CN110220940A - A kind of irregular sample heating conduction test method - Google Patents

A kind of irregular sample heating conduction test method Download PDF

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CN110220940A
CN110220940A CN201910622791.4A CN201910622791A CN110220940A CN 110220940 A CN110220940 A CN 110220940A CN 201910622791 A CN201910622791 A CN 201910622791A CN 110220940 A CN110220940 A CN 110220940A
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CN110220940B (en
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侯德鑫
叶树亮
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China Jiliang University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00Investigating or analyzing materials by the use of thermal means
    • G01N25/20Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity

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Abstract

The invention discloses a kind of heating conduction test methods for the irregular sample such as lithium battery.Three kinds of states such as the present invention allows sample to be tested to be successively in constant temperature T0 state, surface has the constant temperature T1 state of the strong convection coefficient of heat transfer, surface insulation, construct the unsteady-state heat transfer process to exchange heat between environment inside sample to be tested;The test is using sample to be tested itself energy storage as heat source or heat sink, and inside and outside heat transfer testing is realized when not damaging sample, can avoid heterogeneous sample surface layer good heat conducting material bring heat shielding effects, can also solve sample irregular shape bring heating problem.This method can be used for the non-destructive testing of metal shell quadrate lithium battery Equivalent Thermal Conductivities, it can also be used to which other conventional methods are difficult to the irregular shape sample heating conduction non-destructive testing detected.

Description

A kind of irregular sample heating conduction test method
Technical field
The present invention relates to a kind of thermal conductivity of material test methods, more particularly a kind of not advise for quadrate lithium battery etc. The then heating conduction test method of sample.
Background technique
Thermal conductivity of material is most important to thermal design, and accurate test material heating conduction is the basis of system design, It is the foundation for producing quality control.Thermal conductivity of material generally uses thermal coefficient to indicate, thermal diffusivity is also used when a small number of Parameter characterization, in the case where known density and specific heat capacity, the two knows that one can calculate another.
Heating conduction test has many methods and standard at present, but these methods are directed to traditional material mostly, general to require Test sample is isotropic homogeneous material.With the development of technology, various new materials and new process occur, some tradition sides There is the undesirable situation of test effect in method.For example its thermal coefficient is needed in lithium battery thermal design, but lack at present suitably Experimental test procedures.Lithium battery generally comprises several packing forms such as cylinder, Soft Roll, rectangular, and wherein soft package lithium battery is relatively Rule has had some non-destructive testing methods to be seen in document, and the thermal coefficient non-destructive testing method of cylinder and quadrate lithium battery It is also short of very much at present, the main reason is that the two is very irregular.
Lithium battery is irregularly mainly reflected in three aspects.First, lithium battery heating conduction has anisotropy, cylindrical Lithium battery generally axially and radially has different thermal coefficients, and quadrate lithium battery is in parallel lamination direction and vertical lamination side To with different thermal coefficients.Second, cylindrical and quadrate lithium battery has a heterogeneous texture, inside the two generally winding or The inner core of stacking, and there is metal shell in outside;Since the heating conduction of metal shell is preferable, typically much deeper than cylindrical lithium battery diameter To thermal coefficient, also much larger than quadrate lithium battery longitudinal direction thermal coefficient;The heating of conventional non-destructive testing method and thermometric are all arranged On lithium battery surface, metal shell can generate the effect of similar heat shielding, cause test insensitive to inner core thermal coefficient.The Three, cylinder type lithium battery is in irregular shape, it is difficult to be conducted heat by the heat sink structuring one-dimensional of external heat source.
For irregular sample as similar lithium battery, conventional method is difficult to be applicable in.For example steady state method requires construction one Dimension heat transfer, and the atypical characteristic of lithium battery causes heat transfer usually non-uniform, does not meet test model requirement.Cold store enclosure As flicker method is primarily adapted for use in thin slice, and requiring sample is homogeneous material;It is uniform material that Adsorbent By Using Transient Plane Source Technique, which also requires sample, Material, and there is flat surface.
In typical thermal-conductive coefficient or thermal diffusivity non-destructive testing method, the table for being generally placed at sample to be tested is heated and observed Face, therefore the property of sample skin-material is bigger on test result influence than internal material.If sample to be tested is non-homogeneous material Material, such as the lithium battery with metal shell then conduct heat very uneven, and heat mainly passes through metal shell and is transmitted to heat from heat source Heavy, sample interior material properties influences very little to test result.And in practical applications may more concerned with sample to be tested inside and Heating conduction when external heat exchange, so that the equivalent parameters that test obtains can not generate guiding value to practical application.
Summary of the invention
The technical problem to be solved by the present invention is to having for lithium battery is in irregular shape, material is uneven etc. is similar to How the irregular sample of feature is tested its heating conduction using lossless method.
The technical solution adopted for solving the technical problem of the present invention are as follows:
A kind of irregular sample heating conduction test method, test process includes following three step:
Step 1: sample to be tested being placed in environment Env0, Env0 is isoperibol, and temperature is denoted as T0;Sample to be tested exists Enough time is kept in environment Env0, until sample to be tested temperature is T0 and temperature is uniform everywhere.
Step 2: sample to be tested being quickly transferred in environment Env1, Env1 is constant temperature strong convection environment;The temperature of Env1 Different from Env0 temperature, note temperature is T1;Sample to be tested surface film thermal conductance hs1 should be big as far as possible in Env1, generally should be greater than 100;Sample to be tested keeps a period of time in environment Env1 and carries out heat exchange, the value of retention time timTx with environment It should make the ratio of the absolute value of the variation of sample to be tested mean temperature and T1-T0 in the period between 0.2-0.8.
Step 3: sample to be tested being quickly transferred in environment Env2 and is kept for a period of time;Retention time timAd should foot It is enough big, so that sample to be tested internal temperature reaches unanimity substantially to be advisable;Sample to be tested surface should be as far as possible close to exhausted in environment Env2 Heat, degree of insulation should make sample and environment heat exchange bring sample average temperature change in the timAd time be no more than (T1-T0) 0.1 times;It measures and records sample to be tested and enters Env2 rear surface temperature and change with time process Ts (t).
After test, according to the data of parameter and record in test process, including T0, T1, timTx, Ts (t) etc., Sample to be tested heating conduction is assessed using characteristic quantity, or is based on the equivalent thermally conductive system of equivalent heat transfer model Inversion Calculation sample to be tested Number.
Characteristic quantity used in a kind of assessment sample to be tested heating conduction is the heat dissipation capacity of sample to be tested in step 2, calculating side Method is as follows: (1) calculating the maximum value of Ts (t), be denoted as Tsm;(2) heat dissipation capacity RatioLoss is calculated according to following formula:
Characteristic quantity calculating method used in another kind assessment sample to be tested heating conduction is as follows: calculating sample to be tested in step 3 From the shortest time for reaching Tch into Env2 to surface temperature, as characteristic quantity;Wherein temperature Tch are as follows:
Tch=T1+ (T0-T1) C
Wherein parameter C is preset preset parameter, and value is generally between 0~1.
Based on equivalent heat transfer model Inversion Calculation sample to be tested Equivalent Thermal Conductivities: known and thermally conductive using thermal physical property parameter Performance and the close material of sample to be tested, production geometric dimension and the consistent reference sample of sample to be tested;Using reference sample into The capable and identical test of sample to be tested, the skin temperature profile that step 3 records when then being tested according to reference sample, inverting The sample surfaces coefficient of heat transfer hs1 in step 2 is calculated as calibration result, then hs1 is applied to the thermally conductive of sample to be tested test Coefficient Inversion Calculation.
Furtherly, when executing step 3, environment Env2 is free convection environment, and sample to be tested surface is equivalent in the environment Coefficient of heat transfer hs2 is demarcated with the following method and is applied to sample to be tested thermal coefficient Inversion Calculation: good using heating conduction Material production and two reference samples of sample to be tested adjoining dimensions;One electric heating piece is clipped among two reference samples, It is placed in the environment Env2 of step 3 with posture when being similar to sample to be tested test, keeps constant power continuous heating, power Installation warrants are that surface temperature when reference sample being made to reach stable state is suitable with surface temperature in sample to be tested testing procedure 3;When After reference sample reaches thermal balance, record heating power Q, reference sample average surface temperature Tr, environment temperature Ta and sample Total surface area S, the calibration result of surface film thermal conductance hs2 are as follows: hs2=Q/ ((Tr-Ta) * S).
Beneficial effects of the present invention: the present invention between three kinds of ambient conditions by switching sample to be tested, the heat transfer of construction In the process heat source or it is heat sink be sample interior energy storage, rather than external heating device, therefore direction of conducting heat is sample interior and outer Between portion;Even for lithium battery with metal case, heat shielding problem will not occur, test result can be very good reflection sample Inside and outside heat exchange property.In the test method, although test environment may be not ideal enough, for example it cannot achieve in step 2 Sufficiently large surface film thermal conductance, cannot achieve surface insulation in step 3, but by reference to several calibration experiments of sample, can be with The nominal data of surface film thermal conductance in step 2 and step 3 is obtained, phase can be corrected by being updated in the inverse model of sample to be tested Pass factor bring error.
Detailed description of the invention
Fig. 1 is the test method schematic diagram of embodiment of the present invention 1;
Correlated characteristic amount schematic diagram when Fig. 2 is data analysis in embodiment of the present invention 1;
Fig. 3 is the sample to be tested schematic diagram in embodiment of the present invention 2;
Fig. 4 is the test method schematic diagram of embodiment of the present invention 2;
Fig. 5 is that sample to be tested surface equivalent heat transfer coefficient under natural convection air environment is demarcated in embodiment of the present invention 2 Method schematic diagram.
Specific embodiment
In order to keep the objectives, technical solutions, and advantages of the present invention clear, the present invention is done into one below in conjunction with attached drawing Step explanation:
Embodiment 1
Test object has irregular shape in the embodiment, and material may be uneven, hot physical property and ceramic material It is close.If being difficult to meet the heat transfer of test model in lossless situation construction, therefore can not survey using traditional test methods Try its heating conduction.
For the test method of the embodiment as shown in Figure 1, thermocouple 2 is fixed on 1 surface of sample to be tested, thermocouple 2 connects thermometric 3 sample record temperature data of instrument;In addition thermocouple 7 and sample holder 8 connect temperature measuring device 3, for measuring record test Environment temperature in the process.Test process mainly includes three steps:
Step 1: sample to be tested 1 is placed in the water bath with thermostatic control 4 that temperature is "+20 DEG C of room temperature " and is kept for 1 hour, actual measurement note Record bath temperature is T0.
Step 2: it is about that the water in the water-bath 5 of room temperature, in water-bath 5 passes through big function that sample to be tested 1, which is quickly transferred to temperature, Rate water pump 6 drives, and has very high flow rate, so that 1 surface film thermal conductance of sample to be tested is sufficiently large;Water in water-bath 5 is enough, makes Total thermal capacitance of water reaches hundred times of sample to be tested thermal capacitance or more, to guarantee that water temperature will not be because handing over sample to be tested heat in test process It changes and significant changes occurs;The temperature of water-bath 5 is denoted as T1 using thermocouple 7 and the measurement record of temperature measuring device 3;Sample to be tested 1 from Water-bath 4 be switched to water-bath 5 time-consuming less than 2 seconds to reduce sample to be tested, heat-radiation belt carrys out test error in air;From to test sample Product 1 enter water-bath 5 and start timing, are kept for 100 seconds, subsequently into next step.
Step 3: sample to be tested being quickly removed from water-bath 5 and quickly dries surface moisture, air is placed on and is flowed without pressure In dynamic closing indoor environment, sample holder 8 use heat-barrier material, and with 1 contact area very little of sample to be tested, to reduce surface Radiation loss;Since sample to be tested removes the moment of water-bath 5, temperature instrumentation 3 is with the thermometric number of 5Hz rate record thermocouple 2 According to being denoted as Ts (t).
One of the following two kinds method can be used in assessment sample to be tested heating conduction:
(1) method 1: the surface temperature change curve Ts (t) of sample to be tested in step 3 is substantially as shown in Fig. 2, note Ts (t) maximum value of curve is Tsm, calculates following characteristic quantity:
Characteristic quantity RatioLoss indicates heat dissipation capacity of the sample to be tested in circulator bath in step 2, can reflect to test sample The product capacity of heat transmission, the RatioLoss the big, shows that heating conduction is better.
(2) method 2: the surface temperature change curve Ts (t) of sample to be tested in step 3 substantially as shown in Fig. 2, calculate to Sample is fetched into the shortest time tim80 that surface temperature reaches T80 from water-bath 5, as characteristic quantity.Tim80 is reflected Sample to be tested is averaged heat diffusion capabilities, also reflects its capacity of heat transmission indirectly, and the smaller then sample to be tested heating conduction of tim80 is better, Wherein temperature T80 are as follows:
T80=T1+ (T0-T1) × 0.8
Embodiment 2
Test object is metal-back quadrate lithium battery in the embodiment, and atypical characteristic, which is mainly manifested in, macroscopically to be had Inhomogeneities, structure are as shown in Figure 3: battery is made of metal shell 10 and inner core 11, and inner core 11 is complete by metal shell 10 Environmental sealing.Inner core 11 can generate heat when battery works, these heats need to be transmitted to battery outer surface (that is, metal shell 1 outer surface) it further could pass by the measures such as air or water circulation.Heat is transmitted to metal shell 10 inside inner core 11 The heating conduction of outer surface is extremely important to thermal design.If not destroying lithium battery encapsulation, in traditional test methods heating and Thermometric all on metal shell 10, heat transfer occur mainly in metal shell 10 towards metal shell 10 plays inner core material 11 The effect for having arrived heat shielding causes test that can not accurately reflect the performance that internal heat is conducted outward.To make measurement condition as far as possible Close to diabatic process when battery work, the heat transfer direction that when test constructs should be mainly the heat exchange between inside and outside.
The test method of the embodiment is as shown in figure 4, thermocouple 2, thermocouple are fixed in 1 centre of surface position of lithium battery to be measured 2 connection 3 sample record temperature datas of temperature measuring device;In addition thermocouple 7 and thermocouple 9 connect temperature measuring device 3, for measuring note Record environment temperature in test process.Test process mainly includes three steps:
Step 1: lithium battery 1 to be measured is placed on the water bath with thermostatic control 4 that temperature is "+20 DEG C of room temperature " (document testing temperature is T0) In, it is kept for 1 hour.
Step 2: it is about that the water in the water-bath 5 of room temperature, in water-bath 5 passes through greatly that lithium battery 1 to be measured, which is quickly transferred to temperature, Power water pump 6 drives, and has very high flow rate, so that 1 surface film thermal conductance of lithium battery is sufficiently large;Water in water-bath 5 is enough, makes Total thermal capacitance of water reaches hundred times of mesuring battary thermal capacitance or more, to guarantee that water temperature will not be due to battery heat exchange in test process Significant changes occur;The temperature of water-bath 5 is denoted as T1 using thermocouple 7 and the measurement record of temperature measuring device 3;Lithium battery 1 is from water-bath 4 Be switched to water-bath 5 time-consuming less than 2 seconds to reduce battery, heat-radiation belt carrys out test error in air;Enter water-bath 5 from lithium battery 1 Start timing, is kept for 100 seconds, subsequently into next step.
Step 3: lithium battery being quickly removed from water-bath 5 and dried surface moisture, is placed on envelope of the air without forced flow Close in indoor environment, sample holder 8 use heat-barrier material, and with 1 contact area very little of mesuring battary, with reduce surface radiating damage It loses;Since lithium battery removes the moment of water-bath 5, temperature instrumentation 3 is denoted as Ts with the temperature measurement data of 5Hz rate record thermocouple 2 (t);Environment temperature is surveyed using thermocouple 9 and temperature measuring device 3, is denoted as T2.
Inverting lithium battery Equivalent Thermal Conductivities to be measured with the following method.It is as follows to initially set up test model:
Sample interior:
Boundary:If 0 < τ < 100
Boundary:If τ >=100
Original state: T=T0, when τ=0
ρ indicates sample to be tested averag density in formula, can be obtained by total weight divided by volume;C indicates that equivalent specific heat holds, can It is measured using calorimeter;K indicates Equivalent Thermal Conductivities, is the unknown quantity for needing inverting to estimate;Hs1 is circulator bath in step 2 In sample to be tested surface equivalent heat transfer coefficient, can pass through calibration experiment determine;Hs2 is that sample to be tested is in air in step 3 Surface equivalent heat transfer coefficient, can pass through calibration experiment determine;X, y, z representation space coordinate, τ indicate the time, and T is indicated to test sample The Spatio-temporal Evolution of product temperature degree, n indicate the direction of 6 surfaces vertically inwards.Although lithium battery is non-uniform respectively to different in practice Property material, and lithium battery is equivalent to homogeneous isotropism material in the model, but the Equivalent Thermal Conductivities that its assessment obtains are still It is meaningful, the main influence for reflecting thermal contact resistance between lithium battery inner core longitudinal direction thermal coefficient and inner core and metal shell.
Using following error function:
ε=| | Tssim(t)-Ts(t)||2
TssimIt (t) is the temperature prediction value for solving the sample to be tested surface thermocouple temperature measuring point that previous heat transfer model obtains, Error function calculates prediction thermal response and surveys the RMS deviation of thermal response.Existed by gridding method or convenient value searching algorithm Thermal coefficient candidate searches in section, selects to make the smallest thermal coefficient of error function value as inversion result.
Wherein the method for sample to be tested surface equivalent heat transfer coefficient hs2 is as follows in demarcating steps 3: using reference shown in Fig. 5 Sample RB comprising aluminium alloy production thin plate 12 and thin plate 13, the two size it is identical and with lithium battery maximum to be measured surface ruler It is very little consistent, remember that the area on single surface is S;Between thin plate 12 and thin plate 13, three's electric heating piece 14 bonds together, contact Thermal resistance is smaller;Electric heating piece 14 is heated with firm power, power value with thin plate 12 when thermal balance and 13 surface temperature of thin plate with to Surface temperature when sample is tested quite is advisable;When thin plate 12 and thin plate 13 enter thermal balance, recorded using thermal imaging system 15 12 surface temperature field of thin plate, and calculating its average value is Tm1;13 surface temperature field of thin plate is recorded using thermal imaging system 16, and is calculated Its average value is Tm2;Using air themperature near thermocouple 17 and the measurement record thin plate 12 of temperature instrumentation 3, it is denoted as Ta1;It uses Air themperature near thermocouple 18 and the measurement record thin plate 13 of temperature instrumentation 3, is denoted as Ta2;Measurement electric heating piece heating power is Q; Then hs2 calibration result are as follows:
Wherein the method for sample to be tested surface equivalent heat transfer coefficient hs1 is as follows in demarcating steps 2: being made using HDPE plastic With the consistent reference sample RA of 1 size of lithium battery to be measured, the experiment of lithium battery, dependence test before being repeated using reference sample RA Step and test parameter are completely the same, and the temperature measurement data of thermocouple 3 is TsRA (t) in note reference sample RA experiment.Using with The same model of sample to be tested inverting thermal coefficient, but the density of material, specific heat capacity and thermal coefficient use the parameter of HDPE, this A little data can be obtained by document, or be measured using conventional;Hs2 uses calibration result in model, and hs1 is as unique in model Known variables;Using error function and inversion algorithm as before, inverting determines the value of hs1 as calibration result.
Content described in this specification embodiment is only enumerating to the way of realization of inventive concept, protection of the invention Range should not be construed as being limited to the specific forms stated in the embodiments, and protection scope of the present invention is also and in art technology Personnel conceive according to the present invention it is conceivable that equivalent technologies mean.

Claims (5)

1. a kind of irregular sample heating conduction test method, it is characterised in that: test process includes following three step:
Step 1: sample to be tested being placed in environment Env0, Env0 is isoperibol, and temperature is denoted as T0;Sample to be tested is in environment Enough time is kept in Env0, until sample to be tested temperature is T0 and temperature is uniform everywhere;
Step 2: sample to be tested being quickly transferred in environment Env1, Env1 is constant temperature strong convection environment;The temperature of Env1 with Env0 temperature is different, and note temperature is T1;Sample to be tested surface film thermal conductance hs1 should be big as far as possible in Env1;Sample to be tested is in environment A period of time is kept in Env1 and carries out heat exchange with environment, and the value of retention time timTx should make to be measured in the period The ratio of the absolute value of sample average temperature change and T1-T0 is between 0.2-0.8;
Step 3: sample to be tested being quickly transferred in environment Env2 and is kept for a period of time;Retention time, timAd was sufficiently large, So that sample to be tested internal temperature reaches unanimity substantially to be advisable;Sample to be tested surface should be as far as possible close to insulation in environment Env2;It surveys It measures and records sample to be tested and enter Env2 rear surface temperature and change with time process Ts (t);
After test, according to the data of parameter and record in test process, including T0, T1, timTx, Ts (t), spy is used Sign amount assesses sample to be tested heating conduction, or is based on equivalent heat transfer model Inversion Calculation sample to be tested Equivalent Thermal Conductivities.
2. test method according to claim 1, it is characterised in that: assessment sample to be tested heating conduction used in characteristic quantity be to The heat dissipation capacity of sample in step 2 calculates as follows: (1) calculating the maximum value of Ts (t), be denoted as Tsm;(2) according to following formula Calculate heat dissipation capacity RatioLoss:
3. test method according to claim 1, it is characterised in that: characteristic quantity used in assessment sample to be tested heating conduction calculates It is as follows: calculate sample to be tested in step 3 from the shortest time for entering Env2 and reaching to surface temperature Tch, as characteristic quantity, Temperature Tch are as follows:
Tch=T1+ (T0-T1) C
Wherein parameter C is preset preset parameter, and value is between 0~1.
4. test method according to claim 1, it is characterised in that: using material known to thermal physical property parameter, make geometry Size and the consistent reference sample of sample to be tested;It is carried out using reference sample and the identical test of sample to be tested, then root The skin temperature profile that step 3 records when testing according to reference sample, the sample surfaces coefficient of heat transfer hs1 in Inversion Calculation step 2 It is applied to the thermal coefficient Inversion Calculation that sample to be tested is tested as calibration result, then by hs1.
5. test method according to claim 1, it is characterised in that: when executing step 3, environment Env2 is free convection ring Border, sample to be tested surface equivalent heat transfer coefficient hs2 is demarcated with the following method and is applied to the thermally conductive system of sample to be tested in the environment Number Inversion Calculation: two reference samples of heating conduction good material production and sample to be tested adjoining dimensions are used;By one Electric heating piece is clipped among two reference samples, and the environment Env2 of step 3 is placed on posture when being similar to sample to be tested test In, keep constant power continuous heating, power setting according to be surface temperature when reference sample being made to reach stable state with to test sample Surface temperature is suitable in product testing procedure 3;After reference sample reaches thermal balance, record heating power Q, reference sample surface are flat Equal temperature Tr, environment temperature Ta and sample total surface area S, the calibration result of surface film thermal conductance hs2 are as follows: hs2=Q/ ((Tr-Ta)*S)。
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CN115235934A (en) * 2022-07-18 2022-10-25 衡阳凯新特种材料科技有限公司 Method and equipment for detecting thermal shock resistance of silicon nitride ceramic material

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