CN113567865B - Gradient utilization ternary battery thermal runaway energy release estimation method - Google Patents
Gradient utilization ternary battery thermal runaway energy release estimation method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000003792 electrolyte Substances 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 18
- 210000004027 cell Anatomy 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 238000012937 correction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 230000020169 heat generation Effects 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 230000036647 reaction Effects 0.000 claims description 6
- 239000011257 shell material Substances 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 238000012806 monitoring device Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 15
- 238000005259 measurement Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 238000010998 test method Methods 0.000 abstract description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/367—Software therefor, e.g. for battery testing using modelling or look-up tables
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F30/00—Computer-aided design [CAD]
- G06F30/20—Design optimisation, verification or simulation
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- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2119/00—Details relating to the type or aim of the analysis or the optimisation
- G06F2119/08—Thermal analysis or thermal optimisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a gradient utilization ternary battery thermal runaway energy release estimation method. The conventional battery thermal runaway temperature test method has long test time, generally requires tens of hours to twenty hours, and has high test instrument cost and cannot be popularized and used. The invention mainly aims at batteries of ternary/graphite systems with higher gradient utilization potential in the future, and aims at self-heat generation initial temperature T of ternary batteries with different health states 0 Voltage drop temperature T d Trigger temperature T of thermal runaway c And a maximum temperature T of thermal runaway m The method can finish the measurement of the thermal runaway temperature of the ternary battery in a gradient manner within 1 hour, and greatly shortens the time and the cost of the measurement of the thermal runaway temperature of the ternary battery in a gradient manner. According to the invention, the energy released in the thermal runaway process of the ternary battery is calculated through the obtained temperature data.
Description
Technical Field
The invention belongs to the technical field of energy storage of electric automobiles, and particularly relates to a thermal runaway energy release estimation method of a ternary power battery before and during echelon utilization.
Background
At present, the lithium ion battery applied to the new energy automobile is mainly a power battery of a lithium iron phosphate system and a ternary material system, and the ternary power battery has higher energy density, so that the market share of the ternary power battery exceeds that of the lithium iron phosphate battery in 2018, and the ternary power battery becomes the power battery with the largest loading capacity. The ternary batteries are retired from the new energy automobile after long-term vehicle-mounted use, and a lot of retired batteries have higher residual energy, so that the ternary batteries have potential value of echelon utilization.
Compared with a new battery, the safety hidden trouble of the battery used in the echelon is larger in the use process, so that before the echelon is used, the safety performance of the battery needs to be evaluated to determine the proper use mode. The positive electrode material adopted by the ternary battery is alpha-NaFeO 2 The layered structure of the material has poor structural stability due to volume expansion and contraction in the charge and discharge process; meanwhile, oxygen can be released by the ternary material at high temperature, and the ternary material reacts with electrolyte in the battery, so that the thermal runaway trigger temperature of the ternary battery is lower, the probability of occurrence of a safety accident in the use process is higher than that of the lithium iron phosphate battery, and the probability of occurrence of the thermal runaway can be continuously increased along with the reduction of the health state of the battery in the use process. The ternary batteries in different health states are required to be subjected to thermal runaway temperature test before the gradient utilization, so that the critical temperature of the ternary batteries in thermal runaway is determined, and the energy is estimated and released through temperature data, so that the effects of early warning and judging the damage degree of the thermal runaway can be achieved in the gradient utilization process.
Conventional battery thermal runaway temperature testing methods mainly test the self-heat generation onset temperature T of a battery in an adiabatic acceleration calorimeter (ARC) 0 Voltage drop temperature T d Trigger temperature T of thermal runaway c And a maximum temperature T of thermal runaway m The data related to the isothermal runaway is long, the test time is generally from tens of hours to twenty hours, the cost of a test instrument is high, and the popularization and the use cannot be realized.
Therefore, for the ternary battery used in a cascade, a rapid thermal runaway energy release estimation method needs to be developed, so that the battery thermal runaway temperature test time can be greatly shortened, the cost of the ternary battery thermal runaway temperature test used in a cascade is reduced, the economy of the ternary power battery used in a cascade is improved, and the released energy is estimated through temperature data.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for estimating the thermal runaway energy release of a ternary battery in a gradient manner, which can complete test analysis of the thermal runaway temperature parameters of the ternary battery in a gradient manner within 1 hour so as to realize rapid test of the thermal runaway temperature of the ternary battery in different health states in the gradient manner, and the energy release value in the thermal runaway process is estimated by using the thermal runaway temperature data through establishing an energy estimation model.
Therefore, the invention adopts the following technical scheme: a gradient utilization ternary battery thermal runaway energy release estimation method is an overcharge thermal runaway energy release estimation method, and comprises the following steps:
1) Charging the battery in a healthy state to 100% SOC for standby at 0.3 ℃;
2) Sticking a thermocouple and a voltage line at a designated position, connecting a voltage monitoring device at the position of the positive electrode lug and the negative electrode lug, and wrapping a layer of heat insulation cotton on the surface of the battery;
3) Starting a data recorder and an overcharging device to continuously charge the battery at 0.5 ℃;
4) Observing the temperature change by a data recorder when the actual temperature T 'inside the battery' 2 And the theoretical temperature T caused by overcharge 2 Temperature difference DeltaT between 1 At 1 ℃/s or more, the actual temperature T 'inside the battery' 2 Trigger temperature T for battery thermal runaway c At this time, the overcharging device is closed;
5) After the thermal runaway is finished, the battery thermal runaway trigger temperature T is utilized c Calculating the self-heat-generation initial temperature T 0 Voltage drop temperature T d And a maximum temperature T of thermal runaway m ；
6) Substituting the temperature data into an energy release calculation model, and estimating the release energy of the thermal runaway;
the energy release calculation model is as follows:
Q＝η[f(C 1 )α(T 0 -T 1 )+f(C 2 )β(T c -T 0 )+f(C 3 )γ(T m -T c )]， (2)
wherein f (C) 1 )＝k 1 c s m s +k 2 c f m f ，k 1 +k 2 ＝1，
f(C 2 )＝k 3 c f m f +k 4 c g m g +k 5 c z m z +k 6 c d m d +k 7 c n m n ，k 3 +k 4 +k 5 +k 6 +k 7 ＝1，
f(C 3 )＝k 8 c f m f +k 9 c g m g +k 10 c z m z +k 11 c d m d +k 12 c n m n ，k 8 +k 9 +k 10 +k 11 +k 12 ＝1；
Wherein k is n N=1, 2,3 … 12, the extent factor of the cell reaction in each part; η is a correction coefficient, and is related to the health state and heat loss of the battery, and the value range is 0-1; c s Specific heat capacity, m, of SEI film s Is the quality of SEI film; c f Specific heat capacity of anode material, m f The mass of the anode material is that of the cathode material; c g For specific heat capacity of the diaphragm, m g Is the diaphragm mass; c z Specific heat capacity of positive electrode material, m z The mass of the anode material is as follows; c d Specific heat capacity of electrolyte, m d The electrolyte is of the mass; c n To the specific heat capacity of the binder, m n The mass of the adhesive is that of the adhesive; α, γ, β are the percent energy release at each stage, and α+γ+β=1; t (T) 1 At an initial temperature T c For triggering the temperature of the battery thermal runaway, T m For maximum temperature of thermal runaway, T 0 Is the initial temperature from the heat generation.
Further, since constant current charge is used in overcharging, heat Q 1 ＝UI t U represents the voltage at the time of overcharging, I t Representing the current at t, again because of Q 1 ＝mc(T 2 -T 1 ) M represents the mass of the electrode, c represents the heat capacity of the electrode, and the theoretical temperature T caused by overcharge at T is obtained by combining two formulas 2 The method comprises the steps of carrying out a first treatment on the surface of the Due to the self-heat release phenomenon during the thermal runaway of the battery, the actual temperature T 'of the battery at T is caused' 2 ≥T 2 Temperature T actually measured by cell surface thermocouple 3 Which is equal to T' 2 The relationship between them corresponds to the formula (1):
wherein A is a correction coefficient, the value range is 0-1, c 1 C is specific heat capacity of battery material 2 C for specific heat capacity of the shell material 3 The specific heat capacity of the electrolyte, i is the thickness of the battery, and v is the heat transfer speed; k represents a coefficient of heat loss related to the cell thickness l;
from T 3 Calculated T' 2 With the theoretical temperature T caused by overcharge 2 Temperature difference DeltaT between 1 T 'at 0 ℃/s or more' 2 Initial temperature T for self-heat generation of battery 0 ，ΔT 1 T 'at 1 ℃/s or more' 2 Trigger temperature T for battery thermal runaway c 。
The invention adopts another technical scheme that: a gradient utilization ternary battery thermal runaway energy release estimation method is an overheat thermal runaway energy release estimation method, and comprises the following steps:
1) The heating plate is tightly attached to one side of the battery in each health state;
2) Sticking a thermocouple and a voltage line at a designated position, and wrapping a layer of heat insulation cotton on the surface of the battery;
3) Starting a data recorder, and electrifying a heating plate to continuously heat the battery;
4) Observing the temperature change by a data recorder, when the actual temperature T 'of the back of the battery' 6 With the theoretical temperature T of the back surface of the battery caused by overheat 6 Temperature difference DeltaT between 2 At 1 ℃/s or more, the theoretical temperature T between the heating plate and the battery 5 Trigger temperature T for battery thermal runaway c At the moment, the heating plate is powered off, and heating is stopped;
5) After the thermal runaway is finished, the battery thermal runaway trigger temperature T is utilized c Calculating the self-heat-generation initial temperature T 0 Voltage drop temperature T d And a maximum temperature T of thermal runaway m ；
6) Substituting the temperature data into an energy release calculation model, and estimating the release energy of the thermal runaway;
the energy release calculation model is as follows:
Q＝η[f(C 1 )α(T 0 -T 1 )+f(C 2 )β(T c -T 0 )+f(C 3 )γ(T m -T c )] (2)
wherein f (C) 1 )＝k 1 c s m s +k 2 c f m f ，k 1 +k 2 ＝1，
f(C 2 )＝k 3 c f m f +k 4 c g m g +k 5 c z m z +k 6 c d m d +k 7 c n m n ，k 3 +k 4 +k 5 +k 6 +k 7 ＝1，
f(C 3 )＝k 8 c f m f +k 9 c g m g +k 10 c z m z +k 11 c d m d +k 12 c n m n ，k 8 +k 9 +k 10 +k 11 +k 12 ＝1，
Wherein k is n N=1, 2,3 … 12, the extent factor of the cell reaction in each part; η is a correction coefficient, and is related to the health state and heat loss of the battery, and the value range is 0-1; c s Specific heat capacity, m, of SEI film s Is the quality of SEI film; c f Specific heat capacity of anode material, m f The mass of the anode material is that of the cathode material; c g For specific heat capacity of the diaphragm, m g Is of diaphragm typeAn amount of; c z Specific heat capacity of positive electrode material, m z The mass of the anode material is as follows; c d Specific heat capacity of electrolyte, m d The electrolyte is of the mass; c n To the specific heat capacity of the binder, m n The mass of the adhesive is that of the adhesive; α, γ, β are the percent energy release at each stage, and α+γ+β=1; t (T) 1 At an initial temperature T c For triggering the temperature of the battery thermal runaway, T m For maximum temperature of thermal runaway, T 0 Is the initial temperature from the heat generation.
Further, heat Q generated by the heating plate 2 =pt, P represents heating plate power, t represents time, Q 2 ＝mc(T 5 -T 1 ) Calculating the theoretical temperature T between the heating plate and the battery at the time of the available T 5 ，T 1 At the initial temperature, the heat generated by the heating plate is transferred to the inside of the battery, and the theoretical temperature T of the back surface of the battery 6 Which is associated with T 5 The relationship between them corresponds to the formula (3):
wherein A is a correction coefficient, the value range is 0-1, c 1 C is specific heat capacity of battery material 2 C for specific heat capacity of the shell material 3 The specific heat capacity of the electrolyte, i is the thickness of the battery, and v is the heat transfer speed; k represents a coefficient of heat loss related to the cell thickness l;
the heat is released from the inside to the outside due to the self-heat release during the thermal runaway of the battery, so the actual temperature T 'of the back of the battery' 6 ≥T 6 The method comprises the steps of carrying out a first treatment on the surface of the Cell backside actual temperature T' 6 And the theoretical temperature T calculated by the formula (3) 6 Temperature difference DeltaT between 2 T at 0 ℃/s or more 5 Initial temperature T for self-heat generation of battery 0 ，ΔT 2 T at 1 ℃/s or more 5 Trigger temperature T for battery thermal runaway c . The temperature thus measured eliminates errors due to too fast a rate of temperature rise and heat loss when the heating plate heats up.
Further, the thermocouple is positioned between the battery and the heating plate.
Still further, the power of the heating plate is 400-600W.
The thermal runaway temperature of the battery is usually measured in an adiabatic acceleration calorimeter (ARC), and since the temperature change of the surface of the battery is monitored in a heating-waiting-searching mode, the time required for the measurement is long (tens of hours to twenty hours), so that a thermocouple can be fixed at a designated position on the surface of the battery in a specific overcharging or overheating mode, the other end of the thermocouple is connected with a data recorder, and the temperature change of the thermal runaway of the ternary battery caused by overcharging or overheating is monitored, and the temperature of the thermal runaway of the ternary battery can be represented by the temperature change rate of the surface of the battery.
The invention relates to a thermal runaway temperature test method for a ternary battery with cascade utilization, which mainly aims at the self-heat generation initial temperature T of ternary batteries with different health states for batteries with ternary/graphite systems with cascade utilization potential in the future 0 Voltage drop temperature T d Trigger temperature T of thermal runaway c And a maximum temperature T of thermal runaway m The method can finish the measurement of the thermal runaway temperature of the ternary battery in a gradient manner within 1 hour, and greatly shortens the time and the cost of the measurement of the thermal runaway temperature of the ternary battery in a gradient manner.
The invention has the following beneficial effects: the invention adopts simple equipment to measure the self-heat-generation initial temperature T of the thermal runaway of the ternary battery in gradient 0 Voltage drop temperature T d Trigger temperature T of thermal runaway c And a maximum temperature T of thermal runaway m The thermal runaway related data can finish the thermal runaway temperature measurement of the ternary battery in different health states in 1 hour, greatly shorten the thermal runaway temperature measurement time of the ternary battery in the gradient, improve the technical economy of the ternary battery in the gradient, and estimate the energy release value in the thermal runaway process by establishing an energy release calculation model and utilizing the thermal runaway temperature data, thereby achieving the purpose of estimating the damage degree of the thermal runaway.
The method has wide application prospect in the fields of electric automobiles, electrochemical energy storage, gradient utilization of power batteries and the like.
The method adopted by the invention is easy to realize in engineering implementation, and has higher application value.
Drawings
FIG. 1 is a flow chart of a method for testing overcharge thermal runaway temperature of a ternary battery in a cascade;
FIG. 2 is a flow chart of a method for testing the overheat thermal runaway temperature of a ternary battery according to the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings.
Example 1
A testing method for overcharge thermal runaway temperature of a ternary battery in a gradient manner is shown in fig. 1, and comprises the following steps:
1) Charging the battery in a healthy state to 100% SOC for standby at 0.3 ℃;
2) Sticking a thermocouple and a voltage line at a designated position, connecting a voltage monitoring device at the position of the positive electrode lug and the negative electrode lug, and wrapping a layer of heat insulation cotton on the surface of the battery;
3) Starting a data recorder and an overcharging device to continuously charge the battery at 0.5 ℃;
4) Observing the temperature change by a data recorder when the actual temperature T 'inside the battery' 2 And the theoretical temperature T caused by overcharge 2 Temperature difference DeltaT between 1 At 1 ℃/s or more, the actual temperature T 'inside the battery' 2 Trigger temperature T for battery thermal runaway c At this time, the overcharging device is closed;
5) After the thermal runaway is finished, the battery thermal runaway trigger temperature T is utilized c Calculating the self-heat-generation initial temperature T 0 Voltage drop temperature T d And a maximum temperature T of thermal runaway m ；
6) Substituting the temperature data into an energy release calculation model, and estimating the release energy of the thermal runaway;
the energy release calculation model is as follows:
Q＝η[f(C 1 )α(T 0 -T 1 )+f(C 2 )β(T c -T 0 )+f(C 3 )γ(T m -T c )]， (2)
wherein f (C) 1 )＝k 1 c s m s +k 2 c f m f ，k 1 +k 2 ＝1，
f(C 2 )＝k 3 c f m f +k 4 c g m g +k 5 c z m z +k 6 c d m d +k 7 c n m n ，k 3 +k 4 +k 5 +k 6 +k 7 ＝1，
f(C 3 )＝k 8 c f m f +k 9 c g m g +k 10 c z m z +k 11 c d m d +k 12 c n m n ，k 8 +k 9 +k 10 +k 11 +k 12 ＝1；
Wherein k is n N=1, 2,3 … 12, the extent factor of the cell reaction in each part; η is a correction coefficient, and is related to the health state and heat loss of the battery, and the value range is 0-1; c s Specific heat capacity, m, of SEI film s Is the quality of SEI film; c f Specific heat capacity of anode material, m f The mass of the anode material is that of the cathode material; c g For specific heat capacity of the diaphragm, m g Is the diaphragm mass; c z Specific heat capacity of positive electrode material, m z The mass of the anode material is as follows; c d Specific heat capacity of electrolyte, m d The electrolyte is of the mass; c n To the specific heat capacity of the binder, m n The mass of the adhesive is that of the adhesive; α, γ, β are the percent energy release at each stage, and α+γ+β=1; t (T) 1 At an initial temperature T c For triggering the temperature of the battery thermal runaway, T m For maximum temperature of thermal runaway, T 0 Is the initial temperature from the heat generation.
In step 4), since constant current charge is used in overcharging, heat Q 1 ＝UI t U represents the voltage at the time of overcharging, I t Representing the current at t, again because of Q 1 ＝mc(T 2 -T 1 )，mRepresenting the mass of the electrode, c representing the heat capacity of the electrode, and solving the theoretical temperature T caused by overcharge at T through the combination of two formulas 2 The method comprises the steps of carrying out a first treatment on the surface of the Due to the self-heat release phenomenon during the thermal runaway of the battery, the actual temperature T 'of the battery at T is caused' 2 ≥T 2 Temperature T actually measured by cell surface thermocouple 3 Which is equal to T' 2 The relationship between them corresponds to the formula (1):
wherein A is a correction coefficient, the value range is 0-1, c 1 C is specific heat capacity of battery material 2 C for specific heat capacity of the shell material 3 The specific heat capacity of the electrolyte, i is the thickness of the battery, and v is the heat transfer speed; k represents a coefficient of heat loss related to the cell thickness l;
from T 3 Calculated T' 2 With the theoretical temperature T caused by overcharge 2 Temperature difference DeltaT between 1 T 'at 0 ℃/s or more' 2 Initial temperature T for self-heat generation of battery 0 ，ΔT 1 T 'at 1 ℃/s or more' 2 Trigger temperature T for battery thermal runaway c 。
Example 2
A testing method for overheat thermal runaway temperature of a ternary battery in a gradient manner is shown in fig. 2, and comprises the following steps:
1) The heating plate is tightly attached to one side of the battery in each health state;
2) Sticking a thermocouple and a voltage line at a designated position, and wrapping a layer of heat insulation cotton on the surface of the battery;
3) Starting a data recorder, and electrifying a heating plate to continuously heat a battery;
4) Observing the temperature change by a data recorder, when the actual temperature T 'of the back of the battery' 6 With the theoretical temperature T of the back surface of the battery caused by overheat 6 Temperature difference DeltaT between 2 At 1 ℃/s or more, the theoretical temperature T between the heating plate and the battery 5 Trigger temperature T for battery thermal runaway c At the moment, the heating plate is powered off, and heating is stopped;
5) After the thermal runaway is finished, the battery thermal runaway trigger temperature T is utilized c Calculating the self-heat-generation initial temperature T 0 Voltage drop temperature T d And a maximum temperature T of thermal runaway m ；
6) Substituting the temperature data into an energy release calculation model, and estimating the release energy of the thermal runaway;
the energy release calculation model is as follows:
Q＝η[f(C 1 )α(T 0 -T 1 )+f(C 2 )β(T c -T 0 )+f(C 3 )γ(T m -T c )] (2)
wherein f (C) 1 )＝k 1 c s m s +k 2 c f m f ，k 1 +k 2 ＝1，
f(C 2 )＝k 3 c f m f +k 4 c g m g +k 5 c z m z +k 6 c d m d +k 7 c n m n ，k 3 +k 4 +k 5 +k 6 +k 7 ＝1，
f(C 3 )＝k 8 c f m f +k 9 c g m g +k 10 c z m z +k 11 c d m d +k 12 c n m n ，k 8 +k 9 +k 10 +k 11 +k 12 ＝1，
Wherein k is n N=1, 2,3 … 12, the extent factor of the cell reaction in each part; η is a correction coefficient, and is related to the health state and heat loss of the battery, and the value range is 0-1; c s Specific heat capacity, m, of SEI film s Is the quality of SEI film; c f Specific heat capacity of anode material, m f The mass of the anode material is that of the cathode material; c g For specific heat capacity of the diaphragm, m g Is the diaphragm mass; c z Specific heat capacity of positive electrode material, m z The mass of the anode material is as follows; c d Specific heat capacity of electrolyte, m d The electrolyte is of the mass; c n To the specific heat capacity of the binder, m n The mass of the adhesive is that of the adhesive; α, γ, β are the percent energy release at each stage, and α+γ+β=1; t (T) 1 At an initial temperature T c For triggering the temperature of the battery thermal runaway, T m For maximum temperature of thermal runaway, T 0 Is the initial temperature from the heat generation.
Heat Q generated by heating plate 2 =pt, P represents heating plate power, t represents time, Q 2 ＝mc(T 5 -T 1 ) Calculating the theoretical temperature T between the heating plate and the battery at the time of the available T 5 ，T 1 At the initial temperature, the heat generated by the heating plate is transferred to the inside of the battery, and the theoretical temperature T of the back surface of the battery 6 Which is associated with T 5 The relationship between them corresponds to the formula (3):
wherein A is a correction coefficient, the value range is 0-1, c 1 C is specific heat capacity of battery material 2 C for specific heat capacity of the shell material 3 The specific heat capacity of the electrolyte, i is the thickness of the battery, and v is the heat transfer speed; k represents a coefficient of heat loss related to the cell thickness l;
the heat is released from the inside to the outside due to the self-heat release during the thermal runaway of the battery, so the actual temperature T 'of the back of the battery' 6 ≥T 6 The method comprises the steps of carrying out a first treatment on the surface of the Cell backside actual temperature T' 6 And the theoretical temperature T calculated by the formula (3) 6 Temperature difference DeltaT between 2 T at 0 ℃/s or more 5 Initial temperature T for self-heat generation of battery 0 ，ΔT 2 T at 1 ℃/s or more 5 Trigger temperature T for battery thermal runaway c 。
The thermocouple is positioned between the battery and the heating plate, and the power of the heating plate is 400-600W.
The specific embodiments described herein are intended to be illustrative of only some, but not all, of the embodiments of the invention and other embodiments are within the scope of the invention as would be apparent to one of ordinary skill in the art without undue burden.
Claims (6)
1. A gradient utilization ternary battery thermal runaway energy release estimation method is characterized by comprising the following steps of:
1) Charging the battery in a healthy state to 100% SOC for standby at 0.3 ℃;
2) Sticking a thermocouple and a voltage line at a designated position, connecting a voltage monitoring device at the position of the positive electrode lug and the negative electrode lug, and wrapping a layer of heat insulation cotton on the surface of the battery;
3) Starting a data recorder and an overcharging device to continuously charge the battery at 0.5 ℃;
4) Observing the temperature change by a data recorder when the actual temperature T 'inside the battery' 2 And the theoretical temperature T caused by overcharge 2 Temperature difference DeltaT between 1 At 1 ℃/s or more, the actual temperature T 'inside the battery' 2 Trigger temperature T for battery thermal runaway c At this time, the overcharging device is closed;
5) After the thermal runaway is finished, the battery thermal runaway trigger temperature T is utilized c Calculating the self-heat-generation initial temperature T 0 Voltage drop temperature T d And a maximum temperature T of thermal runaway m ；
6) Substituting the temperature data into an energy release calculation model, and estimating the release energy of the thermal runaway;
the energy release calculation model is as follows:
Q＝η[f(C 1 )α(T 0 -T 1 )+f(C 2 )β(T c -T 0 )+f(C 3 )γ(T m -Tc)]， (2)
wherein f (C) 1 )＝k 1 c s m s +k 2 c f m f ，k 1 +k 2 ＝1，
f(C 2 )＝k 3 c f m f +k 4 c g m g +k 5 c z m z +k 6 c d m d +k 7 c n m n ，k 3 +k 4 +k 5 +k 6 +k 7 ＝1，
f(C 3 )＝k 8 c f m f +k 9 c g m g +k 10 c z m z +k 11 c d m d +k 12 c n m n ，k 8 +k 9 +k 10 +k 11 +k 12 ＝1；
Wherein k is n N=1, 2,3 … 12, the extent factor of the cell reaction in each part; η is a correction coefficient, and is related to the health state and heat loss of the battery, and the value range is 0-1; c s Specific heat capacity, m, of SEI film s Is the quality of SEI film; c f Specific heat capacity of anode material, m f The mass of the anode material is that of the cathode material; c g For specific heat capacity of the diaphragm, m g Is the diaphragm mass; c z Specific heat capacity of positive electrode material, m z The mass of the anode material is as follows; c d Specific heat capacity of electrolyte, m d The electrolyte is of the mass; c n To the specific heat capacity of the binder, m n The mass of the adhesive is that of the adhesive; α, γ, β are the percent energy release at each stage, and α+γ+β=1; t (T) 1 At an initial temperature T c For triggering the temperature of the battery thermal runaway, T m For maximum temperature of thermal runaway, T 0 Is the initial temperature from the heat generation.
2. A gradient-utilized ternary battery thermal runaway energy release estimation method according to claim 1, wherein, in step 4),
since constant current charge is used during overcharging, heat Q 1 ＝UI t U represents the voltage at the time of overcharging, I t Representing the current at t, again because of Q 1 ＝mc(T 2 -T 1 ) M represents the mass of the electrode, c represents the heat capacity of the electrode, and the theoretical temperature T caused by overcharge at T is obtained by combining two formulas 2 The method comprises the steps of carrying out a first treatment on the surface of the Due to the self-heat release phenomenon during the thermal runaway of the battery, the actual temperature T 'of the battery at T is caused' 2 ≥T 2 Temperature T actually measured by cell surface thermocouple 3 Which is equal to T' 2 The relationship between them corresponds to the formula (1):
wherein A is a correction coefficient, the value range is 0-1, c 1 C is specific heat capacity of battery material 2 C for specific heat capacity of the shell material 3 The specific heat capacity of the electrolyte, i is the thickness of the battery, and v is the heat transfer speed; k represents a coefficient of heat loss related to the cell thickness l;
from T 3 Calculated T' 2 With the theoretical temperature T caused by overcharge 2 Temperature difference DeltaT between 1 T 'at 0 ℃/s or more' 2 Initial temperature T for self-heat generation of battery 0 ，ΔT 1 T 'at 1 ℃/s or more' 2 Trigger temperature T for battery thermal runaway c 。
3. A gradient utilization ternary battery thermal runaway energy release estimation method is characterized by comprising the following steps of:
1) The heating plate is tightly attached to one side of the battery in each health state;
2) Sticking a thermocouple and a voltage line at a designated position, and wrapping a layer of heat insulation cotton on the surface of the battery;
3) Starting a data recorder, and electrifying a heating plate to continuously heat the battery;
4) Observing the temperature change by a data recorder, when the actual temperature T 'of the back of the battery' 6 With the theoretical temperature T of the back surface of the battery caused by overheat 6 Temperature difference DeltaT between 2 At 1 ℃/s or more, the theoretical temperature T between the heating plate and the battery 5 Trigger temperature T for battery thermal runaway c At the moment, the heating plate is powered off, and heating is stopped;
5) After the thermal runaway is finished, the battery thermal runaway trigger temperature T is utilized c Calculating the self-heat-generation initial temperature T 0 Voltage drop temperature T d And a maximum temperature T of thermal runaway m ；
6) Substituting the temperature data into an energy release calculation model, and estimating the release energy of the thermal runaway;
the energy release calculation model is as follows:
Q＝η[f(C 1 )α(T 0 -T 1 )+f(C 2 )β(T c -T 0 )+f(C 3 )γ(T m -T c )] (2)
wherein f (C) 1 )＝k 1 c s m s +k 2 c f m f ，k 1 +k 2 ＝1，
f(C 2 )＝k 3 c f m f +k 4 c g m g +k 5 c z m z +k 6 c d m d +k 7 c n m n ，k 3 +k 4 +k 5 +k 6 +k 7 ＝1，
f(C 3 )＝k 8 c f m f +k 9 c g m g +k 10 c z m z +k 11 c d m d +k 12 c n m n ，k 8 +k 9 +k 10 +k 11 +k 12 ＝1，
Wherein k is n N=1, 2,3 … 12, the extent factor of the cell reaction in each part; η is a correction coefficient, and is related to the health state and heat loss of the battery, and the value range is 0-1; c s Specific heat capacity, m, of SEI film s Is the quality of SEI film; c f Specific heat capacity of anode material, m f The mass of the anode material is that of the cathode material; c g For specific heat capacity of the diaphragm, m g Is the diaphragm mass; c z Specific heat capacity of positive electrode material, m z The mass of the anode material is as follows; c d Specific heat capacity of electrolyte, m d The electrolyte is of the mass; c n To the specific heat capacity of the binder, m n The mass of the adhesive is that of the adhesive; α, γ, β are the percent energy release at each stage, and α+γ+β=1; t (T) 1 At an initial temperature T c For triggering the temperature of the battery thermal runaway, T m For maximum temperature of thermal runaway, T 0 Is the initial temperature from the heat generation.
4. A gradient-utilized ternary battery thermal runaway energy release estimation method according to claim 3, wherein,
heat Q generated by heating plate 2 =pt, P represents heating plate power, t represents time, Q 2 ＝mc(T 5 -T 1 ) Calculating the theoretical temperature T between the heating plate and the battery at the time of the available T 5 ，T 1 At the initial temperature, the heat generated by the heating plate is transferred to the inside of the battery, and the theoretical temperature T of the back surface of the battery 6 Which is associated with T 5 The relationship between them corresponds to the formula (3):
wherein A is a correction coefficient, the value range is 0-1, c 1 C is specific heat capacity of battery material 2 C for specific heat capacity of the shell material 3 The specific heat capacity of the electrolyte, i is the thickness of the battery, and v is the heat transfer speed; k represents a coefficient of heat loss related to the cell thickness l;
the heat is released from the inside to the outside due to the self-heat release during the thermal runaway of the battery, so the actual temperature T 'of the back of the battery' 6 ≥T b The method comprises the steps of carrying out a first treatment on the surface of the Cell backside actual temperature T' 6 And the theoretical temperature T calculated by the formula (3) 6 Temperature difference DeltaT between 2 T at 0 ℃/s or more 5 Initial temperature T for self-heat generation of battery 0 ，ΔT 2 T at 1 ℃/s or more 5 Trigger temperature T for battery thermal runaway c 。
5. A cascade utilization ternary battery thermal runaway energy release estimation method according to claim 3, wherein said thermocouple is located between the battery and the heating plate.
6. A cascade utilization ternary battery thermal runaway energy release estimation method according to claim 3, characterized in that the power of the heating plate is 400-600W.
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