Experimental researches on thermal runaway in cylindrical LiFePO4 batteries during nail penetration

锂离子电池在发生针刺之后会造成内部短路,进而产生大量热量和浓烟以至引发热失控。本文通过模拟实验剖析圆柱型磷酸铁锂电池针刺后的内部结构,结合理论分析探究针刺热失控产热机理。以自行设计搭建的磷酸铁锂电池针刺热失控实验平台为基础,在初始20℃室温下采用Φ5 mm的钨钢针刺穿电池,观测电池的热失控发展情况以及电池电压、表面温升变化规律。根据实验结果得到以下结论：①针刺对圆柱型磷酸铁锂电池造成的热失控剧烈情况带有随机性;②电池电压在针刺后下降至0V,若破坏过程中电池内部热反应气体泄漏甚至发生爆炸则电压下降更迅速;③电池温度在被刺破后迅速上升,其温升趋势总体随破坏程度增加而加快。综合来看,针刺对磷酸铁锂电池的损坏是不可逆且通常会并发热失控,因此建议在设计电池结构时应当充分考虑防针刺及对电池进行额外保护。     

Experimental simulation of internal short circuit in Li-ion and Li-ion-polymer cells

A multi-parameter controlled pinch test was developed to study the occurrence of internal short circuits in Li-ion and Li-ion-polymer cells. By tuning the control parameters (i.e., cell voltage as well as pinching area, load, and speed), the pinch test can reproducibly create an internal short between a cell jelly-roll's inner layer electrodes as small as 1-mm wide. This recreates conditions similar to those that may occur during service. In this paper we demonstrate the use of the pinch test as a means to assess design and manufacturing changes in Li-ion-polymer cells on their thermal stability and to identify features or characteristics that lower risk of potential thermal events created by internal short circuits.     

Non-invasive blood perfusion measurements using a combined temperature and heat flux surface probe

Non-invasive blood perfusion measurement systems have been developed and tested in a phantom tissue and an animal model. The probes use a small sensor with a laminated flat thermocouple to measure the heat transfer and temperature response to an arbitrary thermal event (convective or conductive) imposed on the tissue surface. Blood perfusion and thermal contact resistance are estimated by comparing heat flux data with a mathematical model of the tissue. The perfusion probes were evaluated for repeatability and sensitivity using both a phantom tissue test stand and exposed rat liver tests. Perfusion in the phantom tissue tests was varied by controlling the flow of water into the phantom tissue test section, and the perfusion in the exposed liver tests was varied by temporarily occluding blood flow through the portal vein. The phantom tissue tests indicated that the probes can be used to detect small changes in perfusion (0.005 ml/ml/s). The probes qualitatively tracked the changes in the perfusion of the liver model due to occlusion of the portal vein.     

Development of the inorganic composite phase change materials for passive thermal management of Li-ion batteries: material characterization

The battery thermal management system based on phase change materials (PCMs) has proven to be a safe, inexpensive, and high-performance technology, which is currently gaining popularity over the other battery thermal management systems. PCMs are able to absorb heat generated by batteries, prolong battery life, and improve their performance. Organic compounds, such as paraffin, are widely used as phase change materials for the battery thermal management systems; however, there are no published data on the application of inorganic PCMs. Therefore, the main objective of this work is developing of two composite inorganic PCMs based on magnesium chloride hexahydrate and characterizing their properties for passive thermal control of lithium-ion battery packs. Moreover, to have a valid baseline and compare the behavior of two inorganic PCMs with currently commercialized and well investigated organic PCM, paraffin wax was used as reference material for both mixtures. All three PCMs were impregnated into the expanded graphite matrix to enhance their thermal conductivity. The material characterization studies, including thermal properties investigation, density and viscosity measurements, soaking and compression testing, evaluation of thermal expansion, thermal conductivity, and micro X-ray fluorescence analysis, were conducted for all PCMs. The results indicate that both inorganic mixtures are appropriate for thermal management of Li-ion battery packs. Future work with the developed and characterized composite inorganic PCMs will include electrical cycling studies and nail penetration tests to reveal their effectiveness for passive thermal management of Li-ion battery packs.     

A three-dimensional thermal abuse model for lithium-ion cells

To understand further the thermal abuse behavior of large format Li-ion batteries for automotive applications, the one-dimensional modeling approach formulated by Hatchard et al. [T.D. Hatchard, D.D. MacNeil, A. Basu, J.R. Dahn, J. Electrochem. Soc. 148(7) (2001) A755–A761] was reproduced. Then it was extended to three dimensions so we could consider the geometrical features, which are critical in large cells for automotive applications. The three-dimensional model captures the shapes and dimensions of cell components and the spatial distributions of materials and temperatures, and is used to simulate oven tests, and to determine how a local hot spot can propagate through the cell. In simulations of oven abuse testing of cells with cobalt oxide cathode and graphite anode with standard LiPF₆ electrolyte, the three-dimensional model predicts that thermal runaway will occur sooner or later than the lumped model, depending on the size of the cell. The model results showed that smaller cells reject heat faster than larger cells; this may prevent them from going into thermal runaway under identical abuse conditions. In simulations of local hot spots inside a large cylindrical cell, the three-dimensional model predicts that the reactions initially propagate in the azimuthal and longitudinal directions to form a hollow cylinder-shaped reaction zone.     

A method of testing for rating thermal storage devices based on thermal performance

This paper describes a proposed test method for determining the “effective capacity” and heat loss characteristics of thermal storage devices. The prescribed series of tests should provide useful data for the rating of thermal storage devices based on thermal performance. The apparatuses and major components used in the tests have been prescribed so a liquid or air can be used as the transfer fluid. The series of tests to be conducted consist of one steady-state test to determine the heat loss characteristics and eight transient tests to determine the “effective capacity” for both heat storage and heat removal. During the transient tests, the entering fluid temperature is changed in a step-wise manner and amount of energy either stored or removed over a specified test time is determined. Sample experimental data are given in the paper to demonstrate the concept of the transient tests.     

An in situ thermal response test for borehole heat exchangers of the ground-coupled heat pump system

Thermal response tests (TRTs) are crucial for the estimation of the ground thermal properties and thermal performance of the borehole heat exchanger (BHE) of the ground-coupled heat pump (GCHP) system. In this article, a TRT apparatus was designed and built to measure the temperature response of inlet and outlet sections of BHE in the test borehole, the apparatus can effectively operate under both constant heating flux modes and heat injection and extraction modes with a constant inlet temperature. A TRT for a project of GCHP located in the Jiangsu province of China was carried out by the experimental apparatus. Based on the experimental data, the heat transfer performances of BHE under heating and cooling modes were evaluated, and the ground thermal properties, which include the ground thermal conductivity, ground volumetric specific heat, borehole thermal resistance and effective soil thermal resistance, were determined by the line source model. The results indicate that the experimental device and analysis model proposed in this article can be effectively applied to estimate the ground thermal properties and thermal performance of BHE. During the process of thermal response of ground, the fluid temperatures vary acutely at the start-stage of 8 h, and then tend to be a steady state after 40 h. The test data during the start-stage should be discarded for improving the estimation accuracy of ground thermal properties. At the same time, the effective soil thermal resistance increases continuously with time and a steady-state value would be reached after the start-time, and this steady-state thermal resistance can be used to evaluate the required length of BHE. In addition, the heat transfer rate of the BHE under different operating conditions can be used for the further evaluation on long-term operation performance of GCHPs.     

An alternative cooling system to enhance the safety of Li-ion battery packs

A passive thermal management system is evaluated for high-power Li-ion packs under stressful or abusive conditions, and compared with a purely air-cooling mode under normal and abuse conditions. A compact and properly designed passive thermal management system utilizing phase change material (PCM) provides faster heat dissipation than active cooling during high pulse power discharges while preserving sufficiently uniform cell temperature to ensure the desirable cycle life for the pack. This study investigates how passive cooling with PCM contributes to preventing the propagation of thermal runaway in a single cell or adjacent cells due to a cell catastrophic failure. Its effectiveness is compared with that of active cooling by forced air flow or natural convection using the same compact module and pack configuration corresponding to the PCM matrix technology. The effects of nickel tabs and spacing between the cells were also studied.     

Understanding cathode flooding and dry-out for water management in air breathing PEM fuel cells

An analysis of water management in air breathing small polymer electrolyte membrane fuel cells (PEMFCs) is presented. Comprehensive understanding of flooding and dry-out limiting phenomena is presented through a combination of analytical modeling and experimental investigations using a small PEMFC prototype. Configurations of the fuel cell with different heat and mass transfer properties are experimentally evaluated to assess the impact of thermal resistance and mass transport resistance on water balance. Manifestation of dry-out and flooding problems, as limiting phenomena, are explained through a ratio between these two resistances. Main conclusions are that decreasing the ratio between thermal and mass transport resistance under a certain point leads to flooding problems in air breathing PEMFC. Increasing this ratio leads to dry-out of the polymer electrolyte membrane. However, too high thermal resistance or too low mass transport resistance reduces the limiting current by pushing forward the dry-out problem. This work provides a framework to achieve the proper balance between thermal rejection and mass transport to optimize the maximum current density of free convection fuel cells.     

Freezing of Water in a Slab with Boundary Conditions of the Third Kind

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Thermal and electrochemical behaviour of C/LixCoO2 cell during safety test

Thermal and electrochemical processes in a 1000 mAh lithium-ion pouch cell with a graphite anode and a Li_xCoO₂ cathode during a safety test are examined. In overcharge tests, the forced current shifts the cell voltage to above 4.2 V. This causes a cell charged at the 1 C rate to lose cycleability and a cell charged at the 3 C rate to undergo explosion. In nail penetration and impact tests, a high discharge current passing through the cells gives rise to thermal runaway. These overcharge and high discharge currents promote joule heat within the cells and leads to decomposition and release of oxygen from the de-lithiated Li_xCoO₂ and combustion of carbonaceous materials. X-ray diffraction analysis reveals the presence of Co₃O₄ in the cathode material of a 4.5 V cell heated to 400 °C. The major cathode product formed after the combustion process cells abused by forced current is Co₃O₄ and by discharge current the products are LiCoO₂ and Co₃O₄. The formation of a trace quantity of CoO through the reduction of Co₃O₄ by virtue of the reducing power of the organic solvent is also discussed.     

Energy,exergy and uncertainty analyses of the thermal response test for a ground heat exchanger

This paper presents energy, exergy and uncertainty analyses for the thermal response test of a ground heat exchanger. In this study, a vertical U‐shaped ground heat exchanger with 80 m depth and 20 cm borehole diameter is installed for the first time at the university premises in Saudi Arabia. A mobile thermal response apparatus is constructed and used to measure the performance of the ground heat exchanger. The thermal response test was carried out four times at different thermal loads from September 2007 to April 2008. The energy and exergy transports of these thermal response tests were analyzed using the experimental results obtained in this period. The analysis provides a better understanding of the overall performance of vertical ground heat exchangers, verifies the thermal response test results and improves the experimental setup. Copyright © 2008 John Wiley & Sons, Ltd.     

Reciprocating air flow for Li-ion battery thermal management to improve temperature uniformity

The thermal management of traction battery systems for electrical-drive vehicles directly affects vehicle dynamic performance, long-term durability and cost of the battery systems. In this paper, a new battery thermal management method using a reciprocating air flow for cylindrical Li-ion (LiMn₂O₄/C) cells was numerically analyzed using (i) a two-dimensional computational fluid dynamics (CFD) model and (ii) a lumped-capacitance thermal model for battery cells and a flow network model. The battery heat generation was approximated by uniform volumetric joule and reversible (entropic) losses. The results of the CFD model were validated with the experimental results of in-line tube-bank systems which approximates the battery cell arrangement considered for this study. The numerical results showed that the reciprocating flow can reduce the cell temperature difference of the battery system by about 4 °C (72% reduction) and the maximum cell temperature by 1.5 °C for a reciprocation period of τ = 120 s as compared with the uni-directional flow case (τ = ∞). Such temperature improvement attributes to the heat redistribution and disturbance of the boundary layers on the formed on the cells due to the periodic flow reversal.     

Modeling of hot gas flow through a feed stream within a horizontal pipe

High heat penetration into a feed stream within a horizontal pipe is described mathematically with a gas flow and heat transfer model. Influences of varied factors on the gas flow and heat transfer in porous media are examined for different conditions. The temperature of the packed‐bed particles and the gas velocity distribution curves are obtained for the feeding service at interruption and at regular charge operating conditions. The numerical results show that the thermal effect to the packed‐bed particles by the seepage flow fluid is high only in the position near the gas entrance. The thermal penetration depth tends to increase with the seepage flow velocity and decrease with the feed rate. The operating conditions and the porosity of solid bed have importance effects on the gas velocity and temperature field in the thermal penetration zone. The model results are found to compare favorably with the experimental data available in the literature. © 2003 Wiley Periodicals, Inc. Heat Trans Asian Res, 32(6): 553–565, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.10109     

Heat extraction thermal response test in groundwater-filled borehole heat exchanger – Investigation of the borehole thermal resistance

In groundwater-filled borehole heat exchangers (BHEs) convective flow influences the heat transfer in the borehole. During heat extraction thermal response tests (TRTs) the effect of the changing convective flow is more dominant than during heat injection tests. Water is heaviest around 4 °C and when exceeding this temperature during the test, the convective flow is stopped and restarted in the opposite direction resulting in a higher borehole thermal resistance during that time. Just before 0 °C the convective flow is the largest resulting in a much lower borehole thermal resistance. Finally, during the freezing period phase change energy is released and material parameters change as water is transformed into ice, resulting in a slightly higher borehole resistance than at a borehole water temperature of 0 °C. The changes in borehole thermal resistance are too large for ordinary analysis methods of thermal response tests to work. Instead another method is introduced where the borehole thermal resistance is allowed to change between different time intervals. A simple 1D model of the borehole is used, which is matched to give a similar mean fluid temperature curve as the measured one while keeping the bedrock thermal conductivity constant during the whole test. This method is more time-consuming than ordinary TRT analyses but gives a good result in showing how the borehole thermal resistance changes. Also, a CFD-model with a section of a simplified borehole was used to further study the effect of convection and phase change while the temperature was decreased below freezing point. The test and the model show similar results with large variations in the borehole thermal resistance. If the knowledge of changing borehole thermal resistance was used together with a design program including the heat pump and its efficiency, a better BHE system design would be possible.     

Prediction of thermal conductivity of ethylene glycol–water solutions by using artificial neural networks

The objective of this study is to develop an artificial neural network (ANN) model to predict the thermal conductivity of ethylene glycol–water solutions based on experimentally measured variables. The thermal conductivity of solutions at different concentrations and various temperatures was measured using the cylindrical cell method that physical properties of the solution are being determined fills the annular space between two concentric cylinders. During the experiment, heat flows in the radial direction outwards through the test liquid filled in the annual gap to cooling water. In the steady state, conduction inside the cell was described by the Fourier equation in cylindrical coordinates, with boundary conditions corresponding to heat transfer between the solution and cooling water. The performance of ANN was evaluated by a regression analysis between the predicted and the experimental values. The ANN predictions yield R² in the range of 0.9999 and MAPE in the range of 0.7984% for the test data set. The regression analysis indicated that the ANN model can successfully be used for the prediction of the thermal conductivity of ethylene glycol–water solutions with a high degree of accuracy.     

Coupling and thermal integration of a solid oxide fuel cell with a magnesium hydride tank

A solid oxide fuel cell (SOFC) based combined heat and power (CHP) system in the power range of 1 kWe fed by pure hydrogen stored in a MgH₂ tank thermally integrated with the SOFC is presented. Different system configurations were first simulated to compare the system performances in each case. An experimental setup specially designed to test the thermal integration of a magnesium hydride tank with a 1 kWe SOFC stack is fully described. The difficulties encountered during the coupling tests are useful to understand how to solve these technical issues.     

Modeling and validation of temperature changes in a pouch lithium-ion battery at various discharge rates

This paper deals with the thermal modeling of temperature rise in a pouch lithium-ion battery with LiFePO₄ (also known as LFP) cathode material. The developed model represents the main thermal phenomena in the cell in terms of temperature change. The proposed model is validated with the collected experimental data from a module composed of 11 cells. In the conducted experiments, the different charge and discharge rates of 1/2C, 1C, 2C and 2.5C are applied. It is seen that, the increased discharge rates result in increased temperature on the surface of the battery. When the discharge rate is doubled, from 1C to 2C, cell temperatures have risen by 3.5 times. A simplified model for determining the heat generation is developed and validated with the test results.     

Performance analysis of organic Rankine cycle based on location of heat transfer pinch point in evaporator

The location of heat transfer pinch point in evaporator is the base of determining operating parameters of organic Rankine cycle (ORC). The physical mathematical model seeking the location of pinch point is established, by which, the temperature variations both of heat source and working fluid with UA can be obtained. Taking heat source with inlet temperature of 160 °C as example, the matching potentials between heat source and working fluid are revealed for subcritical and supercritical cycles with the determined temperature difference of pinch point. Thermal efficiency, exergy efficiency, work output per unit area and maximum work outputs are compared and analyzed based on the locations of heat transfer pinch point either. The results indicate that supercritical ORC has a better performance in thermal efficiency, exergy efficiency and work output while outlet temperature of heat source is low. Otherwise, subcritical performs better. Small heat transfer coefficient results in low value of work output per unit area for supercritical ORC. Introduction of IHX may reduce the optimal evaporating pressure, which has a great influence on heat source outlet temperature and superheat degree. The analysis may benefit the selection of operating parameters and control strategy of ORC.     

Granular phase change materials for thermal energy storage: Experiments and numerical simulations

The present paper reports on the utilization of granular phase change composites (GPCC) of small particle diameter (1–3 mm) in latent heat thermal energy storage (LHTES) systems. The phase changing parameters (phase change temperature, latent heat, and energy storage capacity) of GPCC have been determined using differential scanning calorimeter (DSC) and temperature-history methods. Further analysis of measurement results has been conducted to describe the evolution of latent heat with temperature during phase change in terms of liquid fraction–temperature relationships. Charging and discharging packed bed column experiments have been also carried out for different operating conditions to analyze the potential of GPCC for packed bed thermal energy storage. The present column results clearly demonstrate the dependence of temperature variation along the packed bed and the overall performance of the storage unit on the phase change characteristics of GPCC. Small and non-uniform particles diameters of GPCC and heterogeneity of the bed material complicate the phenomena of heat transfer and evolution of latent heat in the packed bed. Mathematical modeling of the packed bed that considers the GPCC and air as two separate phases with inter-phase heat transfer is presented. Comparisons between experimental and numerical results are used to evaluate the sensitivity of numerical simulations to different model parameters.