CN113432760A - Battery isothermal calorimeter based on power compensation method and baseline correction method thereof - Google Patents

Battery isothermal calorimeter based on power compensation method and baseline correction method thereof Download PDF

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CN113432760A
CN113432760A CN202110692674.2A CN202110692674A CN113432760A CN 113432760 A CN113432760 A CN 113432760A CN 202110692674 A CN202110692674 A CN 202110692674A CN 113432760 A CN113432760 A CN 113432760A
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temperature
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许金鑫
叶树亮
陈录贤
丁炯
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China Jiliang University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K17/00—Measuring quantity of heat
    • G—PHYSICS
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    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
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    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
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    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
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Abstract

The invention discloses a battery isothermal calorimeter based on a power compensation method and a baseline correction method thereof. The isothermal calorimeter comprises an isothermal heat cavity, a heat sink, a heat equalizing block, a temperature sensor and a flexible heater. The invention deduces the relation between the SOC of the battery and the heat transfer coefficient by measuring the baseline power of the battery under different SOC. And measuring the SOC of the battery and the temperature change of the battery in the charging and discharging processes in real time. And (3) applying the parameters and the relational expression to real-time baseline power calculation, and correcting the influence of temperature fluctuation and battery deformation on calorimetric calculation in the experimental process. The invention is based on the power compensation principle, the temperature fluctuation of the battery is small in the charging and discharging calorimetric process, and the isothermal measuring condition is good. Compared with the existing linear interpolation method, the power baseline calculation method corrects the power baseline change caused by the temperature fluctuation and deformation of the battery, so that the calculation of the baseline power is more practical, and the calculation of the heat absorption and discharge power of the battery is more accurate.

Description

Battery isothermal calorimeter based on power compensation method and baseline correction method thereof
Technical Field
The invention relates to the field of battery thermal characteristic detection, in particular to a battery isothermal calorimeter based on a power compensation method and a baseline correction method thereof.
Background
With the wide application of lithium ion batteries and the continuous development of manufacturing technologies, high-performance lithium ion batteries of various materials and formulations are developed, produced and used. How to ensure safety while improving the performance of the lithium ion battery becomes an important direction for studying the lithium ion battery. Lithium ion battery performance and safety issues are closely related to its thermal characteristics. The method has important significance for the optimization design of the battery and the customization of the heat management scheme[1-4]。
The means for researching the heat generation of the lithium ion battery mainly comprises a model simulation method and an experimental test method[5-6]. Both methods have advantages and disadvantages: the experimental means can accurately test the real heat production condition of the battery under a specific working condition, but the test process is usually more complex and the test instrument is more expensive; the model simulation method is simple and has a short period, but the simulation result sometimes has a large difference from the real situation and has a certain error[7]。
At present, experimental instruments applied to research on heat generation of lithium ion batteries mainly comprise adiabatic acceleration calorimeter and isothermal calorimeter[7-8]. Wherein the adiabatic acceleration calorimeter tests and analyzes the thermal behavior and safety of the battery in the charging and discharging process in an adiabatic environment[9]. The isothermal calorimeter tests the thermal behavior of the battery in the charging and discharging process in an isothermal environment, and the instrument utilizes a temperature control system to maintain the temperature of the battery constant in the measuring process and measure the heat exchange between the battery and the outside. Compared with an adiabatic acceleration calorimeter, the isothermal calorimeter can be used for testing the heat generated by charging and discharging of the lithium ion battery within a wider temperature range and analyzing the relation of the characteristics of the lithium ion battery along with the temperature change.
At present, most of isothermal calorimeters on the market are heat flow type isothermal calorimeters, and the heat flow type battery isothermal calorimeters measure heat flow released or taken from a battery to the environment in real time through a heat flow sensor. In the measuring process, only the temperature of the heat sink is controlled to be constant, the battery generates heat and passively dissipates heat through heat conduction, and the temperature of the battery is not actively controlled, so that the temperature fluctuation is large when the heat release power of the battery is large. In addition, the heat flow type isothermal calorimeter usually has a heat flow sensor on only one side and a limited contact area with an object to be measured, so that the calorimeter is difficult to sense all heat flows and has the defect of large measurement result error.
When the isothermal calorimeter is used for data processing, whether the baseline selection is reasonable or not directly influences the accuracy of a measurement result. As known from the existing literature, the current method for selecting the power baseline of the isothermal calorimeter of the battery has no clear standard, usually depends on the experience of experimenters, and solves the power linear interpolation of the baseline before and after the experiment of the instrument[10]. The default premise of solving the baseline by adopting linear interpolation is that the baseline of the calorimeter is linearly changed before and after the experiment, and the baseline change is influenced in many aspects in the actual experiment process and has stronger nonlinearity. Therefore, the use of linear interpolation to obtain the baseline power introduces errors into the battery thermal characteristic calculation.
Reference to the literature
[1] Duguang super, Zheng Li, Zhang Zhi super, research on thermal safety of Li-ion battery progresses [ J ]. science and technology of energy storage, 2019,8(03): 500-.
[2] The research dynamics of the hot model of the Lioubank Hui, Ganbaiyan and He pei Run lithium ion battery is J, Power Source declaration, 2019,17(01):95-103.
[3] Research on electrochemical-thermal characteristics of automotive high specific energy lithium ion batteries [ D ]. Jiangsu university, 2018.
[4] Wu Qing Yuan, Zhang Heng Yun, Lijun Wei, calibration calorimetry measures the specific heat capacity and heat generation rate of lithium battery [ J ]. automobile engineering, 2020,42(01):59-65.
[5] Wuxian chapter, Yang Donghui, Wang Luiping lithium ion battery electrochemical simulation technology review [ J/OL ] energy storage science and technology 1-12[2021-03-13].
[6] Forest depth, experimental study of thermal characteristics and thermal safety of power lithium ion batteries [ D ]. university of beijing industry, 2017.
[7] The research on the heat generation characteristics of the lithium ion battery is advanced [ J ]. energy storage science and technology, 2019,8(S1):49-55.
[8] Wutangqin, Experimental study on heat generation and thermal induction runaway characteristics of lithium ion batteries [ D ]. university of China science and technology, 2018.
[9] The application of Wanghao, Li Jianjun, Wangli adiabatic accelerated calorimeter in the aspect of safety research of lithium ion battery [ J ]. new material industry, 2013(01):53-58.
[10]Khan M R,Swierczynski M J,Kaer S K.Determination of the behavior and performance of commercial Li-Ion pouch cells by means of isothermal calorimeter[C]//Eleventh International Conference on Ecological Vehicles&Renewable Energies.IEEE,2016.
Disclosure of Invention
Aiming at the defects of the existing battery heat absorption and release measurement technology mentioned in the background technology, the invention provides a battery isothermal calorimeter based on a power compensation method and a baseline correction method thereof, which improve the temperature control effect of a battery in the heat absorption and release process and strengthen the isothermal measurement condition. The instrument and the baseline correction method reduce the measurement error of heat generation caused by charge and discharge of the battery due to baseline fluctuation and improve the measurement accuracy of the calorimeter.
One aspect of the present invention provides a battery isothermal calorimeter based on a power compensation method, comprising:
the isothermal heat cavity is used for installing an isothermal heat main body;
the heat sink is used for transferring heat generated by the battery and the flexible heater in the experimental process and providing a determined temperature boundary condition;
the heat equalizing block is used for equalizing the temperature of the battery and providing a determined heat conduction path;
the temperature sensor is arranged in the groove at the side of the uniform heating block close to the battery and is used for measuring the temperature of the battery after the battery is uniformly heated by the uniform heating block;
and the flexible heater is arranged between the heat equalizing block and the battery and is used for maintaining the baseline power.
Furthermore, the isothermal heat cavity is provided with a heat-insulating interlayer, an electrical connector, an oil bath pipeline and a gas replacement pipeline are arranged on the isothermal heat cavity, and the gas replacement pipeline comprises a pressure release valve, an air outlet valve, an air inlet valve and a gas flowmeter.
Furthermore, a flow guide groove is formed in the heat sink and is connected with an external oil bath through an oil bath pipeline. In the experimental process, the oil bath starts external circulation to pump silicone oil with constant temperature into the heat sink in a circulating manner, the heat generated by the flexible heater and the battery is taken away through the silicone oil, the heat sink is controlled at a stable temperature point, and the heat capacity of the heat sink is large enough relative to that of the battery to be measured.
Furthermore, the temperature sensor measures the temperature of the uniform heating block as a feedback signal to control the output power of the flexible heater and maintain the temperature of the battery constant.
Furthermore, the battery isothermal calorimeter records the output power of the flexible heater in real time for calculating the heat generation of the battery during charging and discharging.
The invention also provides a baseline correction method of the battery isothermal calorimeter based on a power compensation method, which comprises the following steps:
step 1: and determining the isothermal calorimetric temperature and the charge-discharge parameters of the battery to be tested. And completely discharging the battery to be tested to 0% SOC.
Step 2: selecting a uniform heating block and a flexible heater with corresponding sizes according to the geometric size of the battery to be measured; and selecting a proper wire diameter charge-discharge wire according to the charge-discharge parameters of the battery to be tested.
And step 3: connecting the battery to be tested with charging and discharging equipment outside the isothermal calorimetric cavity through a charging and discharging wire; installing a temperature sensor in the groove on the side of the battery, wherein the upper and lower uniform heating blocks are close to the groove; and (3) installing the devices in the isothermal heat cavity according to the structure of a constant-temperature heat sink/a uniform heating block/a flexible heater/a battery to be tested/a flexible heater/a uniform heating block/a constant-temperature heat sink. And sealing the calorimetric cavity after the installation is finished.
And 4, step 4: if the isothermal temperature measured by the battery is lower than the room temperature, dry gas replacement needs to be carried out on the calorimetric cavity after the calorimetric cavity is closed, so that the short circuit of the battery caused by condensate water generated in the experimental process is prevented.
During replacement, an external dry gas source is connected to the gas inlet valve, the gas inlet valve and the gas outlet valve are opened, and gas replacement time is adjusted according to the display of the gas flow rate of the gas flowmeter.
And closing the inlet and outlet air valves after replacement is completed.
And 5: and starting the battery isothermal calorimeter, setting the oil bath temperature into an external circulation temperature control mode, and controlling the temperature of the heat sink to be lower than the determined temperature of the isothermal target temperature.
Step 6: and after the temperature of the heat metering cavity is stable, the temperature control system controls the temperature of the uniform heating block to the isothermal target temperature. And operating for a period of temperature control time, and waiting for the output power of the flexible heater and the temperature of the uniform heat block to be stable.
And 7: and substituting the temperature of the uniform heating block and the power data of the flexible heater measured by the temperature sensor into a heat transfer coefficient calculation formula between the uniform heating block and the heat sink to obtain the heat transfer coefficient under the SOC condition.
And 8: and (4) charging and discharging the battery to be tested according to the fixed step length SOC, repeating the steps 6 and 7 to obtain the heat transfer coefficient under different SOC conditions, and fitting a relation between the battery SOC and the heat transfer coefficient.
And step 9: step 6 is repeated, and then the battery is charged and discharged according to the mode required by the experiment. And after the charging and discharging are finished, the operation is carried out for a period of temperature control time, and the output power of the flexible heater and the temperature of the uniform heat block are waited to be stable. And recording the real-time temperature of the uniform heating block, the real-time power of the heater and the SOC data of the battery in the process.
Step 10: and substituting the real-time temperature of the uniform heating block, the real-time power of the flexible heater, the battery SOC data in the step 9 and the relation of the battery SOC and the heat transfer coefficient in the step 8 into the corrected isothermal baseline formula. And eliminating the influence of the heat transfer coefficient change and the temperature fluctuation on the baseline power to obtain the heat release power of the battery.
Step 11: and integrating the real-time power of the battery with time to obtain the heat absorption and release quantity of the battery in the charging and discharging processes.
Further, in step 7, the battery SOC and the heat transfer coefficient R are obtained according to the output power of the flexible heater and the battery temperatureas(SOC), which represents the thermal resistance between the heat spreader and the heat sink at the current SOC:
Figure BDA0003127333290000031
wherein dHh(dt) flexible heater output power; t issIs the heat sink temperature; t isa(t) is the thermoblock temperature.
Further, in step 10, the corrected isothermal baseline is as follows:
Figure BDA0003127333290000041
wherein dHbdH represents the heat absorption and discharge power of the batteryh(dt) Flexible Heater output Power, TsIs the heat sink temperature; t isa(t) is the thermoblock temperature; ras(SOC) is the thermal resistance between the heat equalizing block and the heat sink under the current SOC.
Further, in step 11, the heat absorption and release of the battery are as follows:
Figure BDA0003127333290000042
wherein, Delta HbAbsorbing and discharging heat for the battery; t is t1The initial charge-discharge time point of the battery; t is t2Recovering a stable time point for a power baseline after the battery is charged and discharged and absorbs heat; delta HhIs t1To t2The heater generates heat over a period of time.
To sum up, in order to obtain accurate heat generation data of battery charging and discharging and develop research on battery performance and safety, the invention designs a battery isothermal calorimeter based on a power compensation method, and provides an isothermal calorimeter baseline correction method, which makes up the defects of the existing calorimeter in battery calorimetry, improves the accuracy of battery thermal characteristic measurement, and greatly enriches the application of isothermal calorimetry technology in the field of battery research.
The invention has the beneficial effects that: the instrument is based on a power compensation principle, the temperature fluctuation of the battery is small in the charging and discharging calorimetric process, and the isothermal measuring condition is good. Compared with the existing linear interpolation method, the power baseline calculation method corrects the power baseline change caused by the temperature fluctuation and deformation of the battery, so that the calculation of the baseline power is more practical, and the calculation of the heat absorption and discharge power of the battery is more accurate. The invention provides technical support for accurately measuring the thermal characteristics of the lithium ion battery under the isothermal condition, and has great significance for promoting the healthy development of the battery industry in China.
Drawings
FIG. 1 is a structural diagram of an isothermal calorimeter of a battery of the invention;
FIG. 2 is an equivalent heat transfer model of the isothermal calorimeter of the battery of the invention;
FIG. 3 is a temperature fluctuation diagram of a charge-discharge homothermal block of a 50Ah lithium battery 1C according to the present invention;
FIG. 4 is a graph showing the change of the thermal resistance between the heat equalizing block and the heating sheet with time in the battery charging experiment process according to the present invention;
FIG. 5 is a graph showing the change of the thermal resistance between the heat equalizing block and the heating sheet with time in the battery discharge test process according to the present invention;
FIG. 6 is a graph of exothermic power versus time for a battery charging process using two baseline processing methods;
FIG. 7 is a graph of exothermic power versus time for a battery discharge process using two baseline processing methods;
illustration of the drawings: 1. a battery to be tested; 2. a heat equalizing block; 3. a flexible heater; 4. a charging and discharging wire 5 and a calorimetric cavity; 6. a temperature sensor; 7. a heat sink; 8. a high and low temperature resistant oil bath pipeline; 9. the aviation plug has high air tightness; 10. an intake valve; 11. an air outlet valve; 12. a gas flow meter; 13. and (4) releasing the valve.
Detailed Description
In order to make the steps, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described more clearly, in detail and completely in the following with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are some, not all embodiments of the invention.
In a first aspect, the present invention provides a battery isothermal calorimeter based on a power compensation method, where the battery isothermal calorimeter based on the power compensation method includes:
the isothermal heat cavity is used for installing the isothermal heat main body and has good air tightness.
Furthermore, the isothermal calorimetric cavity is provided with a heat-insulating interlayer design, and has good heat-insulating performance.
Furthermore, an electric joint, an oil bath pipeline and a gas replacement pipeline are arranged on the isothermal calorimetric cavity, and the joints/pipelines have good air tightness.
Furthermore, the isothermal calorimetric cavity is good in air tightness, an external dry air source can be used for being matched with the gas replacement pipeline to replace the air containing water vapor in the calorimetric cavity during low-temperature experiments, and the risk of short circuit of the battery caused by condensed water at low temperature is eliminated.
Further the gas replacement pipeline comprises a pressure release valve, a gas outlet valve, a gas inlet valve and a gas flowmeter.
And the heat sink is used for transferring heat generated by the battery and the flexible heater in the experimental process and providing a determined temperature boundary condition. The heat sink is internally provided with a flow guide groove which is connected with an external oil bath through an oil bath pipeline. In the experimental process, the oil bath opens the extrinsic cycle and pumps the silicone oil cycle of constant temperature into the heat sink, takes away flexible heater and battery heat production through silicone oil, controls the heat sink at the steady temperature point.
Furthermore, the heat capacity of the heat sink is large enough relative to the heat capacity of the battery to be measured, and the temperature control effect of the oil bath on the heat sink is good.
And a heat equalizing block for equalizing the battery temperature, providing a definite heat conduction path. The heat equalizing blocks with corresponding models are matched according to batteries with different models. The side of the heat equalizing block close to the battery is provided with a groove for mounting a temperature sensor.
And the temperature sensor is arranged in the groove at the side of the uniform heating block close to the battery and is used for measuring the temperature of the battery after the battery is uniformly heated by the uniform heating block. In the experimental process, the temperature of the uniform heating block measured by the temperature sensor is used as a feedback signal to control the output power of the flexible heater and maintain the constant temperature of the battery.
And the flexible heater is arranged between the heat equalizing block and the battery and is used for maintaining the baseline power. In the experimental process, the temperature control system takes the temperature measured by the temperature sensor as a feedback signal, controls the output power of the heater in real time to compensate the baseline power and maintains the isothermal condition. Meanwhile, the calorimeter records the output power of the flexible heater in real time for calculating the heat generation of the battery during charging and discharging.
Furthermore, the heaters are designed to have different sizes according to different shapes of the batteries to be tested.
During the experiment, the battery is installed between the flexible heaters, and meanwhile, the battery is connected to an external battery charge and discharge tester through a discharge wire filled in the heat cavity.
In a second aspect, the present invention also provides a power compensation type isothermal calorimeter baseline correction method, including:
and determining the test target temperature and the charge and discharge parameters of the battery to be tested.
And selecting a corresponding type of flexible heater and a corresponding type of uniform heating block according to the shape of the battery to be measured.
The battery was mounted as shown in fig. 1, and was connected to the charging and discharging equipment via the electrical connectors on the thermal chamber for subsequent charging and discharging experiments.
The oil bath temperature is set to a determined temperature point below the target temperature, and the oil bath is waited to control the heat sink temperature to the determined temperature. And starting a calorimeter temperature control program, controlling the temperature of the battery to a target temperature by the output power of the heater, and keeping the power of the heater for keeping the temperature of the battery constant approximately constant after a calorimeter temperature field is stable, wherein the power is called as baseline power.
And starting the battery charging and discharging equipment, and charging and discharging the battery according to the preset charging and discharging parameters. In the process, the battery has a heat absorption/release effect, the temperature of the sensor is subjected to feedback control, the power of the heater is adjusted in real time, the temperature of the battery is kept constant, and the baseline power at the moment consists of the heat absorption and release power of the battery and the power of the heater.
After the charging and discharging of the battery are finished, the output power of the heater is gradually recovered to a baseline state.
In the isothermal experiment data calculation process, the core factor influencing the accuracy of the calculation result is the reasonable selection of the power baseline. Under ideal conditions, the baseline power is consistent before and after charging and discharging of the battery. However, in the actual experiment process, the baseline power is not completely constant, and needs to be obtained according to the power of the heating plate recorded in the experiment process.
The existing isothermal baseline processing method depends on experience of operators, and the power of the heating sheet is linearly fitted at each selected point before and after charging and discharging of the battery. The premise of using the method is that the change of the power baseline in the charging and discharging process is linear, the power baseline in the charging and discharging process of the battery is influenced by multiple aspects under the actual condition and has strong nonlinearity, and meanwhile, the initial point power and the end point power of the linear baseline fitting are selected according to the experience of experimenters and have subjectivity. Therefore, the linear fitting to obtain the power base line can cause a large error in the calorimetric result.
Aiming at the factors influencing the power baseline and aiming at improving the calorimetric accuracy of the battery, the baseline correction method of the power compensation type isothermal calorimeter is provided.
According to the isothermal calorimeter configuration described in FIG. 1, the analysis object is divided into five parts. As shown in fig. 2, the environment of the heat sink, the heat equalizing block, the flexible heater, the battery to be tested and the calorimetric cavity are respectively. Let T be the temperature of each, C be the heat capacity, M be the mass, R be the heat resistance, include various heat transfer methods and mainly heat conduction. Subscripts s, a, h, b, e represent the heat sink, heat spreader, heater, battery, and calorimeter cell environments, respectively.
The heat transfer equation of the isothermal calorimeter is analyzed by taking a heater, a battery, a uniform heating block and a heat sink as main objects. For a battery, the change in internal energy shown by formula (1) is made up of two parts, one part being the heat H generated or absorbed during charging and dischargingbAnd a part of the heat transfer quantity Qb:
Figure BDA0003127333290000061
The thermal power of the heat transfer can be written as:
Figure BDA0003127333290000062
the two terms on the right side of the formula (2) are respectively the heat exchange power of the battery and the heater and the heat exchange power of the battery and the heat measuring cavity.
For a heater, the heat balance equation is as in equation (3):
Figure BDA0003127333290000063
wherein HhElectric power consumed for the heater, dHhThe/dt is the electric power consumed by the heater, QhIs the heat quantity of the heater exchanging heat with the outside.
Figure BDA0003127333290000064
The three terms on the right side of the formula (4) are respectively the heat exchange power of the heater and the uniform heating block, the heater and the battery, and the heater and the calorimetric cavity.
For the thermoblocs, the equation for the heat balance without an internal heat source is shown in equation (5):
Figure BDA0003127333290000065
wherein, the three terms on the right side of the formula (5) are respectively the heat exchange power of the uniform heating block and the heat sink, the uniform heating block and the heater, and the uniform heating block and the calorimetric cavity.
The equations (1), (3) and (5) are combined to obtain the equation (6).
Figure BDA0003127333290000066
Under isothermal conditions, the instrument temperature field is stable, with zero on the left of equation (6). The battery isothermal calorimeter baseline power can be described by equation (7).
Figure BDA0003127333290000071
In the formula (7), HbAbsorbing and discharging heat for the battery; hhHeat is generated for the heater; dHbThe/dt is the heat absorption and release power of the battery; dHh(dt) heater output power; the sum of the battery heat absorption and discharge power and the heater output power is the base line power of the isothermal calorimeter. Right side of equationOne term is heat conduction and heat exchange between the uniform heat block and the heat sink, TsIs the heat sink temperature; t isaIs the temperature of the uniform heating block; rasIs the thermal resistance between the uniform heating block and the heat sink. The second term on the right is the convective heat transfer between the environment of the calorimetric cavity and the battery, TeIs ambient temperature; t isbIs the battery temperature; rebIs the thermal resistance between the environment of the calorimetric cavity and the battery. The third term on the right is the convective heat transfer between the environment of the calorimetric cavity and the heater, ThIs the heater temperature; recIs the thermal resistance between the environment of the calorimetric cavity and the heater. The fourth term of the right formula is the convection heat transfer between the environment of the heat measuring cavity and the uniform heat block ReaIs the thermal resistance between the environment of the calorimetric cavity and the uniform heating block. During the experiment, the calorimetric cavity is sealed, the internal gas is dry, the convective heat transfer coefficient is small, the temperature difference between each component and the environment of the calorimetric cavity is small, and the convective heat transfer can be ignored relative to the heat conduction. Therefore, the baseline power calculation is simplified to equation (8).
Figure BDA0003127333290000072
From the formula (8), the main factors influencing the baseline stability of the isothermal calorimeter are:
temperature difference between the heat equalizing block and the heat sink;
② the thermal resistance between the uniform heating block and the heat sink.
Under ideal isothermal conditions: the thermal resistance between the uniform heating block and the heat sink is constant. The power baseline is constant in the process of measuring the heat of the battery during charging and discharging. In the practical experiment process, due to the hysteresis of heat conduction, the temperature of the uniform heat block fluctuates to a certain degree in the heat absorption and release process of the battery. In the charging and discharging process of the battery, the geometric shape of the battery can deform along with the change of the SOC due to the breathing effect, so that the thermal resistance between the installation position of the temperature sensor and the heat sink changes.
Correcting errors caused by the condition I by recording the real-time temperature difference between the uniform heat block temperature and the heat sink; for the error caused by the condition II, the error is derived from the deformation of the battery in the charging and discharging process, and the existing research shows that the deformation degree of the battery is related to the charging and discharging SOC of the battery and has repeatability. Therefore, by measuring isothermal baseline work under different SOC conditionsThe ratio can be used to reversely deduce R under different SOC conditionsasFitting out SOC and RasRelation function Ras(SOC). The change relation SOC (t) of the battery SOC along with time in the charging and discharging process can be obtained through the data recorded by the charging and discharging equipment. The power baseline formula is modified to formula (9).
Figure BDA0003127333290000073
As shown in the formula (10), the heat absorption and release power of the battery is integrated with time to obtain the heat absorption and release quantity delta H of the battery in the charging and discharging processb. Wherein t is1Is the charge-discharge start time; t is t2The post baseline recovery time; delta HhIs t1-t2The heater generates heat over a period of time.
Figure BDA0003127333290000074
The steps of testing the thermal characteristics of the battery by using the battery isothermal calorimeter based on a power compensation method are as follows:
and selecting the uniform heating block (2) and the flexible heater (3) with corresponding sizes according to the geometric size of the selected battery (1) to be tested. And selecting a proper wire diameter charge-discharge wire (4) according to the selected battery model and the charge-discharge current. The battery to be tested is connected with external charging and discharging equipment through the electric connectors on the conducting wire and the calorimetric cavity (5). A temperature sensor (6) is arranged in the groove on the side of the battery, which is close to the upper and lower uniform heating blocks. The battery is arranged in the heat measuring cavity according to the structure of heat sink (7)/heat equalizing block (temperature sensor)/flexible heater/battery to be measured/flexible heater/heat equalizing block (temperature sensor)/heat sink. And closing the calorimetric cavity after the battery is installed.
Furthermore, the heat sink is connected with the external oil bath through a high-low temperature resistant oil bath pipeline (8).
Furthermore, the oil bath can realize the heat sink temperature control within the range of minus 40 ℃ to 100 ℃.
Furthermore, the heater is soft and thin in texture and is well attached to the battery and the uniform heat block.
Furthermore, the electric connecting wires of the heater and the temperature sensor are connected with the outside through a high-air-tightness aviation plug (9).
Furthermore, the temperature sensor is well embedded with the uniform heating block groove.
If the isothermal temperature measured by the battery is lower than the room temperature, dry gas replacement needs to be carried out on the calorimetric cavity after the calorimetric cavity is closed. During replacement, an external dry gas source is connected to the upper gas inlet valve (10) of the calorimetric cavity, the gas inlet valve and the gas outlet valve (11) are opened, and gas replacement time is adjusted according to the gas flow speed displayed by the gas flowmeter (12) on the wall of the calorimetric cavity. And closing the inlet and outlet air valves after replacement is completed.
Furthermore, a pressure release valve (13) is arranged on the calorimetric cavity and used for avoiding overlarge air pressure in the cavity in the gas replacement process.
And starting the battery isothermal calorimeter, setting the oil bath into an external circulation temperature control mode, and controlling the temperature of the heat sink to be lower than the determined temperature of the target isothermal temperature. And after the heat sink temperature is stable, the temperature control system controls the temperature of the battery to the target isothermal temperature. And operating for a period of time to control the temperature, waiting for the output power of the heater to be stable, and regarding the stable power output in the period of time as the front baseline power. And charging and discharging the battery according to preset charging and discharging parameters by using battery charging and discharging equipment. And after the charging and discharging of the battery are finished, waiting for the output power of the heater to recover to be stable, and regarding the stable power output in the period of time as the post-baseline power.
In the experimental process, the battery isothermal calorimeter records the uniform heating temperature of the battery and the output power of the heater in real time. After the experiment is finished, a power compensation type isothermal calorimeter baseline correction method is adopted to calculate the heat production power and the heat production quantity of the battery during the charge and discharge of the battery in the experiment process.
The power compensation type isothermal calorimeter baseline correction method comprises the following steps:
wherein the real-time heat release power dH in the charging and discharging process of the batterybThe value of/dt is determined according to the formula (10).
Wherein dHh(dt) is the output power of the heater, Ta(t) is the uniform heating temperature of the battery, and is recorded by the isothermal calorimeter of the battery in real time(ii) a SOC (t) is a relation of the SOC of the battery along with time change in the charging and discharging process, and is obtained by recording the real-time charging and discharging capacity fitting of the battery by charging and discharging equipment. T issThe temperature is determined by the oil bath as the heat sink temperature, and the oil bath has stable temperature control performance in the invention, and the temperature is regarded as a constant value. RasThe coefficient is the thermal resistance between the uniform heating block and the heat sink, and is obtained by measuring the isothermal baseline power of the battery under different SOC conditions and performing inverse fitting. R at different SOCasThe calculation formula is shown in formula (11).
Figure BDA0003127333290000081
Ras(SOC) the specific test method was as follows:
before the experiment, the battery to be tested is completely discharged by using a charging and discharging device.
And selecting a uniform heating block and a heater with corresponding sizes according to the geometric size of the selected battery to be tested. And selecting a proper wire diameter charge-discharge wire according to the selected battery model and the charge-discharge current, and connecting the battery to be tested with external charge-discharge equipment through the wire and the electrical connector on the calorimetric cavity. And the temperature sensor is arranged in the groove on the side of the battery, which is close to the upper and lower uniform heating blocks. The battery is arranged in the calorimetric cavity according to the structure of heat sink/uniform heating block (temperature sensor)/heater/battery to be tested/heater/uniform heating block (temperature sensor)/heat sink, and the calorimetric cavity is closed.
If the measured isothermal temperature is lower than the room temperature, after the instrument is installed, dry gas replacement needs to be carried out on the calorimetric cavity. During replacement, external dry gas is connected to the isothermal heat cavity, inlet and outlet air valves on the isothermal heat cavity are opened, and gas replacement time is adjusted according to the gas flow rate displayed by the gas flowmeter. And closing the inlet and outlet air valves after replacement is completed.
And starting the battery isothermal calorimeter, setting the oil bath into an external circulation temperature control mode, and controlling the temperature of the heat sink to be lower than the determined temperature of the isothermal target temperature. And after the heat sink temperature is stable, the temperature control system controls the temperature of the battery to the target isothermal temperature. The temperature is controlled for a period of time, and the temperature T of the uniform heating block is waiteda' (t) and heater output power dHh'/dt Stable, substituting measured Battery temperature and base line Power into equation (11) to obtain R ' under 0% SOC 'as. Then charging the battery with 20% SOC as span by using battery charging and discharging equipment, and obtaining R of the battery under different SOCas'. The least square fitting is adopted to obtain the R of the battery to be measured in the charging process from 0% to 100% of SOCas'and SOC' relation Ras'(SOC'). Similarly, R in the discharge process can be obtained by the methodas'with SOC'. And (4) obtaining the SOC 'time-varying relation SOC' (t) of the battery to be tested according to the charging and discharging capacity variation of the battery recorded by the charging and discharging equipment.
Mixing the above Kas'(SOC')、SOC'(t)、Ta'(t)、dHcAnd the values of'/dt are substituted into the formulas (9) and (10) to obtain the heat absorption and discharge power and the heat absorption and discharge quantity of the battery in the process of charging and discharging under the isothermal condition.
Compared with the existing battery heat production characteristic measuring instrument, the invention has the following advantages: the invention is based on the isothermal principle, and can measure and determine the charge-discharge thermal characteristics of the battery at the temperature. Secondly, the invention has wide testing temperature range which is mainly related to the temperature control range of the external oil bath. The existing instrument can realize the measurement of the charge-discharge thermal characteristics of the battery at each temperature point within the range of-40 ℃ to 100 ℃. Thirdly, the invention overcomes the defect that the heat flow type isothermal calorimeter and the heat flow sensor are easy to drift based on the power compensation principle. The temperature fluctuation of the battery in the charging and discharging process is reduced in principle, and the isothermal measurement condition of the battery is strengthened.
The invention also provides a method for correcting the baseline of the power compensation type isothermal calorimeter, and the method reduces the baseline power error caused by the temperature fluctuation of the battery and the change of the battery volume along with the SOC in principle. Therefore, the accuracy of measuring the thermal characteristics of the battery in the charging and discharging processes of the lithium battery is greatly improved.
The lithium ion battery charging and discharging experiments are carried out by using the measuring device and the measuring method, and the experimental parameters are shown in table 1.
TABLE 1 lithium cell Charge and discharge Experimental parameters
Figure BDA0003127333290000091
The experimental measurement shows that the temperature of the battery after being uniformly heated by the uniform heating block in the charging and discharging process changes along with time as shown in figure 3, wherein a curve I represents the temperature control in the charging process, and a curve II represents the temperature control in the discharging process; r in the process of charging a batteryas' (SOC) variation is shown in FIG. 4; r during battery dischargeas' (SOC) variation is shown in FIG. 5; two baseline processing methods are adopted to obtain the curve of the heat release power of the rechargeable battery along with the time, wherein the curve (a) represents the heat release curve of the linear power baseline battery, and the curve (a) represents the heat release curve of the corrected power baseline battery; two baseline treatment methods are adopted to obtain the discharge battery heat release power change curve with time as shown in figure 7, curve (c) represents the linear power baseline battery heat release curve, and curve (c) represents the corrected power baseline battery heat release curve. The heat absorbed and released by the battery using the linear interpolation to process the baseline and the heat absorbed and released by the battery using the method described herein are shown in table 2. From the second table, it can be seen that there is a certain difference in the heat release amount of the battery charge and discharge obtained by the two power baseline processing methods.
TABLE 2 Heat production quantity of battery during charging and discharging measured by two base line treatment methods
Figure BDA0003127333290000101
In order to further verify the measurement accuracy of the isothermal calorimeter provided by the invention and the effectiveness of the provided baseline optimization method, the isothermal calorimeter is verified by adopting a joule heat calibration method. During calibration, a cast aluminum heater similar in geometry and heat capacity to the battery was mounted at the battery location. The power is supplied to the cast aluminum heater through the high-precision constant current source, and the heat release of the battery is simulated. The deformation of the cast aluminum heating block can be ignored in the calibration process, and the heat transfer coefficient R isasAlmost constant, but due to Ta(t) dynamic changes, with corresponding changes in baseline. After the calibration experiment is finished, two baseline processing methods are adopted to process calorimeter experimental data. The heat release of the cast aluminum heating block obtained by the two baseline processing methods is compared with the electric energy output by the high-precision constant current source, and the comparison result is measured by the two baseline processing methods in the table 3 to calibrate the heatingThe heat production is shown. Compared with the conventional method for solving the power baseline through linear interpolation, the method for correcting the power baseline of the isothermal calorimeter, which is provided by the invention, is closer to the reality in the experiment for solving the heat release.
TABLE 3 calibrated heating heat production measured by two baseline treatment methods
Figure BDA0003127333290000102
In summary, the battery isothermal calorimeter based on the power compensation method and the baseline correction method thereof provided by the invention include an instrument capable of measuring heat generated by charging and discharging of a battery under an isothermal condition and a method for correcting the power baseline of the isothermal calorimeter. The isothermal calorimeter of the battery provides technical support for measuring the heat production of the battery during charging and discharging at each temperature point between-40 ℃ and 100 ℃. The battery isothermal calorimeter designed by the invention overcomes the disadvantage that an adiabatic acceleration calorimeter cannot measure the heat absorption of the battery and the thermal characteristics of the battery at a fixed temperature point; the defects that the temperature fluctuation of the battery heat release battery is large and the heat flow sensor is easy to drift when the heat flow type isothermal calorimeter is used for measuring the battery heat are overcome. Therefore, the method has great significance for the research on the thermal characteristics of the battery under different temperatures and different charging and discharging conditions. In addition, the method for correcting the baseline power solves the problem that errors exist in the heat absorption and discharge power of the battery due to the fact that the power baseline is simply calculated in the linear interpolation mode in the prior art in principle. Therefore, the achievement of the invention has great significance for improving the accuracy of the measurement of the thermal characteristics of the lithium battery under the isothermal condition.

Claims (9)

1. A battery isothermal calorimeter based on a power compensation method is characterized by comprising the following steps:
the isothermal heat cavity is used for installing an isothermal heat main body;
the heat sink is used for transferring heat generated by the battery and the flexible heater in the experimental process and providing a determined temperature boundary condition;
the heat equalizing block is used for equalizing the temperature of the battery and providing a determined heat conduction path;
the temperature sensor is arranged in the groove at the side of the uniform heating block close to the battery and is used for measuring the temperature of the battery after the battery is uniformly heated by the uniform heating block;
and the flexible heater is arranged between the heat equalizing block and the battery and is used for maintaining the baseline power.
2. The battery isothermal calorimeter based on the power compensation method according to claim 1, wherein the isothermal calorimetry cavity is provided with a heat-insulating interlayer, and an electrical connector, an oil bath pipeline and a gas replacement pipeline are arranged on the isothermal calorimetry cavity, and the gas replacement pipeline comprises a pressure release valve, a gas outlet valve, a gas inlet valve and a gas flowmeter.
3. The battery isothermal calorimeter based on the power compensation method according to claim 1, wherein a flow guide groove is formed in the heat sink and is connected with an external oil bath through an oil bath pipeline; in the experimental process, the oil bath starts external circulation to pump silicone oil with constant temperature into the heat sink in a circulating manner, the heat generated by the flexible heater and the battery is taken away through the silicone oil, the heat sink is controlled at a stable temperature point, and the heat capacity of the heat sink is large enough relative to that of the battery to be measured.
4. The battery isothermal calorimeter based on the power compensation method according to claim 1, wherein the temperature sensor measures the temperature of the thermoblock as a feedback signal to control the output power of the flexible heater, so as to maintain the battery temperature constant.
5. The battery isothermal calorimeter based on the power compensation method according to claim 1, wherein: the battery isothermal calorimeter records the output power of the flexible heater in real time for calculating the heat generation of the battery during charging and discharging.
6. A baseline correction method of a battery isothermal calorimeter based on a power compensation method is characterized by comprising the following steps:
step 1: determining isothermal calorimetric temperature and charge-discharge parameters of the battery to be tested; completely discharging the battery to be tested to 0% SOC;
step 2: selecting a uniform heating block and a flexible heater with corresponding sizes according to the geometric size of the battery to be measured; selecting a proper wire diameter charge-discharge wire according to charge-discharge parameters of the battery to be tested;
and step 3: connecting the battery to be tested with charging and discharging equipment outside the isothermal calorimetric cavity through a charging and discharging wire; installing a temperature sensor in the groove on the side of the battery, wherein the upper and lower uniform heating blocks are close to the groove; installing the devices in the isothermal heat cavity according to the structure of a constant-temperature heat sink/a uniform heating block/a flexible heater/a battery to be tested/a flexible heater/a uniform heating block/a constant-temperature heat sink; sealing the calorimetric cavity after the installation is finished;
and 4, step 4: if the isothermal temperature measured by the battery is lower than the room temperature, dry gas replacement needs to be carried out on the calorimetric cavity after the calorimetric cavity is closed, so that the short circuit of the battery caused by condensate water generated in the experimental process is prevented;
during replacement, connecting an external dry gas source to the gas inlet valve, opening the gas inlet valve and the gas outlet valve, and adjusting gas replacement time according to the gas flow rate displayed by the gas flowmeter;
closing the inlet and outlet air valves after replacement is completed;
and 5: starting the battery isothermal calorimeter, setting the oil bath temperature to be an external circulation temperature control mode, and controlling the heat sink temperature to be lower than the determined temperature of the isothermal target temperature;
step 6: after the temperature of the heat metering cavity is stable, the temperature control system controls the temperature of the uniform heat block to the isothermal target temperature; operating for a period of temperature control time, and waiting for the output power of the flexible heater and the temperature of the uniform heat block to be stable;
and 7: substituting the temperature of the uniform heating block and the power data of the flexible heater measured by the temperature sensor into a heat transfer coefficient calculation formula between the uniform heating block and the heat sink to obtain the heat transfer coefficient under the SOC condition;
and 8: charging and discharging the battery to be tested according to the fixed step length SOC, repeating the steps 6 and 7 to obtain the heat transfer coefficient under different SOC conditions, and fitting a relation between the battery SOC and the heat transfer coefficient;
and step 9: repeating the step 6, and then charging and discharging the battery according to the mode required by the experiment; after the charging and discharging are finished, the operation is carried out for a period of temperature control time, and the output power of the flexible heater and the temperature of the uniform heat block are waited to be stable; recording the real-time temperature of the uniform heating block, the real-time power of the heater and the SOC data of the battery in the process;
step 10: substituting the real-time temperature of the uniform heating block, the real-time power of the flexible heater and the battery SOC data in the step 9 and the relation between the battery SOC and the heat transfer coefficient in the step 8 into a corrected isothermal baseline power formula; eliminating the influence of heat transfer coefficient change and temperature fluctuation on baseline power to obtain the heat release power of the battery;
step 11: and integrating the real-time power of the battery with time to obtain the heat absorption and release quantity of the battery in the charging and discharging processes.
7. The baseline correction method of the battery isothermal calorimeter based on the power compensation method according to claim 6, wherein:
in the step 7, the battery SOC and the heat transfer coefficient R are obtained according to the output power of the flexible heater and the battery temperatureas(SOC), which represents the thermal resistance between the heat spreader and the heat sink at the current SOC:
Figure FDA0003127333280000021
wherein dHh(dt) Flexible Heater output Power, TsIs the heat sink temperature, Ta(t) is the thermoblock temperature.
8. The baseline correction method of the battery isothermal calorimeter based on the power compensation method according to claim 6, wherein:
in step 10, the corrected isothermal baseline power is as follows:
Figure FDA0003127333280000022
wherein dHbdH represents the heat absorption and discharge power of the batteryh(dt) Flexible Heater output Power, TsIs the heat sink temperature, Ta(t) is the uniform hot block temperature, Ras(SOC) is the thermal resistance between the heat equalizing block and the heat sink under the current SOC.
9. The baseline correction method of the battery isothermal calorimeter based on the power compensation method according to claim 6, wherein:
in step 11, the heat absorption and release of the battery are as follows:
Figure FDA0003127333280000023
in the formula (3), Δ HbFor absorbing and discharging heat of the battery, t1Is the initial time point of charging and discharging of the battery, t2The power baseline recovers the stable time point after the heat absorption and release of the battery charge and discharge, delta HhIs t1To t2The heater generates heat over a period of time.
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