田油墨有限公司 Quantitative detection method for Co element in printing ink
CN115629057A (en) * 2022-10-19 2023-01-20 杭州谱育科技发展有限公司 Lithium battery positive electrode material analysis method based on LIBS technology
CN118671116A (en) * 2024-08-05 2024-09-20 南通瑞翔新材料有限公司 Method for measuring element content by using energy dispersion X-ray spectrometer

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