Lithium ore component analysis series standard sample and preparation method thereof

Abstract

The present application relates to the technical field of standard sample, in particular to a lithium ore component analysis series standard sample and a preparation method thereof, the chemical component composition and content range of the standard sample are as follows: Li2O: 0.80~6.2%; Na2O: 0.2~4.0%; K2O: 0.4~4.4%; Rb2O: 0.05~0.7%; Cs2O: 0.02~0.3%; SiO2: 49~69%; Al2O3: 14~19%; TiO2: 0.004~0.05%; Fe2O3: 0.3~1.3%; P2O5: 0.1~1.1%; BeO: 0.01~0.05%; CaO: 0.5~7%; MgO: 0.1~0.6%; MnO: 0.04~0.2%; S: 0.005~3%; Ta2O5: 0.01~0.07%; Nb2O5: 0.003~0.02%; F: 0.04~2.2%; ignition loss: 2.0~14%. The lithium ore standard sample prepared by the present application has many fixed values, and the linear relationship of main components is good, and the problem of poor uniformity caused by the segregation of characteristic elements is avoided, the needs of different users, different instruments, different analysis methods can be met, and the lithium ore standard sample can be widely applied to the analysis and quality monitoring of lithium ore.

Description

Technical Field

[0001] This invention relates to the field of standard sample technology, specifically to a series of standard samples for lithium ore composition analysis and their preparation method. Background Technology

[0002] The development of the new energy vehicle industry has greatly promoted the development of the lithium battery industry and brought positive impacts to lithium resource development. China imports a large amount of lithium ore every year to meet its lithium production needs. Therefore, developing standard samples compatible with domestic and international lithium ore resources has become an urgent task.

[0003] The search revealed that the following types of standard samples of lithium ore currently exist:

[0004] The lithium ore standard sample GSB04-3891-2021 developed by SGS-CSTC Standards Technical Services Co., Ltd. has determined the standard values ​​for 14 elements, but has not determined the standard values ​​for Nb2O5, BeO, Ta2O5, etc.

[0005] The lithium ore standard reference materials (GBW07152 and GBW07153) and rare earth ore composition analysis standard reference materials (GBW07184) from Shenyang Rock and Mineral Testing Center did not have sulfur values ​​assigned, and the lithium oxide content was 0.460% and 2.29%, respectively.

[0006] The spodumene standard materials GBW07733, GBW07734, and GBW07735 from the National Geological Experiment and Testing Center have lithium oxide contents of 6.30%, 6.23%, and 1.30%, respectively, but no values ​​for fluorine or other components have been assigned.

[0007] The National Institute of Standards and Technology (NIST) in the United States developed lithium ore standard samples 181, 182, and 183, which only assigned values ​​to Li2O. The values ​​for four components, namely Na2O, K2O, Rb2O, and Cs2O, were used as reference values. Values ​​for other components, such as SiO2, Al2O3, Ta2O5, and Nb2O5, were not assigned.

[0008] It is evident that many characteristic element values ​​are missing in the current lithium ore standard samples on the market, which cannot meet the needs of different instruments and analytical methods, especially the lack of serialized lithium ore standard samples with multiple component contents.

[0009] In addition, some elements in existing lithium ore standard samples are prone to segregation and are unstable. How to set the coverage range of the main elements and the content range of each element in the lithium ore standard samples to avoid the problem of poor uniformity caused by the segregation of characteristic elements remains a technical challenge. Summary of the Invention

[0010] To address the shortcomings of existing technologies, this invention provides a series of standard samples for lithium ore composition analysis and their preparation method. The lithium ore standard samples not only have a wide range of quantifiable components, but also avoid the problem of poor homogeneity caused by the segregation of characteristic elements. They can meet the needs of different users, different instruments and equipment, and different analytical methods, and can be widely used in the analysis, testing, and quality monitoring of lithium ore.

[0011] This invention is achieved through the following technical solution:

[0012] A series of standard samples for lithium ore composition analysis is provided, with the following chemical composition and content range:

[0013] Li2O: 0.80~6.2%; Na2O: 0.2~4.0%; K2O: 0.4~4.4%; Rb2O: 0.05~0.7%; Cs2O: 0.02 ~0.3%; SiO2: 49~69%; Al2O3: 14~19%; TiO2: 0.004~0.05%; Fe2O3: 0.3~1.3%; P2O 5: 0.1–1.1%; BeO: 0.01–0.05%; CaO: 0.5–7%; MgO: 0.1–0.6%; MnO: 0.04–0.2%; S: 0.005–3%; Ta₂O₅: 0.01–0.07%; Nb₂O₅: 0.003–0.02%; Loss on ignition: 2.0–14%; F: 0.04–2.2%.

[0014] The lithium ore composition analysis series of standard samples of the present invention consists of the following 13 standard samples, including 9 samples of lithium feldspar, numbered ZBK466, ZBK466A, ZBK467, ​​ZBK467A, ZBK469, ZBK469A, ZBK469B, ZBK468 and ZBK489; 3 samples of lepidolite, numbered ZBK487, ZBK488 and ZBK486; and 1 sample of spodumene, numbered ZBK479.

[0015] Specifically, the chemical composition and mass percentage of each standard sample are as follows:

[0016] ZBK466 (lithium feldspar) has the following mass percentages of components: Li₂O: 0.863±0.006%; Na₂O: 0.32±0.007%; K₂O: 0.444±0.003%; Rb₂O: 0.066±0.004%; Cs₂O: 0.029±0.003%; SiO₂: 57.53±0.11%; Al₂O₃: 19.29±0.08%; TiO₂: 0.039±0.003%; Fe₂O₃: 0.68%. 2±0.004%; P2O5: 0.146±0.003%; BeO: 0.017±0.003%; CaO: 6.06±0.05%; MgO: 0.410±0.004%; MnO: 0.054±0.003%; S: 2.73±0.05%; Ta2O5: 0.015±0.03%; Nb2O5: 0.0046±0.0004%; Loss on ignition: 7.19±0.10%; F: 0.057±0.004%;

[0017] ZBK466A (lithium feldspar), the mass percentages of its components are as follows: Li₂O: 0.819±0.005%; Na₂O: 0.326±0.005%; K₂O: 0.502±0.003%; Rb₂O: 0.065±0.004%; Cs₂O: 0.026±0.005%; SiO₂: 57.50±0.14%; Al₂O₃: 18.38±0.08%; TiO₂: 0.044±0.003%; Fe₂O₃: 0.7%. 83±0.005%; P2O5: 0.139±0.003%; BeO: 0.018±0.002%; CaO: 6.61±0.05%; MgO: 0.532±0.004%; MnO: 0.062±0.004%; S: 2.66±0.05%; Ta2O5: 0.017±0.003%; Nb2O5: 0.0045±0.0004%; Loss on ignition: 7.73±0.10%; F: 0.053±0.004%;

[0018] ZBK467 (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.50±0.04%; Na₂O: 2.55±0.03%; K₂O: 3.96±0.05%; Rb₂O: 0.653±0.004%; Cs₂O: 0.222±0.005%; SiO₂: 66.43±0.14%; Al₂O₃: 17.40±0.08%; TiO₂: 0.036±0.003%; Fe₂O₃: 0.584±0. 0.004%; P2O5: 0.912±0.008%; BeO: 0.029±0.003%; CaO: 1.44±0.05%; MgO: 0.221±0.003%; MnO: 0.115±0.003%; S: 0.0061±0.0004%; Ta2O5: 0.059±0.004%; Nb2O5: 0.012±0.002%; Loss on ignition: 3.60±0.08%; F: 1.59±0.04%;

[0019] ZBK467A (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.64±0.04%; Na₂O: 2.37±0.05%; K₂O: 4.29±0.06%; Rb₂O: 0.728±0.005%; Cs₂O: 0.236±0.005%; SiO₂: 66.38±0.14%; Al₂O₃: 17.62±0.08%; TiO₂: 0.027±0.004%; Fe₂O₃: 0.588%. ±0.005%; P2O5: 0.722±0.006%; BeO: 0.028±0.005%; CaO: 1.01±0.02%; MgO: 0.176±0.004%; MnO: 0.134±0.004%; S: 0.015±0.002%; Ta2O5: 0.047±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 3.29±0.08%; F: 1.77±0.04%;

[0020] ZBK469 (lithium feldspar), the mass percentages of its components are as follows: Li₂O: 1.21±0.04%; Na₂O: 3.59±0.04%; K₂O: 2.19±0.03%; Rb₂O: 0.397±0.004%; Cs₂O: 0.205±0.003%; SiO₂: 67.90±0.14%; Al₂O₃: 16.91±0.08%; TiO₂: 0.0041±0.0004%; Fe₂O₃: 1.22± 0.03%; P2O5: 1.04±0.03%; BeO: 0.047±0.003%; CaO: 1.15±0.04%; MgO: 0.113±0.005%; MnO: 0.166±0.004%; S: 0.0065±0.0005%; Ta2O5: 0.022±0.002%; Nb2O5: 0.0078±0.0005%; Loss on ignition: 2.10±0.07%; F: 1.67±0.06%;

[0021] ZBK469A (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.60±0.04%; Na₂O: 3.58±0.04%; K₂O: 3.09±0.05%; Rb₂O: 0.576±0.004%; Cs₂O: 0.264±0.004%; SiO₂: 68.28±0.14%; Al₂O₃: 16.13±0.08%; TiO₂: 0.020±0.002%; Fe₂O₃: 0.330± 0.003%; P2O5: 1.05±0.04%; BeO: 0.042±0.005%; CaO: 1.22±0.04%; MgO: 0.137±0.003%; MnO: 0.052±0.004%; S: 0.0074±0.0006%; Ta2O5: 0.028±0.004%; Nb2O5: 0.012±0.002%; Loss on ignition: 2.12±0.09%; F: 2.24±0.06%;

[0022] ZBK469B (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.38±0.05%; Na₂O: 3.79±0.04%; K₂O: 2.81±0.06%; Rb₂O: 0.499±0.006%; Cs₂O: 0.245±0.006%; SiO₂: 68.17±0.12%; Al₂O₃: 16.27±0.08%; TiO₂: 0.03±0.003%; Fe₂O₃: 0.419± 0.005%; P2O5: 1.06±0.04%; BeO: 0.049±0.004%; CaO: 1.07±0.05%; MgO: 0.237±0.003%; MnO: 0.048±0.003%; S: 0.0062±0.0005%; Ta2O5: 0.028±0.005%; Nb2O5: 0.011±0.002%; Loss on ignition: 2.22±0.09%; F: 1.64±0.05%;

[0023] ZBK468 (lithium feldspar), the mass percentages of its components are as follows: Li₂O: 1.38±0.04%; Na₂O: 2.50±0.04%; K₂O: 3.83±0.05%; Rb₂O: 0.610±0.005%; Cs₂O: 0.220±0.005%; SiO₂: 65.95±0.12%; Al₂O₃: 17.37±0.08%; TiO₂: 0.048±0.004%; Fe₂O₃: 0.729±0. 0.006%; P2O5: 0.826±0.008%; BeO: 0.024±0.004%; CaO: 1.52±0.05%; MgO: 0.271±0.007%; MnO: 0.115±0.004%; S: 0.0061±0.0004%; Ta2O5: 0.067±0.004%; Nb2O5: 0.013±0.002%; Loss on ignition: 3.82±0.08%; F: 1.29±0.04%;

[0024] ZBK487 (lithium mica), the mass percentages of each component are as follows: Li₂O: 2.51±0.06%; Na₂O: 2.31±0.03%; K₂O: 3.87±0.05%; Rb₂O: 0.638±0.006%; Cs₂O: 0.224±0.005%; SiO₂: 66.04±0.12%; Al₂O₃: 16.11±0.08%; TiO₂: 0.035±0.003%; Fe₂O₃: 0.586±0. 0.004%; P2O5: 0.607±0.004%; BeO: 0.028±0.003%; CaO: 0.825±0.007%; MgO: 0.188±0.004%; MnO: 0.108±0.005%; S: 0.014±0.003%; Ta2O5: 0.049±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 4.51±0.08%; F: 1.61±0.04%;

[0025] The mass percentages of each component in ZBK488 (lithium mica) are as follows: Li₂O: 3.50±0.05%; Na₂O: 2.24±0.05%; K₂O: 3.82±0.05%; Rb₂O: 0.633±0.005%; Cs₂O: 0.222±0.003%; SiO₂: 64.28±0.12%; Al₂O₃: 15.94±0.07%; TiO₂: 0.038±0.003%; Fe₂O₃: 0.610±0. 0.008%; P2O5: 0.600±0.005%; BeO: 0.028±0.005%; CaO: 0.802±0.006%; MgO: 0.173±0.004%; MnO: 0.107±0.004%; S: 0.016±0.004%; Ta2O5: 0.053±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 6.05±0.08%; F: 1.45±0.04%;

[0026] ZBK489 (lithium feldspar) has the following mass percentages of components: Li₂O: 1.51±0.04%; Na₂O: 2.04±0.04%; K₂O: 4.34±0.05%; Rb₂O: 0.700±0.004%; Cs₂O: 0.230±0.004%; SiO₂: 68.56±0.14%; Al₂O₃: 16.58±0.08%; TiO₂: 0.035±0.003%; Fe₂O₃: 0.502±0. 0.005%; P2O5: 0.475±0.003%; BeO: 0.035±0.003%; CaO: 0.574±0.004%; MgO: 0.155±0.004%; MnO: 0.121±0.005%; S: 0.0054±0.0006%; Ta2O5: 0.034±0.004%; Nb2O5: 0.010±0.002%; Loss on ignition: 2.89±0.08%; F: 1.75±0.04%;

[0027] ZBK486 (lithium mica), the mass percentages of each component are as follows: Li₂O: 4.49±0.05%; Na₂O: 3.19±0.04%; K₂O: 2.75±0.03%; Rb₂O: 0.530±0.005%; Cs₂O: 0.243±0.004%; SiO₂: 63.41±0.12%; Al₂O₃: 14.91±0.08%; TiO₂: 0.018±0.002%; Fe₂O₃: 0.290±0. 0.003%; P2O5: 0.993±0.006%; BeO: 0.045±0.004%; CaO: 1.15±0.05%; MgO: 0.118±0.003%; MnO: 0.047±0.003%; S: 0.011±0.002%; Ta2O5: 0.029±0.003%; Nb2O5: 0.0095±0.0005%; Loss on ignition: 6.08±0.10%; F: 2.15±0.04%;

[0028] ZBK479 (spodumene), the mass percentages of each component are as follows: Li₂O: 6.10±0.05%; Na₂O: 0.283±0.003%; K₂O: 0.456±0.005%; Rb₂O: 0.057±0.004%; Cs₂O: 0.027±0.002%; SiO₂: 49.42±0.15%; Al₂O₃: 16.02±0.08%; TiO₂: 0.040±0.003%; Fe₂O₃: 0.687 ±0.005%; P2O5: 0.125±0.004%; BeO: 0.019±0.002%; CaO: 5.73±0.06%; MgO: 0.425±0.008%; MnO: 0.051±0.004%; S: 2.29±0.08%; Ta2O5: 0.013±0.002%; Nb2O5: 0.0037±0.0004%; Loss on ignition: 14.01±0.20%; F: 0.043±0.002%.

[0029] This invention also provides a method for preparing a series of standard samples for lithium ore composition analysis, comprising the following steps:

[0030] S1. Investigation phase: Collect physicochemical property data of target samples and determine the composition range and uncertainty requirements of standard samples;

[0031] S2. Component design: Based on the survey data, at least 3 different component gradients are designed using orthogonal experimental design, with the component content difference between each group not less than 5%;

[0032] S3. Based on the design range of the composition, raw materials from different domestic and foreign mineral sources (Yichun, Jiangxi; Altay, Xinjiang; Atacama, Chile; Uyuni Mine, Bolivia, Argentina; Zimbabwe; Xuelong Mountain, Xinjiang; Green Bushes, Australia; Nigeria; Dahongliutan, Xinjiang; Maiki, Ganzi Prefecture, Sichuan; Suining, Sichuan) are selected. The composition is verified using X-ray fluorescence spectrometry, infrared absorption spectrometry, atomic absorption spectrometry, and ion-selective electrode method to ensure that the main components and trace element components are within the design range.

[0033] S4. Drying treatment: Place the raw materials in a drying oven and dry them at 105±5℃ for 4 to 6 hours to make the moisture content ≤0.1%;

[0034] S5. Crushing and Grinding: A three-stage crushing system is adopted, including: jaw crusher for coarse crushing to particle size ≤5mm, double roll crusher for fine crushing to particle size ≤1mm, and ball mill for grinding to D90≤74μm;

[0035] S6. Sieving process: The material is classified through a 200-mesh standard sieve (74μm), and the material on the sieve is returned to the ball mill for secondary grinding.

[0036] S7. Mechanical mixing: Use a three-dimensional mixer at a speed of 20-30 rpm for 2-4 hours to mix the material. The coefficient of variation of the mixing uniformity CV ≤ 1%.

[0037] S8. Sealed storage: Place the mixed sample in an aluminum foil bag. Materials with a sulfur content exceeding 2% should be vacuum-packed. The ambient humidity should be controlled below RH 50%.

[0038] Furthermore, it also includes: S9, uniformity test: including:

[0039] S9.1 Initial inspection stage: Randomly select 5 samples for XRD detection. If the relative standard deviation (RSD) is greater than 3%, return to step S7.

[0040] S9.2 Final inspection stage: Sampling inspection shall be carried out in accordance with GB / T 15000 series standards, and the pass standard is RSD≤1.5%;

[0041] Furthermore, it also includes:

[0042] S10. Stability Study: After storage at 40℃ for 30 days, the monthly component change rate should be <0.5%; multiple stability studies should be conducted on the standard sample within two years, and the absolute value of the maximum difference between the measured value of the standard sample and the standard value should be less than or equal to the uncertainty of the set value.

[0043] S11. Mathematical Statistics: Use the Grubbs test to remove outliers and calculate the expanded uncertainty (k=2);

[0044] S12. Value determination analysis: Value determination is carried out jointly by at least 8 laboratories, and the final standard value is the weighted average.

[0045] Preferably, in step S5, the ball mill uses zirconia grinding balls, and the ball-to-material ratio is controlled at 3 to 5:1.

[0046] Furthermore, in step S9.2, stratified random sampling is used to take at least 10 samples from each of the 3 different packaging batches for ICP-OES testing.

[0047] The beneficial effects of this invention are:

[0048] The lithium ore standard sample developed in this invention is a multi-point standard sample, containing 9 points of lithium feldspar, 3 points of lepidolite, and 1 point of spodumene. Values ​​were assigned to 19 components, including Li₂O, Na₂O, K₂O, TiO₂, SiO₂, Al₂O₃, CaO, MgO, S, P₂O₅, MnO, Fe₂O₃, Rb₂O, Cs₂O, BeO, Ta₂O₅, Nb₂O₅, loss on ignition, and F. This standard sample has a wide range of assigned components, meeting the needs of different users, instruments, and analytical methods. It is widely used in the analysis, testing, and quality monitoring of lithium ore.

[0049] The standard samples prepared by this invention have a rationally designed chemical composition and a scientifically advanced preparation and processing technology. Multi-stage crushing and three-dimensional mechanical mixing and sieving processes were employed to ensure the homogeneity of the chemical composition of the standard samples. Rigorous initial and re-inspections of homogeneity show that this series of standard samples exhibits good homogeneity. Multiple laboratories, using accurate and reliable analytical methods based on different principles, have determined standard values ​​for 19 components in lithium ore, with accurate and reliable values.

[0050] The standard sample of this invention has been tested for stability and shows good stability. This standard sample has a wide range of applications, suitable for both routine chemical analysis of lithium ore and instrumental analysis of lithium ore composition.

[0051] The standard samples of this invention have undergone homogeneity testing, handling of doubtful values, and statistical calculation of average value and standard uncertainty, all of which comply with the requirements of ISO Guide 34, ISO Guide 35, ISO Guide 31, GB / T 15000 series "Standard Sample Working Guidelines", and YS / T 409-2012 "Technical Specifications for Standard Samples for Analysis of Non-ferrous Metal Products", ensuring the accuracy of the standard samples. Attached Figure Description

[0052] Figure 1 This is a fluorescence spectrum curve of Al2O3, a series of lithium ore standard samples in this invention.

[0053] Figure 2 This is a fluorescence spectrum curve of CaO, a series of lithium ore standard samples in this invention.

[0054] Figure 3 This is a fluorescence spectrum curve of K2O, a series of lithium ore standard samples in this invention.

[0055] Figure 4 This is a fluorescence spectrum curve of the lithium ore series standard sample P2O5 in this invention.

[0056] Figure 5 This is a fluorescence spectrum curve of the lithium ore series standard sample Rb2O in this invention.

[0057] Figure 6 This is a fluorescence spectrum curve of the lithium ore series standard sample Ta2O5 in this invention.

[0058] Figure 7 This is a fluorescence spectrum curve of SiO2, a series of lithium ore standard samples in this invention.

[0059] Figure 8 This is a fluorescence spectrum curve of Fe2O3, a series of lithium ore standard samples in this invention.

[0060] Figure 9 The image shows the fluorescence spectrum of MnO, a series of lithium ore standard samples, used in this invention.

[0061] Figure 10 This is a fluorescence spectrum curve of Na2O, a series of lithium ore standard samples used in this invention. Detailed Implementation

[0062] To clearly illustrate the technical features of this solution, the following detailed implementation method will be used to explain the solution.

[0063] Example 1:

[0064] A series of standard samples for lithium ore composition analysis, with chemical composition and content range as shown below:

[0065] Li2O: 0.80~6.2%; Na2O: 0.2~4.0%; K2O: 0.4~4.4%; Rb2O: 0.05~0.7%; Cs2O: 0.02 ~0.3%; SiO2: 49~69%; Al2O3: 14~19%; TiO2: 0.004~0.05%; Fe2O3: 0.3~1.3%; P2O 5: 0.1–1.1%; BeO: 0.01–0.05%; CaO: 0.5–7%; MgO: 0.1–0.6%; MnO: 0.04–0.2%; S: 0.005–3%; Ta₂O₅: 0.01–0.07%; Nb₂O₅: 0.003–0.02%; Loss on ignition: 2.0–14%; F: 0.04–2.2%.

[0066] In this embodiment, the series of standard samples for lithium ore composition analysis mainly consists of the following thirteen types of standard samples.

[0067] The results include 9 points of lithium feldspar, numbered ZBK466, ZBK466A, ZBK467, ​​ZBK467A, ZBK469, ZBK469A, ZBK469B, ZBK468, and ZBK489; 3 points of lepidolite, numbered ZBK487, ZBK488, and ZBK486; and 1 point of spodumene, numbered ZBK479.

[0068] Specifically, the chemical composition and mass percentage of each standard sample are as follows:

[0069] (1) ZBK466 (lithium feldspar), the mass percentages of each component are as follows: Li2O: 0.863±0.006%; Na2O: 0.32±0.007%; K2O: 0.444±0.003%; Rb2O: 0.066±0.004%; Cs2O: 0.029±0.003%; SiO2: 57.53±0.11%; Al2O3: 19.29±0.08%; TiO2: 0.039±0.003%; Fe2O3: 0. 682±0.004%; P2O5: 0.146±0.003%; BeO: 0.017±0.003%; CaO: 6.06±0.05%; MgO: 0.410±0.004%; MnO: 0.054±0.003%; S: 2.73±0.05%; Ta2O5: 0.015±0.03%; Nb2O5: 0.0046±0.0004%; Loss on ignition: 7.19±0.10%; F: 0.057±0.004%;

[0070] (2) ZBK466A (lithium feldspar), the mass percentages of each component are as follows: Li2O: 0.819±0.005%; Na2O: 0.326±0.005%; K2O: 0.502±0.003%; Rb2O: 0.065±0.004%; Cs2O: 0.026±0.005%; SiO2: 57.50±0.14%; Al2O3: 18.38±0.08%; TiO2: 0.044±0.003%; Fe2O3: 0. 783±0.005%; P2O5: 0.139±0.003%; BeO: 0.018±0.002%; CaO: 6.61±0.05%; MgO: 0.532±0.004%; MnO: 0.062±0.004%; S: 2.66±0.05%; Ta2O5: 0.017±0.003%; Nb2O5: 0.0045±0.0004%; Loss on ignition: 7.73±0.10%; F: 0.053±0.004%;

[0071] (3) ZBK467 (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.50±0.04%; Na₂O: 2.55±0.03%; K₂O: 3.96±0.05%; Rb₂O: 0.653±0.004%; Cs₂O: 0.222±0.005%; SiO₂: 66.43±0.14%; Al₂O₃: 17.40±0.08%; TiO₂: 0.036±0.003%; Fe₂O₃: 0.584%. ±0.004%; P2O5: 0.912±0.008%; BeO: 0.029±0.003%; CaO: 1.44±0.05%; MgO: 0.221±0.003%; MnO: 0.115±0.003%; S: 0.0061±0.0004%; Ta2O5: 0.059±0.004%; Nb2O5: 0.012±0.002%; Loss on ignition: 3.60±0.08%; F: 1.59±0.04%;

[0072] (4) ZBK467A (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.64±0.04%; Na₂O: 2.37±0.05%; K₂O: 4.29±0.06%; Rb₂O: 0.728±0.005%; Cs₂O: 0.236±0.005%; SiO₂: 66.38±0.14%; Al₂O₃: 17.62±0.08%; TiO₂: 0.027±0.004%; Fe₂O₃: 0.58 8±0.005%; P2O5: 0.722±0.006%; BeO: 0.028±0.005%; CaO: 1.01±0.02%; MgO: 0.176±0.004%; MnO: 0.134±0.004%; S: 0.015±0.002%; Ta2O5: 0.047±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 3.29±0.08%; F: 1.77±0.04%;

[0073] (5) ZBK469 (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.21±0.04%; Na₂O: 3.59±0.04%; K₂O: 2.19±0.03%; Rb₂O: 0.397±0.004%; Cs₂O: 0.205±0.003%; SiO₂: 67.90±0.14%; Al₂O₃: 16.91±0.08%; TiO₂: 0.0041±0.0004%; Fe₂O₃: 1.2 2±0.03%; P2O5: 1.04±0.03%; BeO: 0.047±0.003%; CaO: 1.15±0.04%; MgO: 0.113±0.005%; MnO: 0.166±0.004%; S: 0.0065±0.0005%; Ta2O5: 0.022±0.002%; Nb2O5: 0.0078±0.0005%; Loss on ignition: 2.10±0.07%; F: 1.67±0.06%;

[0074] (6) ZBK469A (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.60±0.04%; Na₂O: 3.58±0.04%; K₂O: 3.09±0.05%; Rb₂O: 0.576±0.004%; Cs₂O: 0.264±0.004%; SiO₂: 68.28±0.14%; Al₂O₃: 16.13±0.08%; TiO₂: 0.020±0.002%; Fe₂O₃: 0.33%. 0±0.003%; P2O5: 1.05±0.04%; BeO: 0.042±0.005%; CaO: 1.22±0.04%; MgO: 0.137±0.003%; MnO: 0.052±0.004%; S: 0.0074±0.0006%; Ta2O5: 0.028±0.004%; Nb2O5: 0.012±0.002%; Loss on ignition: 2.12±0.09%; F: 2.24±0.06%;

[0075] (7) ZBK469B (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.38±0.05%; Na₂O: 3.79±0.04%; K₂O: 2.81±0.06%; Rb₂O: 0.499±0.006%; Cs₂O: 0.245±0.006%; SiO₂: 68.17±0.12%; Al₂O₃: 16.27±0.08%; TiO₂: 0.03±0.003%; Fe₂O₃: 0.41 9±0.005%; P2O5: 1.06±0.04%; BeO: 0.049±0.004%; CaO: 1.07±0.05%; MgO: 0.237±0.003%; MnO: 0.048±0.003%; S: 0.0062±0.0005%; Ta2O5: 0.028±0.005%; Nb2O5: 0.011±0.002%; Loss on ignition: 2.22±0.09%; F: 1.64±0.05%;

[0076] (8) ZBK468 (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.38±0.04%; Na₂O: 2.50±0.04%; K₂O: 3.83±0.05%; Rb₂O: 0.610±0.005%; Cs₂O: 0.220±0.005%; SiO₂: 65.95±0.12%; Al₂O₃: 17.37±0.08%; TiO₂: 0.048±0.004%; Fe₂O₃: 0.729 ±0.006%; P2O5: 0.826±0.008%; BeO: 0.024±0.004%; CaO: 1.52±0.05%; MgO: 0.271±0.007%; MnO: 0.115±0.004%; S: 0.0061±0.0004%; Ta2O5: 0.067±0.004%; Nb2O5: 0.013±0.002%; Loss on ignition: 3.82±0.08%; F: 1.29±0.04%;

[0077] (9) ZBK487 (lithium mica), the mass percentages of each component are as follows: Li₂O: 2.51±0.06%; Na₂O: 2.31±0.03%; K₂O: 3.87±0.05%; Rb₂O: 0.638±0.006%; Cs₂O: 0.224±0.005%; SiO₂: 66.04±0.12%; Al₂O₃: 16.11±0.08%; TiO₂: 0.035±0.003%; Fe₂O₃: 0.586%. ±0.004%; P2O5: 0.607±0.004%; BeO: 0.028±0.003%; CaO: 0.825±0.007%; MgO: 0.188±0.004%; MnO: 0.108±0.005%; S: 0.014±0.003%; Ta2O5: 0.049±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 4.51±0.08%; F: 1.61±0.04%;

[0078] (10) The mass percentages of each component in ZBK488 (lithium mica) are as follows: Li₂O: 3.50±0.05%; Na₂O: 2.24±0.05%; K₂O: 3.82±0.05%; Rb₂O: 0.633±0.005%; Cs₂O: 0.222±0.003%; SiO₂: 64.28±0.12%; Al₂O₃: 15.94±0.07%; TiO₂: 0.038±0.003%; Fe₂O₃: 0.610 ±0.008%; P2O5: 0.600±0.005%; BeO: 0.028±0.005%; CaO: 0.802±0.006%; MgO: 0.173±0.004%; MnO: 0.107±0.004%; S: 0.016±0.004%; Ta2O5: 0.053±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 6.05±0.08%; F: 1.45±0.04%;

[0079] (11) ZBK489 (lithium feldspar), the mass percentages of each component are as follows: Li₂O: 1.51±0.04%; Na₂O: 2.04±0.04%; K₂O: 4.34±0.05%; Rb₂O: 0.700±0.004%; Cs₂O: 0.230±0.004%; SiO₂: 68.56±0.14%; Al₂O₃: 16.58±0.08%; TiO₂: 0.035±0.003%; Fe₂O₃: 0.502± 0.005%; P2O5: 0.475±0.003%; BeO: 0.035±0.003%; CaO: 0.574±0.004%; MgO: 0.155±0.004%; MnO: 0.121±0.005%; S: 0.0054±0.0006%; Ta2O5: 0.034±0.004%; Nb2O5: 0.010±0.002%; Loss on ignition: 2.89±0.08%; F: 1.75±0.04%;

[0080] (12) ZBK486 (lithium mica), the mass percentages of each component are as follows: Li₂O: 4.49±0.05%; Na₂O: 3.19±0.04%; K₂O: 2.75±0.03%; Rb₂O: 0.530±0.005%; Cs₂O: 0.243±0.004%; SiO₂: 63.41±0.12%; Al₂O₃: 14.91±0.08%; TiO₂: 0.018±0.002%; Fe₂O₃: 0.290 ±0.003%; P2O5: 0.993±0.006%; BeO: 0.045±0.004%; CaO: 1.15±0.05%; MgO: 0.118±0.003%; MnO: 0.047±0.003%; S: 0.011±0.002%; Ta2O5: 0.029±0.003%; Nb2O5: 0.0095±0.0005%; Loss on ignition: 6.08±0.10%; F: 2.15±0.04%;

[0081] (13) ZBK479 (spodumene), the mass percentages of each component are as follows: Li₂O: 6.10±0.05%; Na₂O: 0.283±0.003%; K₂O: 0.456±0.005%; Rb₂O: 0.057±0.004%; Cs₂O: 0.027±0.002%; SiO₂: 49.42±0.15%; Al₂O₃: 16.02±0.08%; TiO₂: 0.040±0.003%; Fe₂O₃: 0.6 87±0.005%; P2O5: 0.125±0.004%; BeO: 0.019±0.002%; CaO: 5.73±0.06%; MgO: 0.425±0.008%; MnO: 0.051±0.004%; S: 2.29±0.08%; Ta2O5: 0.013±0.002%; Nb2O5: 0.0037±0.0004%; Loss on ignition: 14.01±0.20%; F: 0.043±0.002%.

[0082] Example 2:

[0083] A method for preparing a series of standard samples for lithium ore composition analysis includes the following steps:

[0084] S1. Select niobium-, tantalum-, beryllium-, and lithium-containing ores with the chemical composition of each standard sample in claim 2 as raw materials and perform drying treatment. Considering the characteristics of lithium resources at home and abroad and referring to product standards such as YS / T 261-2011 "Spodumene Concentrate", YS / T 236-2009 "Lithium Mica Concentrate", and YS / T 722-2009 "Lithium Feldspar", etc., due to the significant differences in the composition of lithium ores from different mining areas and veins, to ensure the specific representativeness, applicability, and applicability of the project's products, multiple series of samples were taken from representative mining areas at home and abroad. The ore sources were selected from Yichun, Jiangxi; Altay, Xinjiang; Atacama, Chile; Uyuni Mine, Bolivia, Argentina; Zimbabwe; Xuelong Mountain, Xinjiang; Green Bushes, Australia; Nigeria; Dahongliutan, Xinjiang; Makitan, Ganzi Prefecture, Sichuan; and Suining, Sichuan.

[0085] S2. The dried raw material is first coarsely crushed by a jaw crusher, and then finely crushed by a double roll crusher.

[0086] S3. The ore sample after fine crushing in step S2 is fed into a ball mill for grinding and then screened to obtain a sample with a particle size of less than 200 mesh (74 micrometers).

[0087] S4. After mechanically mixing the sample obtained from step S3 using a three-dimensional vibrating screen, seal and store it.

[0088] S5. Conduct homogeneity tests and stability studies on the samples in sequence;

[0089] S6. After performing statistical analysis on the tested samples, a series of standard samples for lithium ore composition analysis were obtained, numbered ZBK466, ZBK466A, ZBK467, ​​ZBK467A, ZBK469, ZBK469A, ZBK469B, ZBK468, ZBK487, ZBK488, ZBK489, ZBK486 and ZBK479 in Example 1.

[0090] The lithium ore composition analysis standard samples prepared in this embodiment have a particle size of less than 74 μm (confirmed by laser particle size analyzer). After statistical testing of uniformity and stability, the standard samples with a particle size of less than 200 mesh (74 μm) show uniform distribution of each component and good stability.

[0091] Each type of lithium ore is produced in 25kg batches, and each type of finished product is packaged in 500 bottles, each containing 50g.

[0092] The particle size and uniformity, stability, and accuracy of chemical composition of the lithium ore composition analysis series of standard samples prepared in Example 2 were verified by data analysis.

[0093] I. Examination of the uniformity of particle size distribution

[0094] Three bottles (small packages) were randomly selected from the mixed sample to investigate the particle size distribution uniformity. The sample was sieved using a standard sieve into three particle sizes: 74 μm (200 mesh)–53 μm (280 mesh), 53 μm (280 mesh)–45 μm (320 mesh), and <45 μm (320 mesh). The mass percentage of each particle size was calculated, and the principal components were tested. The results are listed in Table 1.

[0095] For samples of different particle sizes, lithium ore standard samples were analyzed using accurate and reliable methods to determine Li2O, Na2O, K2O, SiO2, Al2O3, CaO, MgO, Rb2O, and Cs2O (SiO2 and Al2O3 – titration, Li2O, Na2O, K2O, CaO, MgO, and Rb2O – ICP-AES, Cs2O – AAS).

[0096] Table 1. Particle size distribution of lithium ore standard samples

[0097]

[0098] Continued table

[0099]

[0100] Continued table

[0101]

[0102] As shown in Table 1, the chemical composition segregation of each component in the standard samples is relatively small in terms of particle size. More than 90% of the samples have a particle size below 74 μm, indicating stable chemical composition. The particle size-weighted average value is close to the average value of the homogeneity test after mixing and the standard value, indicating that the particle size distribution of the mixed samples is uniform. This standard sample uses particles <74 μm as the raw material.

[0103] II. Uniformity Test

[0104] According to the technical specifications, 20 bottles were randomly selected from the packaging samples using a random number table, numbered sequentially, and subjected to uniformity testing. The measurement plan is as follows:

[0105] First time: 1-3-5-7-9-11-13-15-17-19-2-4-6-8-10-12-14-16-18-20;

[0106] Second time: 20-18-16-14-12-10-8-6-4-2-19-17-15-13-11-9-7-5-3-1;

[0107] Third time: 2-4-6-8-10-12-14-16-18-20-1-3-5-7-9-11-13-15-17-19.

[0108] The methods and minimum sample weights used for the analysis of each component are shown in Table 2 below.

[0109] Table 2. Methods and minimum sample quantities used for component analysis in lithium ore homogeneity testing.

[0110]

[0111] The test results were statistically analyzed using the variance method.

[0112] When the statistic F < F α(0.05) If the data within and between groups are not significantly different, the homogeneity test is passed.

[0113] When the statistic F>F α(0.05) If the data within and between groups are significantly different, the homogeneity test will fail.

[0114] According to the variance method, the F-value of each element is less than F. α(0.05) The uniformity test results are satisfactory, and the F-values ​​of the uniformity test are shown in Table 3 below.

[0115] Table 3. Statistics of lithium ore uniformity test data

[0116]

[0117] Continued table

[0118]

[0119] Continued table

[0120]

[0121] Continued table

[0122]

[0123] Continued table

[0124]

[0125] Continued table

[0126]

[0127] Note: In the table The standard deviation (MS) represents the deviation caused by sample inhomogeneity. among MS represents the sum of squares between groups divided by the degrees of freedom between groups. within This represents the sum of squares within a group divided by the degrees of freedom within the group.

[0128] As shown in Table 3, the F values ​​of each element in the standard samples prepared in this embodiment are all less than 1.84, and the F values ​​are distributed in the range of 0.8 to 1.18. The uniformity test is qualified and the uniformity is good.

[0129] III. Stability Analysis

[0130] This embodiment involves conducting multiple stability studies on the standard sample over two years. The measurement results are then subjected to a statistical stability test using a linear fitting method. If the slope |b1| < t α，(n-2) If ×s(b1) is not significant, it indicates that the sample is stable. In the formula, b1 is the slope of the fitted line, s(b1) is the uncertainty of the slope, and t... α，(n-2) It is a t-distribution with n-2 degrees of freedom and a certain confidence level.

[0131] Table 4. Results of Stability Study of Lithium Ore Standard Samples (%)

[0132]

[0133] Continued table

[0134]

[0135] Continued table

[0136]

[0137] Continued table

[0138]

[0139] Continued table

[0140]

[0141] Continued table

[0142]

[0143] Continued table

[0144]

[0145] Continued table

[0146]

[0147] Continued table

[0148]

[0149] Continued table

[0150]

[0151] Continued table

[0152]

[0153] Continued table

[0154]

[0155] Continued table

[0156]

[0157] Note: In the table, b1 is the slope of the fitted line, s(b1) is the uncertainty of the slope, and t α,(n-2) A t-distribution with n-2 degrees of freedom and a certain confidence level; |X CRM -X meas | represents the absolute value of the difference between the measured value and the standard value.

[0158] This embodiment calculates the values ​​from five stability tests conducted between 2022 and 2024 (the results are shown in Table 4). The results indicate that the stability test data for the standard sample are consistent over the two years, indicating good sample stability. Furthermore, comparing the stability test results with the uncertainty of the final value, the differences between the two measurements for all stability test items do not exceed the uncertainty of the final value. According to ISO Guide 35, if the following conditions are met:

[0159]

[0160] In the formula: X CRM X represents the characteristic value of CRM. meas The measured observations are given, k is the coverage factor, and the confidence level is 95%. Let k = 2, u CRM u represents the uncertainty of the characteristic value. meas This refers to measurement uncertainty. Ideally, the measurement uncertainty u... meas Than u CRM Much smaller.

[0161] Compare the measured values ​​of the standard sample from September 2022 to September 2024 with the standard values, and find the absolute value of the maximum difference |X CRM -X meas | Uncertainties that are all less than or equal to a constant value (results are shown in Table 4), and the calculated stability uncertainty u t The smaller value indicates good stability.

[0162] Based on similar standard samples, the validity period of the standard sample of this invention can be set at ten years.

[0163] IV. Constant Value Analysis

[0164] In this Example 2, the standard samples prepared were prepared in accordance with the requirements of ISO Guide 35 and GB / T 15000 series "Standard Sample Working Guidelines" and YS / T 409-2012 "Technical Specifications for Standard Samples for Analysis of Non-ferrous Metal Products". In addition to our own unit, we specially invited domestic units with certain testing capabilities to participate in the value determination analysis, and selected one or more accurate and reliable analytical methods for collaborative value determination analysis.

[0165] Four data points are reported for each element (using the same method), and the range of the four data points in each group should be less than the precision of the corresponding analytical method. The lithium ore standard sample determination method developed in this application employs multiple national standard methods and reliable methods based on different principles—gravimetric method, spectrophotometry, AAS, ICP-AES, ICP-MS, and titration. All standard sample determination methods are validated using national first-class lithium ore standard reference materials, nationally approved standard solutions, and Na2SO4 standard reference materials. The analytical determination uses the working curve method, and the measured values ​​of the validation standard samples are in good agreement with the standard values, proving the accuracy and reliability of the adopted methods.

[0166] Four independent data points were used. Their ranges were checked for outliers according to the method's r or permissible error in the national standard. The average of these data points was then calculated. The Cochrane criterion was used to verify the equal precision of the results in each group; the conclusion was satisfactory. The Shapiro-Wilke method was used to examine whether the averages conformed to a normal distribution; the conclusion was satisfactory. The Grubbs method was used to check for outliers in the averages; the conclusion was satisfactory. When no outliers were found in any group of data, the arithmetic mean and standard deviation of each group were calculated. The significant figures of the standard values ​​were rounded according to the method precision in GB / T 8170-2008 "Rules for Rounding Off Numerical Values ​​and Expression and Judgment of Limiting Values." The standard deviation was rounded only to the nearest whole number, and the number of decimal places of the standard value was aligned with the number of decimal places of the standard value. The standard values ​​and uncertainty data of the lithium ore standard samples are shown in Table 5 below.

[0167] Table 5. Standard values ​​and uncertainties (%) of lithium ore standard samples

[0168]

[0169] Continued table

[0170]

[0171] Continued table

[0172]

[0173] Note: Expanded uncertainty, coverage factor is 2. Number of measurement groups is 8.

[0174] Reliability verification of the above-mentioned setpoint data and setpoint analysis methods - comparison with similar standard samples at home and abroad; comparison data of domestic and foreign standard samples are shown in Table 6.

[0175] Table 6 Comparison of lithium ore standard samples with similar domestic and international standard samples

[0176]

[0177] Comparative analysis revealed that the lithium ore standard samples developed in this project are multi-point standard samples, containing 9 points of lithium feldspar, 3 points of lepidolite, and 1 point of spodumene. Values ​​were assigned to 19 components, including Li₂O, Na₂O, K₂O, TiO₂, SiO₂, Al₂O₃, CaO, MgO, S, P₂O₅, MnO, Fe₂O₃, Rb₂O, Cs₂O, BeO, Ta₂O₅, Nb₂O₅, loss on ignition, and F. The wide range of components in the standard samples from this project meets the needs of different users, instruments, and analytical methods. They are widely used in the analysis, testing, and quality control of lithium ore.

[0178] The method used for the determination analysis of lithium ore standard samples in this project is accurate and reliable. The uncertainty of each element is close to that of similar foreign standard samples, and the uncertainty of some elements is better than that of similar foreign standard samples.

[0179] like Figures 1-10 As shown, the working curves for the multi-point series standard samples of this project were obtained using X-ray fluorescence spectrometry. The linear correlation coefficients (r) for the lithium ore series standard samples are as follows: Al₂O₃: 0.995; CaO: 0.999; K₂O: 0.999; P₂O₅: 0.999; Rb₂O: 0.999; Ta₂O₅: 0.993; SiO₂: 0.997; Fe₂O₃: 0.994; MnO: 0.996; and Na₂O: 0.993. This indicates that the 10 principal components exhibit good linear relationships.

[0180] In summary, the standard samples of this invention have a rationally designed chemical composition and a scientifically advanced preparation and processing technology. The use of multi-stage crushing and three-dimensional mechanical mixing and sieving processes ensures the homogeneity of the chemical composition of the standard samples. The standard samples prepared by this invention have undergone rigorous initial and re-inspections for homogeneity, and stability studies have shown good stability, indicating that this series of standard samples exhibits excellent homogeneity. Multiple laboratories have used accurate and reliable analytical methods based on different principles to determine standard values ​​for 19 components in lithium ore, with accurate and reliable values. This standard sample has a wide range of applications, suitable for both routine chemical analysis and instrumental analysis of lithium ore components.

[0181] Furthermore, the development of this standard sample, including homogeneity testing, handling of doubtful values, and statistical calculation of the average value and standard uncertainty, all comply with the requirements of ISO Guide 34, ISO Guide 35, ISO Guide 31, GB / T 15000 series "Guidelines for the Work of Standard Samples", and YS / T 409-2012 "Technical Specifications for Standard Samples for Analysis of Non-ferrous Metal Products". Accurate and reliable analytical methods were employed in the value determination, ensuring the accuracy of this standard sample.

[0182] Of course, the above description is not limited to the examples above. Technical features not described in this invention can be implemented by or using existing technology, and will not be repeated here. The above embodiments and drawings are only used to illustrate the technical solutions of this invention and are not intended to limit this invention. This invention has been described in detail with reference to preferred embodiments. Those skilled in the art should understand that any changes, modifications, additions or substitutions made by those skilled in the art within the scope of this invention do not depart from the spirit of this invention and should also fall within the scope of protection of the claims of this invention.

Claims

1. A series of standard samples for lithium ore composition analysis, characterized in that: The chemical composition and content range are as follows: Li₂O: 0.80~6.2%; Na₂O: 0.2~4.0%; K₂O: 0.4~4.4%; Rb₂O: 0.05~0.7%; Cs₂O: 0.02~0.3%; SiO₂: 49~69%; Al₂O₃: 14~19%; TiO₂: 0.004~0.05%; Fe₂O₃: 0.3~1.3%; P₂O₅: 0.1~1.1%; BeO: 0.01~0.05%. CaO: 0.5–7%; MgO: 0.1–0.6%; MnO: 0.04–0.2%; S: 0.005–3%; Ta₂O₅: 0.01–0.07%; Nb₂O₅: 0.003–0.02%; Loss on ignition: 2.0–14%; F: 0.04–2.2%; It consists of the following 13 standard substances: (1) ZBK466, the mass percentages of each component are as follows: Li2O: 0.863±0.006%; Na2O: 0.320±0.007%; K2O: 0.444±0.003%; Rb2O: 0.066±0.004%; Cs2O: 0.029±0.003%; SiO2: 57.53±0.11%; Al2O3: 19.29±0.08%; TiO2: 0.039±0.003%; Fe2O3: 0.682 ±0.004%; P2O5: 0.146±0.003%; BeO: 0.017±0.003%; CaO: 6.06±0.05%; MgO: 0.410±0.004%; MnO: 0.054±0.003%; S: 2.73±0.05%; Ta2O5: 0.015±0.003%; Nb2O5: 0.0046±0.0004%; Loss on ignition: 7.19±0.10%; F: 0.057±0.004%; (2) ZBK466A, the weight percentages of each component are as follows: Li2O: 0.819±0.005%; Na2O: 0.326±0.005%; K2O: 0.502±0.003%; Rb2O: 0.065±0.004%; Cs2O: 0.026±0.005%; SiO2: 57.50±0.14%; Al2O3: 18.38±0.08%; TiO2: 0.044±0.003%; Fe2O3: 0.78 3±0.005%; P2O5: 0.139±0.003%; BeO: 0.018±0.002%; CaO: 6.61±0.05%; MgO: 0.532±0.004%; MnO: 0.062±0.004%; S: 2.66±0.05%; Ta2O5: 0.017±0.003%; Nb2O5: 0.0045±0.0004%; Loss on ignition: 7.73±0.10%; F: 0.053±0.004%; (3) ZBK467, ​​the weight percentages of each component are as follows: Li2O: 1.50±0.04%; Na2O: 2.55±0.03%; K2O: 3.96±0.05%; Rb2O: 0.653±0.004%; Cs2O: 0.222±0.005%; SiO2: 66.43±0.14%; Al2O3: 17.40±0.08%; TiO2: 0.036±0.003%; Fe2O3: 0.584±0. 0.004%; P2O5: 0.912±0.008%; BeO: 0.029±0.003%; CaO: 1.44±0.05%; MgO: 0.221±0.003%; MnO: 0.115±0.003%; S: 0.0061±0.0004%; Ta2O5: 0.059±0.004%; Nb2O5: 0.012±0.002%; Loss on ignition: 3.60±0.08%; F: 1.59±0.04%; (4) ZBK467A, the weight percentages of each component are as follows: Li2O: 1.64±0.04%; Na2O: 2.37±0.05%; K2O: 4.29±0.06%; Rb2O: 0.728±0.005%; Cs2O: 0.236±0.005%; SiO2: 66.38±0.14%; Al2O3: 17.62±0.08%; TiO2: 0.027±0.004%; Fe2O3: 0.588± 0.005%; P2O5: 0.722±0.006%; BeO: 0.028±0.005%; CaO: 1.01±0.02%; MgO: 0.176±0.004%; MnO: 0.134±0.004%; S: 0.015±0.002%; Ta2O5: 0.047±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 3.29±0.08%; F: 1.77±0.04%; (5) ZBK469, the weight percentages of each component are as follows: Li2O: 1.21±0.04%; Na2O: 3.59±0.04%; K2O: 2.19±0.03%; Rb2O: 0.397±0.004%; Cs2O: 0.205±0.003%; SiO2: 67.90±0.14%; Al2O3: 16.91±0.08%; TiO2: 0.0041±0.0004%; Fe2O3: 1.22±0. 0.03%; P2O5: 1.04±0.03%; BeO: 0.047±0.003%; CaO: 1.15±0.04%; MgO: 0.113±0.005%; MnO: 0.166±0.004%; S: 0.0065±0.0005%; Ta2O5: 0.022±0.002%; Nb2O5: 0.0078±0.0005%; Loss on ignition: 2.10±0.07%; F: 1.67±0.06%; (6) ZBK469A, the weight percentages of each component are as follows: Li2O: 1.60±0.04%; Na2O: 3.58±0.04%; K2O: 3.09±0.05%; Rb2O: 0.576±0.004%; Cs2O: 0.264±0.004%; SiO2: 68.28±0.14%; Al2O3: 16.13±0.08%; TiO2: 0.020±0.002%; Fe2O3: 0.330±0. 0.003%; P2O5: 1.05±0.04%; BeO: 0.042±0.005%; CaO: 1.22±0.04%; MgO: 0.137±0.003%; MnO: 0.052±0.004%; S: 0.0074±0.0006%; Ta2O5: 0.028±0.004%; Nb2O5: 0.012±0.002%; Loss on ignition: 2.12±0.09%; F: 2.24±0.06%; (7) ZBK469B, the weight percentages of each component are as follows: Li2O: 1.38±0.05%; Na2O: 3.79±0.04%; K2O: 2.81±0.06%; Rb2O: 0.499±0.006%; Cs2O: 0.245±0.006%; SiO2: 68.17±0.12%; Al2O3: 16.27±0.08%; TiO2: 0.03±0.003%; Fe2O3: 0.419±0. 0.005%; P2O5: 1.06±0.04%; BeO: 0.049±0.004%; CaO: 1.07±0.05%; MgO: 0.237±0.003%; MnO: 0.048±0.003%; S: 0.0062±0.0005%; Ta2O5: 0.028±0.005%; Nb2O5: 0.011±0.002%; Loss on ignition: 2.22±0.09%; F: 1.64±0.05%; (8) ZBK468, the weight percentages of each component are as follows: Li2O: 1.38±0.04%; Na2O: 2.50±0.04%; K2O: 3.83±0.05%; Rb2O: 0.610±0.005%; Cs2O: 0.220±0.005%; SiO2: 65.95±0.12%; Al2O3: 17.37±0.08%; TiO2: 0.048±0.004%; Fe2O3: 0.729±0. 0.006%; P2O5: 0.826±0.008%; BeO: 0.024±0.004%; CaO: 1.52±0.05%; MgO: 0.271±0.007%; MnO: 0.115±0.004%; S: 0.0061±0.0004%; Ta2O5: 0.067±0.004%; Nb2O5: 0.013±0.002%; Loss on ignition: 3.82±0.08%; F: 1.29±0.04%; (9) ZBK487, the weight percentages of each component are: Li2O: 2.51±0.06%; Na2O: 2.31±0.03%; K2O: 3.87±0.05%; Rb2O: 0.638±0.006%; Cs2O: 0.224±0.005%; SiO2: 66.04±0.12%; Al2O3: 16.11±0.08%; TiO2: 0.035±0.003%; Fe2O3: 0.586±0.0 0.04%; P2O5: 0.607±0.004%; BeO: 0.028±0.003%; CaO: 0.825±0.007%; MgO: 0.188±0.004%; MnO: 0.108±0.005%; S: 0.014±0.003%; Ta2O5: 0.049±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 4.51±0.08%; F: 1.61±0.04%; (10) ZBK488, the weight percentages of each component are as follows: Li2O: 3.50±0.05%; Na2O: 2.24±0.05%; K2O: 3.82±0.05%; Rb2O: 0.633±0.005%; Cs2O: 0.222±0.003%; SiO2: 64.28±0.12%; Al2O3: 15.94±0.07%; TiO2: 0.038±0.003%; Fe2O3: 0.610±0. 0.008%; P2O5: 0.600±0.005%; BeO: 0.028±0.005%; CaO: 0.802±0.006%; MgO: 0.173±0.004%; MnO: 0.107±0.004%; S: 0.016±0.004%; Ta2O5: 0.053±0.004%; Nb2O5: 0.011±0.002%; Loss on ignition: 6.05±0.08%; F: 1.45±0.04%; (11) ZBK489, the weight percentages of each component are as follows: Li2O: 1.51±0.04%; Na2O: 2.04±0.04%; K2O: 4.34±0.05%; Rb2O: 0.700±0.004%; Cs2O: 0.230±0.004%; SiO2: 68.56±0.14%; Al2O3: 16.58±0.08%; TiO2: 0.035±0.003%; Fe2O3: 0.502±0. 0.005%; P2O5: 0.475±0.003%; BeO: 0.035±0.003%; CaO: 0.574±0.004%; MgO: 0.155±0.004%; MnO: 0.121±0.005%; S: 0.0054±0.0006%; Ta2O5: 0.034±0.004%; Nb2O5: 0.010±0.002%; Loss on ignition: 2.89±0.08%; F: 1.75±0.04%; (12) ZBK486, the weight percentages of each component are as follows: Li2O: 4.49±0.05%; Na2O: 3.19±0.04%; K2O: 2.75±0.03%; Rb2O: 0.530±0.005%; Cs2O: 0.243±0.004%; SiO2: 63.41±0.12%; Al2O3: 14.91±0.08%; TiO2: 0.018±0.002%; Fe2O3: 0.290±0. 0.003%; P2O5: 0.993±0.006%; BeO: 0.045±0.004%; CaO: 1.15±0.05%; MgO: 0.118±0.003%; MnO: 0.047±0.003%; S: 0.011±0.002%; Ta2O5: 0.029±0.003%; Nb2O5: 0.0095±0.0005%; Loss on ignition: 6.08±0.10%; F: 2.15±0.04%; (13) ZBK479, the weight percentages of each component are as follows: Li2O: 6.10±0.05%; Na2O: 0.283±0.003%; K2O: 0.456±0.005%; Rb2O: 0.057±0.004%; Cs2O: 0.027±0.002%; SiO2: 49.42±0.15%; Al2O3: 16.02±0.08%; TiO2: 0.040±0.003%; Fe2O3: 0.687± 0.005%; P2O5: 0.125±0.004%; BeO: 0.019±0.002%; CaO: 5.73±0.06%; MgO: 0.425±0.008%; MnO: 0.051±0.004%; S: 2.29±0.08%; Ta2O5: 0.013±0.002%; Nb2O5: 0.0037±0.0004%; Loss on ignition: 14.01±0.20%; F: 0.043±0.002%.

2. A method for preparing a series of standard samples for lithium ore composition analysis as described in any one of claims 1, characterized in that: Includes the following steps: S1. Investigation phase: Collect physicochemical property data of target samples and determine the composition range and uncertainty requirements of standard samples; S2. Component Design: Based on the survey data, at least 3 different component gradients are designed using orthogonal experimental design, with the component content difference between each group not less than 5%; S3. Raw Material Selection: Based on the design range of the composition, raw materials from different domestic and international mineral sources were selected, including Yichun in Jiangxi, Altay in Xinjiang, Atacama in Chile, Uyuni mine in Bolivia, Argentina, Zimbabwe, Xuelong Mountain in Xinjiang, Green Bushes in Australia, Nigeria, Dahongliutan in Xinjiang, Maiki in Ganzi Prefecture of Sichuan, and Suining in Sichuan. The composition was verified using X-ray fluorescence spectrometry, infrared absorption spectrometry, atomic absorption spectrometry, and ion-selective electrode method to ensure that the main components and trace element components are within the design range. S4. Drying treatment: Place the raw materials in a drying oven and dry them at 105±5℃ for 4 to 6 hours until the moisture content is ≤0.1%; S5. Crushing and Grinding: A three-stage crushing system is adopted, including: jaw crusher for coarse crushing to particle size ≤5mm, double roll crusher for fine crushing to particle size ≤1mm, and ball mill for grinding to D90≤74μm; S6. Screening: The material is classified through a 200-mesh standard sieve (74μm), and the material on the sieve is returned to the ball mill for secondary grinding. S7. Mechanical mixing: Use a three-dimensional mixer at a speed of 20-30 rpm for 2-4 hours to mix the materials. The coefficient of variation (CV) of the mixing uniformity is ≤1%. S8. Sealed storage: Place the mixed sample in an aluminum foil bag. Materials with a sulfur content exceeding 2% should be vacuum-packed. The ambient humidity should be controlled below RH50%.

3. The method for preparing a series of standard samples for lithium ore composition analysis according to claim 2, characterized in that: Also includes: S9. Uniformity test: including: S9.1 Initial inspection stage: Randomly select 5 samples for XRD detection. If the relative standard deviation RSD > 3%, return to step S7. S9.2 Final inspection stage: Sampling inspection shall be carried out in accordance with the GB / T 15000 series standards, and the pass standard is RSD≤1.5%.

4. The method for preparing a series of standard samples for lithium ore composition analysis according to claim 3, characterized in that: Also includes: S10. Stability Study: After storage at 40℃ for 30 days, the monthly change rate of the components should be <0.5%; the standard sample should be subjected to multiple stability studies within two years, and the absolute value of the maximum difference between the measured value of the standard sample and the standard value should be less than or equal to the uncertainty of the set value. S11. Mathematical Statistics: Outliers were removed using the Grubbs test, and the expanded uncertainty k=2 was calculated. S12. Value determination analysis: Value determination is carried out jointly by at least 8 laboratories, and the final standard value is the weighted average.

5. The method for preparing a series of standard samples for lithium ore composition analysis according to claim 2, characterized in that: In step S5, the ball mill uses zirconia grinding balls, and the ball-to-material ratio is controlled at 3~5:

1.

6. The method for preparing a series of standard samples for lithium ore composition analysis according to claim 3, characterized in that: In step S9.2, stratified random sampling is used to take at least 10 samples from each of the three different packaging batches for testing.

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