A method, device, medium and product for qualitative and quantitative analysis of thermal runaway initial spray substances of energy storage batteries

Abstract

This application discloses a method, equipment, medium, and product for qualitative and quantitative analysis of substances initially released during thermal runaway of energy storage batteries, relating to the field of explosion medium tracing. The method includes: preparing multiple sets of standard mixed electrolyte samples with different proportions; detecting each set of standard mixed electrolyte samples using a gas chromatograph to obtain the chromatographic peak area of ​​each component and constructing a standard curve equation; placing a single energy storage battery cell in a sealed container and then placing it in the constant-temperature chamber of an adiabatic accelerating calorimeter, heating it at a constant temperature until the electrolyte is completely vaporized, condensing and recovering the liquid electrolyte and weighing the total mass of the electrolyte; diluting and adjusting the volume of the recovered liquid electrolyte, and performing gas chromatographic detection using the same detection parameters as the standard mixed electrolyte samples to obtain the chromatographic peak retention time and peak area of ​​each component of the sample to be tested, for qualitative identification, calculating the total release amount of electrolyte initially released from all runaway batteries, generating an analysis report, and realizing the qualitative identification and quantitative detection of substances initially released during thermal runaway of energy storage batteries.

Description

Technical Field

[0001] This application relates to the field of tracing the source of explosive media, and in particular to a method, equipment, medium and product for qualitative and quantitative analysis of substances ejected during the initial thermal runaway of an energy storage battery. Background Technology

[0002] As the global energy structure shifts towards cleaner and lower-carbon energy, electrochemical energy storage systems, as a core support for renewable energy consumption and grid peak and frequency regulation, are being widely adopted in China. Currently, the batteries used in China's electrochemical energy storage systems are mainly lithium iron phosphate (LFP) batteries. These batteries, with their high safety and long cycle life, have become the mainstream choice for energy storage power stations. However, under extreme conditions (such as high temperature, overcharging, mechanical damage, or cooling system failure), there is still a risk of thermal runaway, which could lead to serious safety accidents such as combustion and explosion, threatening human life and property safety and hindering the healthy and orderly development of the energy storage industry.

[0003] Studies have shown that the thermal runaway process of LFP batteries exhibits distinct phases, clearly divided into two core stages: initial ejection and main ejection. The composition of the substances released in these two stages differs significantly. The initial ejection stage primarily releases electrolyte vapor, corresponding to the initial opening of the battery's safety valve. Increased internal pressure causes rapid vaporization of the electrolyte, which is then ejected. Its main components are carbonate organic solvent vapors such as ethylene carbonate (EC) and dimethyl carbonate (DMC). The main ejection stage, on the other hand, is dominated by flammable and explosive gases such as hydrogen (H2), methane (CH4), ethylene (C2H4), and carbon monoxide (CO). This stage represents a concentrated manifestation of deep decomposition reactions of the battery's internal materials, resulting in a larger gas production volume and a higher risk of combustion and explosion. It is noteworthy that the ejected material during LFP battery thermal runaway is actually a binary mixture of "electrolyte vapor + flammable gas." This multiphase mixing characteristic significantly increases the explosion risk—when electrolyte vapor mixes with flammable gas, the lower explosive limit of the mixture is significantly lowered, greatly increasing the probability of an explosion.

[0004] Following an explosion at an energy storage power station, accurate tracing of the explosive medium is a core prerequisite for accident investigation, liability determination, and subsequent safety control optimization. It is also a crucial step in implementing the "data collection → reverse tracing → simulation verification" accident investigation process. Currently, the industry has developed several relatively mature detection and analysis methods for the combustible gas mixture released during the main thermal runaway phase, enabling qualitative identification and quantitative detection of each combustible gas component. However, there are currently no effective analytical methods for the electrolyte vapor released during the initial injection phase, resulting in significant technical blind spots in the accident investigation process: on the one hand, it is impossible to accurately determine the specific types of electrolyte contained in the explosive mixture (e.g., the electrolytes used in different energy storage batteries may contain different proportions of EC, DMC, EMC, etc.); on the other hand, it is impossible to quantify the amount of electrolyte vapor released during the initial injection phase. The content of electrolyte vapor directly affects key parameters such as the explosion limit and combustion rate of the mixture. Unknown content leads to an inability to accurately reconstruct the explosion process and to clarify the role and weight of electrolyte vapor in the explosion accident.

[0005] The aforementioned deficiencies in existing technologies make it difficult to accurately trace the source of thermal runaway explosions in LFP batteries at energy storage power stations. The analysis of accident causes lacks scientific and comprehensive data support, hindering targeted optimization of energy storage system safety design, improvement of accident prevention measures, and effective reduction of the recurrence probability of similar accidents. Against this backdrop, to address the technical pain points of existing technologies—the inability to qualitatively identify and quantitatively detect the initial ejection material during LFP battery thermal runaway—and to support accurate tracing of the explosion medium in energy storage systems, thereby facilitating comprehensive investigation, liability determination, and safety control optimization of explosion accidents, developing a method capable of accurately performing qualitative and quantitative analysis of the initial ejection material during thermal runaway of energy storage batteries has become an urgent technical need in the field of energy storage safety. Summary of the Invention

[0006] The purpose of this application is to provide a method, equipment, medium, and product for qualitative and quantitative analysis of substances ejected during the initial thermal runaway of energy storage batteries, so as to solve the problem that substances ejected during the initial thermal runaway of LFP batteries cannot be qualitatively identified and quantitatively detected in the prior art.

[0007] To achieve the above objectives, this application provides the following solution: In a first aspect, this application provides a method for qualitative and quantitative analysis of substances ejected during the initial thermal runaway of an energy storage battery, including: Based on the sample to be tested and the adjusted equipment, multiple sets of standard mixed electrolyte samples with different proportions were prepared; the total mass of each set was uniformly m. 标 The sample to be tested is a single energy storage battery cell. The peak areas (A) of each component in the standard mixed electrolyte samples were obtained by gas chromatography. i Construct the standard curve equation; The individual energy storage battery cells are placed in a sealed container and then placed in the constant temperature chamber of an adiabatic accelerated calorimeter. They are heated at a constant temperature until the electrolyte is completely vaporized. The liquid electrolyte is then condensed and recovered, and the total mass m of the electrolyte is measured. 液 ; After diluting and bringing the volume to a suitable level, the recovered liquid electrolyte was subjected to gas chromatography detection using the same detection parameters as the standard mixed electrolyte sample to obtain the retention time t of each component of the test sample. r and chromatographic peak area A 测 ; Based on the retention time t of each component's chromatographic peak r Qualitative identification is performed, and based on the standard curve equation and the total mass m of the electrolyte... 液 and the chromatographic peak area A 测 Calculate the total amount of electrolyte released during the initial spraying of all runaway batteries and generate an analysis report.

[0008] Secondly, this application provides a computer device, including: a memory, a processor, and a computer program stored in the memory and executable on the processor, wherein the processor executes the computer program to implement the above-described qualitative and quantitative analysis method for the initial ejection of substances during thermal runaway of an energy storage battery.

[0009] Thirdly, this application provides a computer-readable storage medium storing a computer program thereon, which, when executed by a processor, implements the above-mentioned qualitative and quantitative analysis method for the initial ejection of substances during thermal runaway of an energy storage battery.

[0010] Fourthly, this application provides a computer program product, including a computer program that, when executed by a processor, implements the aforementioned qualitative and quantitative analysis method for the initial ejection of substances during thermal runaway of an energy storage battery.

[0011] According to the specific embodiments provided in this application, this application has the following technical effects: This application involves preparing multiple sets of standard mixed electrolyte samples with different proportions based on the sample to be tested and the adjusted equipment; the total mass of each set is uniformly m. 标 The standard mixed electrolyte samples of each group were analyzed by gas chromatography (GC) to obtain the chromatographic peak area A of each component. i A standard curve equation was constructed; the individual energy storage battery cells were placed in a sealed container and then placed in the constant temperature chamber of an adiabatic accelerated calorimeter, and heated at a constant temperature until the electrolyte was completely vaporized. The liquid electrolyte was condensed and recovered, and the total mass m of the electrolyte was measured. 液 After diluting and bringing the volume of the recovered liquid electrolyte to a suitable level, gas chromatography was performed using the same detection parameters as the standard mixed electrolyte sample to obtain the retention time t of each component in the test sample. r and chromatographic peak area A测 According to the retention time t of each component's chromatographic peak r Qualitative identification is performed, and based on the standard curve equation and the total mass m of the electrolyte... 液 and the chromatographic peak area A 测 This application calculates the total amount of electrolyte released during the initial discharge from all runaway batteries and generates an analysis report. Using a standard curve equation as the qualitative and quantitative benchmark, and employing a sealed container and an adiabatic accelerated calorimeter to ensure complete electrolyte collection, this application achieves the technical goals of accurate qualitative and quantitative analysis of the initially discharged electrolyte, calculable volume, and predictable total amount through liquid-vapor volume conversion. It completely solves the pain points of existing technologies, such as vague qualitative analysis, large quantitative errors, unreliable data, and inability to support accident investigations. This provides a precise and reliable technical means for tracing the source and analyzing the causes of thermal runaway explosions in energy storage batteries, possessing extremely high practical value and widespread application significance. Attached Figure Description

[0012] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0013] Figure 1 A flowchart illustrating a method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery, provided as an embodiment of this application; Figure 2 This is a flowchart illustrating how various devices collaboratively complete the analysis process, as provided in an embodiment of this application. Detailed Implementation

[0014] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0015] To make the objectives, features and advantages of this application more apparent and understandable, the application will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0016] like Figure 1 As shown in the embodiments of this application, a method for qualitative and quantitative analysis of substances ejected during the initial thermal runaway of an energy storage battery is provided, including: S1: Based on the sample to be tested and the adjusted equipment, prepare multiple sets of standard mixed electrolyte samples with different proportions; the total mass of each set is uniformly m. 标The sample to be tested is a single energy storage battery cell.

[0017] S2: The peak areas A of each component in the standard mixed electrolyte samples were obtained by gas chromatography. i Construct the standard curve equation.

[0018] S3: After placing the energy storage battery cell into a sealed container, place it in the constant temperature chamber of an adiabatic accelerated calorimeter and heat it at a constant temperature until the electrolyte is completely vaporized. Condense and recover the liquid electrolyte and weigh the total mass m of the electrolyte. 液 .

[0019] S4: After diluting and bringing the recovered liquid electrolyte to a fixed volume, perform gas chromatography detection using the same detection parameters as the standard mixed electrolyte sample to obtain the retention time t of each component of the sample. r and chromatographic peak area A 测 .

[0020] S5: Based on the retention time t of each component's chromatographic peak r Qualitative identification is performed, and based on the standard curve equation and the total mass m of the electrolyte... 液 and the chromatographic peak area A 测 Calculate the total amount of electrolyte released during the initial spraying of all runaway batteries and generate an analysis report.

[0021] This application applies to LFP batteries and other types of lithium-ion batteries. The core technology involves using an adiabatic accelerating rate calorimeter (ARC) in conjunction with a sealed container. The individual battery cells are placed in the sealed container, and all the electrolyte is evaporated and collected under constant temperature conditions above the boiling point of the electrolyte. By pre-mixing the electrolyte with conventional lithium-ion batteries of known composition and content, a GC analysis standard curve is established using a multi-point method. The initial electrolyte release is qualitatively identified and quantitatively detected by comparing it with the standard curve. Furthermore, the total amount of initial electrolyte released can be inferred by correlating it with all runaway batteries.

[0022] In one exemplary embodiment, based on the sample to be tested and the adjusted device, multiple sets of standard mixed electrolyte samples with different proportions are prepared, which further includes: Select a single energy storage battery cell and weigh its initial mass m1.

[0023] Prepare a stainless steel sealed container, an adiabatic accelerated calorimeter, a gas chromatograph, an electronic balance, and standard reagents for lithium-ion battery electrolytes of known purity.

[0024] The airtightness of the sealed container was tested and found to be qualified. The adiabatic accelerating calorimeter was adjusted to a constant temperature T, which was higher than the boiling point of the electrolyte. The gas chromatograph was adjusted to a detection accuracy of not less than 0.01 μg / mL.

[0025] In one exemplary embodiment, constructing the standard curve equation specifically includes: The mass concentration of each component c i The x-axis represents the peak area A. i Using the ordinate as the vertical axis, the standard curve equation A is obtained by linear fitting using the multi-point method. i =k i ×c i +b i The correlation coefficient R of the control standard curve 2 ≥0.999; where k i Let b be the slope of the standard curve. i This is the intercept.

[0026] In one exemplary embodiment, based on the retention time t of each component's chromatographic peak r Qualitative identification is performed, and based on the standard curve equation and the chromatographic peak area A... 测 Calculate the total amount of electrolyte released during the initial discharge from all runaway batteries and generate an analysis report, including: The retention time t of each component chromatographic peak r The retention times of the chromatographic peaks were compared with those of the standard components. Qualitative identification was performed based on the comparison results, and the chromatographic peak area A was determined. 测 Substitute into the standard curve equation to calculate the mass concentration c. 测 Determine the mass of each component.

[0027] Based on the sum of the masses of all components and the total mass m of the electrolyte. 液 The deviation is used to determine the total amount of electrolyte released during the initial spraying of the energy storage cell.

[0028] According to the total mass m of the electrolyte 液 Determine the initial electrolyte vapor volume of a single cell.

[0029] Based on the total number of out-of-control batteries at the accident site, the total amount of electrolyte released during the initial spray, and the volume of electrolyte vapor from the initial spray in each individual battery, the total amount of electrolyte released during the initial spray and the total volume of vapor from all out-of-control batteries are calculated, and an analysis report is generated.

[0030] In one exemplary embodiment, based on the total mass m of the electrolyte 液 Determining the initial electrolyte vapor volume of a single battery cell includes: Based on the ideal gas law, combined with the total mass m of the electrolyte 液 The amount of substance n is calculated from the average molar mass M, and then the initial volume V of the electrolyte vapor injected into the single cell is obtained. 单 .

[0031] In one exemplary embodiment, the total release amount M 总 For M总 =N×m 单 The total steam volume V 总 For V 总 =N×V 单 Where N is the total number of out-of-control batteries at the accident site.

[0032] In one exemplary embodiment, the mass concentration c of each component i =(m 标 ×ω i ×10 6 ) / V 溶 , where ω i V represents the mass percentage of the components. 溶 This is the final volume of the standard mixed electrolyte sample.

[0033] In one exemplary embodiment, the mass m of each component 组分 =(c 测 ×V' 溶 ) / 10 6 ,V' 溶 This is the final volume of the sample to be tested.

[0034] In an exemplary embodiment, the average molar mass M = Σ(ω i ×M i ), where ω i M represents the mass percentage of the components. i The molar mass of the component.

[0035] In one exemplary embodiment, the standard mixed electrolyte sample contains at least one of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC).

[0036] In practical applications, this application achieves accurate analysis of the initial sprayed electrolyte through the steps of "sample pretreatment - standard curve establishment - qualitative and quantitative detection - liquid-vapor conversion - total amount inference". The main components include a computer, an adiabatic accelerating calorimeter, a sealed container, a gas chromatograph (GC), an electronic balance, and a constant temperature water bath, etc. These devices work together to complete the analysis process, such as... Figure 2 As shown, the specific steps are as follows: Step 1: Preparation of test samples and equipment The equipment preparation includes preparing individual energy storage battery cells, a GC gas chromatograph, an ARC accelerated calorimeter, a condensation recovery device, and a computer.

[0037] The execution entity is the test operator (with the computer assisting in parameter setting), and the specific operation is as follows: 1.1 Select the energy storage battery cell to be analyzed (which can be an LFP battery or other lithium-ion battery), and remove unqualified cells with surface damage or leakage. Accurately weigh the initial mass of the battery cell using an electronic balance and record it as m1 (unit: g). The weighing accuracy should not be less than 0.001 g. Upload the weighing data to the computer for storage.

[0038] 1.2 Prepare a sealed container (made of corrosion-resistant and high-temperature resistant stainless steel, with a volume denoted as V container, unit: L, known quantity), an adiabatic accelerated calorimeter, a gas chromatograph, an electronic balance, and conventional electrolytes for lithium-ion batteries (including common components such as ethylene carbonate EC, dimethyl carbonate DMC, and ethyl methyl carbonate EMC, all of which are standard reagents with known purity).

[0039] 1.3 Perform an airtightness test on the sealed container: Inject nitrogen into the container to a pressure of 0.1 MPa, let it stand for 30 minutes, and observe the pressure change. If the pressure drop does not exceed 0.005 MPa, the airtightness is deemed to be qualified; if it is not qualified, replace the seal and retest until it is qualified. The test results are recorded and archived by computer.

[0040] 1.4 Debug the adiabatic accelerated calorimeter and gas chromatograph. Set the temperature of the isothermal chamber of the adiabatic accelerated calorimeter to T (unit: °C, known quantity) by computer, and ensure that T is higher than the boiling point of the electrolyte of the battery to be analyzed (to ensure that the electrolyte can be completely vaporized). Set the temperature control accuracy of the adiabatic accelerated calorimeter to ±0.1 °C and the detection accuracy of the gas chromatograph to not less than 0.01 μg / mL. After debugging, conduct a no-load test run to ensure that the equipment is operating normally.

[0041] The purpose of step 1 is to ensure that the test sample is undamaged, the equipment is airtight, and the parameters meet the standards, laying the foundation for the complete vaporization, accurate collection, and detection of the electrolyte, and avoiding distortion of analysis results due to equipment errors or sample problems.

[0042] Step 2: Establish the GC standard curve and determine the R-value of the GC standard curve. 2 Is it ≥0.999?

[0043] The execution is carried out by a computer (which controls the gas chromatograph and electronic balance to complete the operation and simultaneously processes the data), and the specific operation is as follows: 2.1 Preparation of Standard Mixed Electrolyte: Select the components (EC, DMC, EMC, etc.) of a conventional lithium-ion battery electrolyte, accurately weigh the mass of each component using an electronic balance, and prepare at least 5 sets of standard mixed electrolyte samples in different proportions (the mass percentage of each component in each sample is known and denoted as ω). i(i=1,2,...n, where n is the number of component types and known quantities), the total mass of each group of samples is m standard (unit: g, known quantity, uniformly set to 10g). Each group of samples is placed into a sealed sample bottle, labeled, and the component and mass data of each group of samples are uploaded to the computer.

[0044] 2.2 Standard Sample Detection: Each group of standard mixed electrolyte samples was injected into the gas chromatograph. The detection parameters (column temperature, carrier gas flow rate, detection time, etc.) of the gas chromatograph were kept consistent under computer control. After detection, the gas chromatograph output the chromatographic peak area A of each component in each sample group. i (Unit: mV·min, unknown quantity, obtained by detection), the computer automatically collects and stores all chromatographic peak area data.

[0045] 2.3 Establishing a standard curve: The computer uses the mass concentration c of each component in each group of standard samples as the standard curve. i (Unit: μg / mL, known quantity, calculation formula is c) i =(m 标 ×ω i ×10 6 ) / V 溶 V 溶 The x-axis represents the final volume of the standard sample (in mL, known quantity), and the y-axis represents the corresponding peak area A. i Using the ordinate as the vertical axis, a multi-point method (at least 5 data points) is employed for linear fitting to obtain the standard curve equations for each component: A i =k i ×c i +b i , where k i b is the slope of the standard curve (an unknown quantity, obtained through fitting). i Calculate the correlation coefficient R for each standard curve, given the intercept (an unknown quantity, obtained from the fitting). 2 Requires R 2 ≥0.999, to ensure the accuracy of the standard curve; if R 2 If the value is less than 0.999, prepare a new standard sample and repeat steps 2.2-2.3 until the requirement is met.

[0046] The purpose of step 2 is to establish the correspondence between "component mass concentration and chromatographic peak area", providing a benchmark for the qualitative identification (by matching the chromatographic peak retention time) and quantitative detection (by calculating the concentration through the standard curve) of the unknown initial sprayed electrolyte, and solving the technical pain point that gas chromatographs cannot directly qualitatively and quantitatively identify unknown electrolytes.

[0047] Step 3: Collection and testing of the initial sprayed electrolyte.

[0048] The main operator is the test personnel (with the assistance of the computer to complete the parameter setting). The specific operation is as follows: 3.1 Electrolyte vaporization and collection: The test operator puts the battery cell prepared in step 1 into a qualified sealed container, tightens the container cap to ensure a seal, and then puts the sealed container into the constant temperature chamber of the adiabatic accelerated calorimeter (ARC). The computer controls the adiabatic accelerated calorimeter to maintain a constant temperature T and continues to heat until the electrolyte inside the battery cell is completely vaporized (the heating time is recorded as t, unit: h, determined through pre-testing to ensure that there is no electrolyte residue and the amount is known).

[0049] 3.2 Condensation and Recovery: Connect a condensation device (with computer-controlled condensation temperature to ensure complete condensation of electrolyte vapor into liquid) to the outlet of the sealed tank. Collect the condensed liquid electrolyte and accurately weigh the total mass of the collected electrolyte using an electronic balance. Record the mass as m_liquid (unit: g, unknown quantity). Upload the weighing data to the computer.

[0050] 3.3 Sample Detection: The collected liquid electrolyte was diluted with an organic solvent (the same solvent used for volume adjustment of the standard sample, known quantity) to a fixed volume Vsolvent (the same volume used for volume adjustment of the standard sample, known quantity) to obtain the electrolyte sample to be tested. The sample was injected into a gas chromatograph, and the computer-controlled gas chromatograph was used to perform detection according to the same parameters as in step 2.2, outputting the retention time ts of each component in the sample. r (Unit: min, unknown quantity) and chromatographic peak area A 测 (Unit: mV·min, unknown quantity), and automatically store the detection data.

[0051] The purpose of step 3 is to achieve complete vaporization and condensation recovery of the initial electrolyte sprayed into the battery, ensuring no electrolyte residue remains. At the same time, the chromatographic data of the sample to be tested is obtained by gas chromatography, providing raw data for subsequent qualitative and quantitative analysis.

[0052] Step 4: Qualitative and quantitative analysis of the initial sprayed electrolyte, and determine whether the retention time deviation range does not exceed ±0.05 min.

[0053] The execution entity is a computer (which performs data comparison and calculation), and the specific operations are as follows: 4.1 Qualitative Identification: The computer analyzes the retention times t of the chromatographic peaks of each component in the sample obtained in step 3.3. r The retention times of each component's chromatographic peaks are compared with those of the standard curve established in step 2. If the retention time of a certain component's t... r If the retention time deviation from that of a known component in the standard curve does not exceed ±0.05 min, the sample to be tested is determined to contain that component, thus completing the qualitative identification of the initial sprayed electrolyte and determining the specific component type of the initial sprayed electrolyte.

[0054] 4.2 Quantitative Detection: For each electrolyte component qualitatively identified, the computer substitutes the chromatographic peak area A of that component into the corresponding standard curve equation A. i =k i ×c i +b i The mass concentration of the component in the sample, cmeasured (unit: μg / mL, unknown quantity), is calculated. Then, according to the formula mcomponent = (cmeasured × Vsolution) / 10, the concentration of the component is calculated. 6 The mass of the component is calculated (unit: g, unknown quantity); the sum of the masses of all components is the total mass m of the electrolyte collected in step 3.2, which is used to verify the accuracy of the calculation results (the deviation does not exceed ±0.5%); if the deviation exceeds ±0.5%, steps 3-4 are repeated until the requirements are met.

[0055] 4.3 Determination of the total amount of electrolyte released in the initial spray of a single cell: The computer determines the total amount of electrolyte released in the initial spray stage of thermal runaway of the single cell as m_liquid obtained by weighing in step 3.2 (unit: g), and records it as m_single (m_single = m_liquid, unknown quantity).

[0056] The purpose of step 4 is to accurately identify (determine the components) and quantitatively detect (determine each component and the total mass) the initial sprayed electrolyte by benchmarking against the standard curve, thus solving the problem that the initial sprayed electrolyte cannot be qualitatively or quantitatively identified in the existing technology.

[0057] Step 5: Convert the volume of electrolyte liquid to vapor.

[0058] The executing entity is the computer (which performs data calculations), and the specific operations are as follows: 5.1 Determine the conversion parameters: The computer calls the ideal gas law PV=nRT, where P: pressure of electrolyte vapor (unit: Pa, known quantity, taken as standard atmospheric pressure 101325 Pa); V: volume of electrolyte vapor (unit: L, unknown quantity, i.e., the initial volume of electrolyte vapor to be calculated); n: amount of substance of electrolyte vapor (unit: mol, unknown quantity); R: gas constant (unit: J / (mol·K), known quantity, taken as 8.314 J / (mol·K)); T: thermodynamic temperature of electrolyte vaporization (unit: K, known quantity, calculated by the formula T=273.15+T (°C), where T (°C) is the constant temperature water bath temperature set in step 1.4).

[0059] 5.2 Calculate the amount of substance n: According to the formula n=m 液 / M, where m 液M is the total mass of the electrolyte collected in step 3.2 (unit: g, known amount), and M is the average molar mass of the electrolyte (unit: g / mol, known amount, calculated based on the types and mass percentages of each component qualitatively identified in step 4.1, using the formula M = Σ(ω i ×M i ), where ω i M represents the mass percentage of each component. i (where represents the molar mass of each component, all of which are known quantities).

[0060] 5.3 Calculate the vapor volume V: Substitute n, P, R, and T into the ideal gas law and transform it to obtain V = nRT / P. Input the data into the computer for calculation and obtain the volume (unit: L) of the electrolyte after the initial spray of the single cell is completely vaporized into vapor, denoted as V_single (unknown quantity).

[0061] The purpose of step 5 is to complete the volume conversion of the initial sprayed electrolyte from liquid to vapor state, clarify the actual volume of the initial sprayed electrolyte vapor, and provide key data support for subsequent tracing of the explosion medium and reconstruction of the explosion process.

[0062] Step 6: Estimation of the total amount of electrolyte released and the total volume of vapor from all runaway batteries.

[0063] The execution entity is a computer (for data statistics and calculations), and the specific operations are as follows: 6.1 The computer obtains the total number of all uncontrolled batteries in the energy storage power station explosion accident, denoted as N (unit: number, known quantity, determined through on-site investigation of the accident).

[0064] 6.2 Assuming that the initial electrolyte release amount of all runaway batteries is the same (if there are different battery models, the calculation can be performed by grouping them by model and then summing), the computer calculates the total initial electrolyte release amount m of the individual battery obtained in step 4.3. 单 Calculate the total initial electrolyte release M of all runaway batteries. 总 (Unit: g, unknown quantity), the calculation formula is M 总 =N×m 单 .

[0065] 6.3 The computer calculates the initial electrolyte vapor volume V of the single cell obtained in step 5.3. 单 Calculate the total initial electrolyte vapor volume V of all runaway batteries. 总 (Unit: L, unknown quantity), the calculation formula is V 总 =N×V 单 .

[0066] 6.4 The computer summarizes all analysis results (initial electrolyte composition, mass of each component, monomer and total release amount, monomer and total vapor volume) and generates an analysis report to support accurate tracing of the explosive medium and accident investigation.

[0067] The purpose of step 6 is to infer the initial electrolyte release and vapor volume from individual cells to all runaway cells, providing comprehensive and systematic data support for accident investigation and helping to clarify the total amount and risk weight of the explosive medium.

[0068] In summary, the analysis of electrolytes that initially leak during thermal runaway of energy storage batteries often relies on a single detection method and lacks a unified qualitative benchmark. This frequently leads to problems such as "misidentification of components" and "missed identification of components." In particular, for mixed-component electrolytes, it is difficult to accurately identify the specific types of each component, making it hard to support the accuracy of tracing the source of the explosion medium.

[0069] This application addresses the aforementioned problem by establishing a standard curve equation using a multi-point method with a pre-existing mixed electrolyte of known composition and content from conventional lithium-ion batteries. The specific causes are as follows: 1. This application selects the core components of conventional lithium-ion battery electrolytes (such as ethylene carbonate EC, dimethyl carbonate DMC, ethyl methyl carbonate EMC, etc.) and prepares at least 5 sets of standard mixed electrolyte samples in different proportions to ensure that the standard curve covers the possible composition and content range of the actual initial sprayed electrolyte and avoids qualitative deviations caused by a single standard sample.

[0070] 2. Use a multi-point method (at least 5 data points) to perform linear fitting to establish a standard curve, requiring a correlation coefficient R0. 2 ≥0.999 ensures the fitting accuracy of the standard curve, providing a precise benchmark for qualitative identification.

[0071] 3. In qualitative identification, by comparing the retention time of the chromatographic peak of the initial sprayed electrolyte to be tested with the retention time of each known component in the standard curve, and setting a deviation threshold (±0.05 min), the specific components contained in the electrolyte to be tested can be accurately determined, which completely solves the problems of vague qualitative identification, misjudgment and omission in the existing technology, and ensures the uniqueness and accuracy of the qualitative results.

[0072] The quantitative analysis of the initial electrolyte is mostly a rough estimate, which cannot accurately calculate the specific mass of each component and the total amount of electrolyte released. Furthermore, there is a lack of effective means to verify the results, resulting in a large quantitative error (usually exceeding 5%), which fails to provide accurate data support for accident investigations.

[0073] This application addresses the aforementioned problems by establishing a GC standard curve (i.e., standard curve equation) using a multi-point method and combining it with a closed, sealed container and an adiabatic accelerated calorimeter for complete vaporization-condensation recovery. The specific causes are as follows: 1. Based on a precise GC standard curve, the chromatographic peak areas of each component in the electrolyte to be tested can be substituted into the standard curve equation (A...). i =k i ×c i +b i Accurately calculate the mass concentration of each component, and then combine it with the dilution volume using the formula m 组分 =(c 测 ×V 溶 ) / 10 6 It accurately calculates the actual mass of each component, achieving precise quantification at the component level.

[0074] 2. A closed, sealed container combined with an adiabatic accelerated calorimeter is used to place the individual cells in a sealed environment. Under constant temperature conditions above the boiling point of the electrolyte, all the electrolyte is evaporated, ensuring no electrolyte residue or leakage. The vapor is then completely condensed and recovered using a condenser, and the total mass of the recovered electrolyte is weighed. This method not only achieves complete collection of the initially sprayed electrolyte but also further corrects quantitative errors through a verification mechanism that ensures the accuracy of the quantitative results (error controlled within ±0.5%) by verifying that "the sum of the masses of each component deviates from the total mass".

[0075] 3. Determine the total amount of electrolyte released during the initial injection of a single battery cell (m³). 单 =m 液 This provides a precise individual data foundation for subsequent total inference, avoiding the total distortion problem caused by "estimation bias" in existing technologies.

[0076] The current technology only allows for a rough assessment of the liquid mass of the initial electrolyte spray, and cannot accurately convert the liquid electrolyte to vapor volume. However, the volume of electrolyte vapor is a core data point for tracing the source of the explosion medium and reconstructing the explosion process. The lack of existing technology makes it impossible for accident investigations to accurately determine key information such as the explosion power and the range of medium diffusion.

[0077] This application combines qualitative and quantitative results with the ideal gas law to achieve accurate conversion of electrolyte liquid-vapor volume and solve the above problems. The specific reasons are as follows: 1. Based on the qualitative results of step 4, the types and mass percentages of each component in the initial electrolyte spray can be determined, and then the average molar mass of the electrolyte (M=Σ(ω)) can be calculated. i ×M i (), providing accurate parameters for the calculation of the amount of substance.

[0078] 2. Based on the quantitative results of step 3, the total mass of the initial sprayed electrolyte (m) can be obtained. 液 Combining the average molar mass, the formula n=m 液 / M, accurately calculates the amount of substance (n) of electrolyte vapor.

[0079] 3. By applying the ideal gas law (PV=nRT), and substituting known parameters such as standard atmospheric pressure (P=101325Pa), gas constant (R=8.314J / (mol·K)), and the isothermal temperature set by the adiabatic accelerating calorimeter (converted to thermodynamic temperature T), we obtain V=nRT / P. This allows for the precise calculation of the volume (Vt) of the electrolyte after complete vaporization in the initial spray of the single-cell battery. 单 This fills the gap in existing technologies that cannot accurately convert liquid and vapor volumes, and provides key data support for tracing the source of explosive media and reconstructing the explosion process.

[0080] Existing technologies can only perform rough detection of the initial electrolyte spray in a single battery, and cannot correlate all out-of-control batteries at the accident site. They also cannot infer the total release amount and total vapor volume of the initial electrolyte spray, making it difficult to meet the core requirement of "determining the total amount of explosive medium" in the investigation of energy storage power station explosion accidents.

[0081] This application addresses the aforementioned problem by correlating the analysis results of individual cells with the total number of runaway cells and inferring the total release amount and total vapor volume. The specific causes are as follows: 1. The total amount of electrolyte released during initial injection into a single cell (m³) obtained in step 4.3. 单 ), combined with the total number of out-of-control batteries (N) determined by the accident site investigation, and using the formula M 总 =N×m 单 It accurately calculates the total amount of electrolyte released during the initial spraying of all runaway batteries.

[0082] 2. Based on the initial electrolyte vapor volume (V) of the single cell obtained in step 5.3 单 ), through formula V 总 =N×V 单 Accurately calculate the total volume of electrolyte vapor initially sprayed from all runaway batteries.

[0083] 3. Summarize all analysis results (components, mass of each component, monomer and total release, monomer and total vapor volume) to generate a complete analysis report, which can be directly used for accurate tracing of the explosive medium in energy storage power station explosion accidents, solving the pain point that existing technologies cannot support accident investigation.

[0084] Existing analytical methods lack standardized operating procedures, and there are no clear standards for equipment debugging, sample processing, and testing parameters. This leads to significant deviations in analytical results from different operators and different equipment, and poor adaptability, making it difficult to apply to the initial spraying material analysis of LFP batteries and other types of lithium-ion batteries.

[0085] This application solves the above problems through standardized procedure design, clear equipment parameter settings, and constant temperature control of the adiabatic accelerated calorimeter. The specific causes are as follows: 1. The experiment operators are clearly defined as the core execution body (with the computer assisting in parameter setting). The entire process from sample preparation, equipment debugging, electrolyte vaporization and recovery, detection and analysis to total inference is standardized. Each step has clear operating standards (such as airtightness testing standards, temperature control accuracy of ±0.1℃, and detection accuracy of not less than 0.01μg / mL), ensuring the standardization and repeatability of the operation.

[0086] 2. The constant temperature chamber of the adiabatic accelerated calorimeter is used to replace the traditional constant temperature water bath, which can accurately control the constant temperature (T is higher than the boiling point of the electrolyte) and has high temperature control accuracy. This avoids problems such as incomplete vaporization and incomplete recovery of the electrolyte caused by temperature fluctuations, and improves the controllability of the entire analysis process.

[0087] 3. The core analysis process (standard curve establishment, qualitative and quantitative analysis, liquid-vapor conversion) is not dependent on a specific battery model and can be adapted to LFP batteries and other types of lithium-ion batteries. There is no need to adjust the core process for different battery models. It is highly versatile and has a wide range of applications.

[0088] In the analysis process of existing technologies, data records are incomplete and there is no clear verification mechanism, resulting in analysis results that are untraceable, have low credibility, and are difficult to use as effective evidence in accident investigations.

[0089] This application addresses the aforementioned issues through full-process data recording and a dual-result verification mechanism. The specific causes are as follows: 1. All data throughout the process (sample weighing data, equipment debugging parameters, standard curve data, test data, calculation data, etc.) are stored and archived by computer, enabling data traceability and facilitating subsequent review and verification.

[0090] 2. Set up a dual verification mechanism: one is the R-value of the standard curve. 2 The first verification step is to ensure the accuracy of the standard curve by ≥0.999; the second verification step is to ensure the reliability of the quantitative results by verifying the deviation of the quantitative results by ≤±0.5% (comparing the sum of the masses of each component with the total mass of the electrolyte). If the verification requirements are not met, the results can be corrected by re-preparing the standard sample and re-testing to further improve the credibility of the analysis results, which can be directly used as effective technical evidence in the accident investigation.

[0091] In an exemplary embodiment, a computer device is provided, including a memory and a processor. The memory stores a computer program, and the processor executes the computer program to implement the steps in the above-described method embodiments. The computer device can be a server or a terminal. The computer device includes a processor, a memory, an input / output interface (I / O), and a communication interface. The processor, memory, and I / O interface are connected via a system bus, and the communication interface is connected to the system bus via the I / O interface. The processor of the computer device provides computing and control capabilities. The memory of the computer device includes a non-volatile storage medium and internal memory. The non-volatile storage medium stores an operating system, a computer program, and a database. The internal memory provides an environment for the operation of the operating system and computer program in the non-volatile storage medium. The database of the computer device stores data to be processed. The I / O interface of the computer device is used for exchanging information between the processor and external devices. The communication interface of the computer device is used for communicating with an external terminal via a network connection. When the computer program is executed by the processor, it implements the above-described methods.

[0092] In one exemplary embodiment, a computer-readable storage medium is provided storing a computer program that, when executed by a processor, implements the steps in the above-described method embodiments.

[0093] In one exemplary embodiment, a computer program product is provided, including a computer program that, when executed by a processor, implements the steps in the above-described method embodiments.

[0094] It should be noted that the user information (including but not limited to user device information, user personal information, etc.) and data (including but not limited to data used for analysis, data stored, data displayed, etc.) involved in this application are all information and data authorized by the user or fully authorized by all parties, and the collection, use and processing of the relevant data must comply with relevant regulations.

[0095] Those skilled in the art will understand that all or part of the processes in the above embodiments can be implemented by hardware related to computer program instructions. The computer program can be stored in a non-volatile computer-readable storage medium, and when executed, it can include the processes of the embodiments described above. Any references to memory, databases, or other media used in the embodiments provided in this application can include at least one of non-volatile and volatile memory. Non-volatile memory can include read-only memory (ROM), magnetic tape, floppy disk, flash memory, optical memory, high-density embedded non-volatile memory, resistive random access memory (ReRAM), magnetic random access memory (MRAM), ferroelectric random access memory (FRAM), phase change memory (PCM), graphene memory, etc. Volatile memory can include random access memory (RAM) or external cache memory, etc. By way of illustration and not limitation, RAM can take many forms, such as Static Random Access Memory (SRAM) or Dynamic Random Access Memory (DRAM).

[0096] The databases involved in the embodiments provided in this application may include at least one type of relational database and non-relational database. Non-relational databases may include, but are not limited to, blockchain-based distributed databases. The processors involved in the embodiments provided in this application may be general-purpose processors, central processing units, graphics processing units, digital signal processors, programmable logic devices, quantum computing-based data processing logic devices, etc., and are not limited to these.

[0097] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0098] This document uses specific examples to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. Furthermore, those skilled in the art will recognize that, based on the ideas of this application, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A method for qualitative and quantitative analysis of substances ejected during the initial thermal runaway of an energy storage battery, characterized in that, include: Based on the sample to be tested and the adjusted equipment, multiple sets of standard mixed electrolyte samples with different proportions were prepared. The total mass of each group is uniformly m 标 The sample to be tested is a single energy storage battery cell. The peak areas (A) of each component in the standard mixed electrolyte samples were obtained by gas chromatography. i Construct the standard curve equation; The individual energy storage battery cells are placed in a sealed container and then placed in the constant temperature chamber of an adiabatic accelerated calorimeter. They are heated at a constant temperature until the electrolyte is completely vaporized. The liquid electrolyte is then condensed and recovered, and the total mass m of the electrolyte is measured. 液 ; After diluting and bringing the volume to a suitable level, the recovered liquid electrolyte was subjected to gas chromatography detection using the same detection parameters as the standard mixed electrolyte sample to obtain the retention time t of each component of the test sample. r and chromatographic peak area A 测 ; Based on the retention time t of each component's chromatographic peak r Qualitative identification is performed, and based on the standard curve equation and the total mass m of the electrolyte... 液 and the chromatographic peak area A 测 Calculate the total amount of electrolyte released during the initial spraying of all runaway batteries and generate an analysis report.

2. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 1, characterized in that, Based on the sample to be tested and the adjusted equipment, multiple sets of standard mixed electrolyte samples with different proportions were prepared. This also included: Select a single energy storage battery cell and weigh its initial mass m1. Prepare a stainless steel sealed container, an adiabatic accelerated calorimeter, a gas chromatograph, an electronic balance, and standard reagents for lithium-ion battery electrolyte of known purity. The airtightness of the sealed container was tested and found to be qualified. The adiabatic accelerating calorimeter was adjusted to a constant temperature T, which was higher than the boiling point of the electrolyte. The gas chromatograph was adjusted to a detection accuracy of not less than 0.01 μg / mL.

3. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 1, characterized in that, Constructing the standard curve equation specifically includes: The mass concentration of each component c i The x-axis represents the peak area A. i Using the ordinate as the vertical axis, the standard curve equation A is obtained by linear fitting using the multi-point method. i =k i ×c i +b i The correlation coefficient R of the control standard curve 2 ≥0.999; where k i Let b be the slope of the standard curve. i This is the intercept.

4. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 1, characterized in that, Based on the retention time t of each component's chromatographic peak r Qualitative identification is performed, and based on the standard curve equation and the chromatographic peak area A... 测 Calculate the total amount of electrolyte released during the initial discharge from all runaway batteries and generate an analysis report, including: The retention time t of each component chromatographic peak r The retention times of the chromatographic peaks were compared with those of the standard components. Qualitative identification was performed based on the comparison results, and the chromatographic peak area A was determined. 测 Substitute the values ​​into the standard curve equation to calculate the mass concentration c. 测 Determine the mass of each component; Based on the sum of the masses of all components and the total mass m of the electrolyte. 液 The deviation is used to determine the total amount of electrolyte released during the initial spraying of the energy storage cell; Based on the total mass m of the electrolyte 液 Determine the initial electrolyte vapor volume of a single battery cell; Based on the total number of out-of-control batteries at the accident site, the total amount of electrolyte released during the initial spray, and the volume of electrolyte vapor from the initial spray in each individual battery, the total amount of electrolyte released during the initial spray and the total volume of vapor from all out-of-control batteries are calculated, and an analysis report is generated.

5. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 4, characterized in that, Based on the total mass m of the electrolyte 液 Determining the initial electrolyte vapor volume of a single battery cell includes: Based on the ideal gas law, combined with the total mass m of the electrolyte 液 The amount of substance n is calculated from the average molar mass M, and then the initial volume V of the electrolyte vapor injected into the single cell is obtained. 单 .

6. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 5, characterized in that, The total release amount M 总 For M 总 =N×m 单 ; The total steam volume V 总 For V 总 =N×V 单 ; Where N represents the total number of out-of-control batteries at the accident site.

7. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 1, characterized in that, Mass concentration of each component c i =(m 标 ×ω i ×10 6 ) / V 溶 , where ω i V represents the mass percentage of the components. 溶 This is the final volume of the standard mixed electrolyte sample.

8. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 4, characterized in that, Mass of each component m 组分 =(c 测 ×V' 溶 ) / 10 6 ,V' 溶 This is the final volume of the sample to be tested.

9. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 5, characterized in that, Average molar mass M = Σ (ω i ×M i ), where ω i M represents the mass percentage of the components. i The molar mass of the component.

10. The method for qualitative and quantitative analysis of substances initially ejected during thermal runaway of an energy storage battery according to claim 1, characterized in that, The standard mixed electrolyte sample contains at least one of the following components: ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC).

11. A computer device, comprising: A memory, a processor, and a computer program stored in the memory and executable on the processor, characterized in that the processor executes the computer program to implement the qualitative and quantitative analysis method for the initial ejection of thermal runaway substances from an energy storage battery as described in any one of claims 1-10.

12. A computer-readable storage medium having a computer program stored thereon, characterized in that, When executed by a processor, the computer program implements the qualitative and quantitative analysis method for the initial ejection of substances during thermal runaway of an energy storage battery as described in any one of claims 1-10.

13. A computer program product, comprising a computer program, characterized in that, When executed by a processor, the computer program implements the qualitative and quantitative analysis method for the initial ejection of substances during thermal runaway of an energy storage battery as described in any one of claims 1-10.

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