CN117577978B - Method for determining battery thermal stability condition and battery storage method - Google Patents

Method for determining battery thermal stability condition and battery storage method Download PDF

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CN117577978B
CN117577978B CN202410076798.1A CN202410076798A CN117577978B CN 117577978 B CN117577978 B CN 117577978B CN 202410076798 A CN202410076798 A CN 202410076798A CN 117577978 B CN117577978 B CN 117577978B
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battery
energy
thermal stability
voltage
determining
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CN117577978A (en
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高艺珂
邱越
朱高龙
赵常
刘青青
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Sichuan New Energy Vehicle Innovation Center Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/385Arrangements for measuring battery or accumulator variables
    • G01R31/387Determining ampere-hour charge capacity or SoC
    • G01R31/388Determining ampere-hour charge capacity or SoC involving voltage measurements
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/374Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] with means for correcting the measurement for temperature or ageing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4285Testing apparatus
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of battery storage, and particularly relates to a method for determining a battery thermal stability condition and a battery storage method. The method comprises the following steps: 1) Obtaining rated energy E and a discharge curve of a battery to be characterized, wherein the discharge curve is a discharge curve of energy and voltage; 2) Obtaining the thermal runaway trigger temperature T of the battery to be characterized 2 The method comprises the steps of carrying out a first treatment on the surface of the 3) Obtaining the mass of each material of the battery to be characterized in the step 1) and the specific heat capacity of each material, and then calculating the temperature rise of the battery to be characterized from the storage temperature to T 2 Total energy E required for temperature T The method comprises the steps of carrying out a first treatment on the surface of the 4) According to the rated energy E and the total energy E T And the discharge curve is calculated to obtain the thermal stability voltage V range of the battery to be characterized, or according to the rated energy E and the total energy E T Calculating to obtain the heat stable residual energy SOE of the battery to be characterized S Range. The invention can obtain the battery thermal stability condition.

Description

Method for determining battery thermal stability condition and battery storage method
Technical Field
The invention belongs to the technical field of battery storage, and particularly relates to a method for determining a battery thermal stability condition and a battery storage method.
Background
At present, the lithium battery or the new energy automobile has spontaneous combustion in the storage process, and the lithium battery or the new energy automobile is not only the new energy automobile, but also has thermal runaway in the storage process before the battery leaves the factory. And the spontaneous combustion in the storage process is mostly caused by micro-short circuit inside the battery cell. After micro-short circuit is generated in the battery core, self-discharge can be started and the temperature is gradually increased, so that the diaphragm is contracted, large-area short circuit is generated, and finally, the battery core burns and fires after the temperature is too high. Therefore, it is necessary to develop a new technology to avoid the risk of spontaneous combustion caused by micro-short circuit of the battery cell and to improve the safety of the battery cell and the new energy automobile during storage.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for determining the thermal stability condition of a battery and a battery storage method. According to the invention, the thermal stability voltage stored in the battery can be determined, the spontaneous combustion risk caused by micro short circuit of the battery is avoided, and the safety of the battery and the new energy automobile during storage is greatly improved.
The technical scheme provided by the invention is as follows:
a method for determining a battery thermal stability condition, comprising the steps of:
1) Obtaining rated energy E and a discharge curve of a battery to be characterized, wherein the discharge curve is a discharge curve of energy and voltage;
2) Obtaining the thermal runaway trigger temperature T of the battery to be characterized 2
3) Obtaining the mass of each material of the battery to be characterized in the step 1) and the specific heat capacity of each material, and then calculating the temperature rise of the battery to be characterized from the storage temperature to T 2 Total energy E required for temperature T
4) According to the rated energy E and the total energy E T And the discharge curve is calculated to obtain the thermal stability voltage V range of the battery to be characterized, or according to the rated energy E and the total energy E T Calculating to obtain the heat stable residual energy SOE of the battery to be characterized S Range.
Based on the technical scheme, the battery thermal stability voltage V or the battery thermal stability residual energy SOE can be obtained S . Will beThe voltage of the battery is regulated to be less than V or the electric quantity of the battery is regulated to SOE S And the spontaneous combustion risk caused by micro short circuit of the battery can be avoided, the safety of the battery and the new energy automobile during storage is greatly improved, and safe storage is realized.
Specifically, in step 4), the method for calculating the battery thermal stability voltage V includes the steps of:
4a) Calculating the rated energy E and the total energy E T Is the difference E of (2) S
4b) Determining energy as E according to the discharge curve obtained in the step 1) S The corresponding critical safety voltage V on the discharge curve S
4c) Obtaining the battery to be characterized with the heat stable voltage V range of V less than or equal to V S
The principle of the technical scheme is as follows:
the battery is subjected to discharge measurement through the charge and discharge motor, so that rated energy E can be obtained, and an energy-voltage curve of the battery can be obtained;
t of the cell can be obtained by ARC test 2 Temperature (trigger thermal runaway temperature, which occurs when the battery reaches this temperature);
the temperature of the battery rises during the storage process, and the internal short-circuit discharge of the battery generates gradual temperature rise except the influence of the surrounding environment, so that the temperature of the battery needs to be calculated to rise to T 2 The energy required for the temperature is E T
Controlling the remaining energy of the battery to be less than E T It is ensured that the battery temperature does not reach T even if the internal circuit is broken 2 No thermal runaway occurs;
since the basis is an energy-voltage curve query, it is necessary to calculate E-E T Energy value of (E) S Then according to E S Inquiring the corresponding voltage value on the energy-voltage curve to obtain the critical safety voltage V S Thus controlling the battery thermal stability voltage V < V S And (3) obtaining the product.
Specifically, in step 4), the battery is calculated to be thermally stableResidual energy SOE S The method comprises the following steps:
4A) Calculating the total energy E T Ratio E to the nominal energy E w
4B) Obtaining the heat stable residual energy SOE of the battery to be characterized S SOE in the range of 0% to less than or equal to S <E w %。
Based on the technical scheme, the residual electric quantity value is convenient to serve as a standard, and the storage condition of the battery is set.
Specifically, in step 1), the battery to be characterized is a ternary lithium battery, a lithium iron phosphate battery, a lithium cobalt oxide battery or a lithium titanate battery, and may also be a sodium ion battery.
Based on the technical scheme, the method for determining the battery thermal stability condition is suitable for batteries of various systems.
Specifically, in step 2), the battery to be characterized tested in step 1) is subjected to a battery adiabatic acceleration calorimeter test (ARC test) to obtain a thermal runaway trigger temperature T of the battery to be characterized 2
Specifically, in step 1), the rated energy of the battery to be characterized and the discharge curve of the battery to be characterized are measured according to the method specified in GB/31486.
Specifically, in step 3), all materials of the battery to be characterized include, but are not limited to: positive electrode material, negative electrode material, positive electrode foil, negative electrode foil, diaphragm, electrolyte, conductive agent, adhesive and aluminum plastic film.
Specifically, in the step 3),
the total energy E is calculated according to the following formula T
Wherein m is x C for each material mass x And the specific heat capacity corresponding to each material is T, the storage temperature is 0-50 ℃, and n is the number of the types of materials contained in the battery to be characterized.
Preferably, the storage temperature T is 25 ℃, and the common storage standard can be met.
The invention also provides a battery storage method, which comprises the following steps:
1) The battery thermal stability voltage V is obtained by adopting the method for determining the battery thermal stability condition, or the residual energy SOE of the battery thermal stability is obtained S
2) Regulating the battery to a voltage less than or equal to V or to an electric quantity less than or equal to SOE S And then stored.
Further, in step 2), the stored temperature is less than or equal to the stored temperature in the battery thermally stable voltage determination method.
Based on the above technical scheme, the method for determining the thermal stability condition of the battery provided by the invention adopts the storage temperature for calculation, so that the actual storage temperature of the battery can be set according to the temperature.
The beneficial effects of the invention are as follows:
the invention can determine the battery thermal stability voltage V or the residual energy SOE of the battery thermal stability, which can cause the thermal runaway of the battery S The voltage of the battery is regulated to be less than V or the electric quantity of the battery is regulated to SOE S In the following, the risk of thermal runaway during storage of the battery can be avoided.
Drawings
FIG. 1 is a graph of the discharge obtained in step 1) in example 1 of the present invention.
FIG. 2 is a discharge graph of the process used in step 5) of example 1 of the present invention.
FIG. 3 is a graph of the discharge obtained in step 1) in example 2 of the present invention.
FIG. 4 is a discharge graph of the process used in step 5) of example 2 of the present invention.
Fig. 5 is a flowchart of a method of determining battery thermal stability conditions provided by the present invention.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Example 1
Ternary lithium battery thermal stability voltage determination
1) The ternary lithium battery is tested according to the method specified in GB/31486, the rated energy E=51Wh (183600J) of the battery is tested, and the discharge curve is shown in figure 1;
2) ARC test is carried out on the battery tested in the step 1) to obtain a battery T 2 Temperature = 190 ℃;
3) The mass and specific heat capacity of each material in the ternary lithium battery are obtained as shown in table 1:
TABLE 1
Positive electrode Weight of (E) (g) Specific heat of positive electrode Capacity (J- kg.K) Aluminum foil weight Quantity (g) Specific heat capacity of aluminum foil (J/kg.K) Negative electrode conduction Weight of agent (g) Negative electrode conductive agent ratio Heat capacity (J/kg.K) Negative electrode bonding Weight of agent (g) Binder ratio of negative electrode Heat capacity (J/kg.K)
68.66 200 5.5 220 0.313 500 0.928 1800
Diaphragm Weight of (E) (g) Specific heat of diaphragm Capacity (J- kg.K) Electrolyte solution Weight (g) Specific heat of electrolyte Container (J/kg.K) Positive electrode conduction Weight of agent (g) Positive electrode conductive agent ratio Heat capacity (J/kg.K) Positive electrode bonding Weight of agent (g) Binder ratio of positive electrode Heat capacity (J/kg.K)
5.06 1900 24 1000 1.08 500 1.423 1000
Negative electrode Weight of (E) (g) Specific heat of negative electrode Capacity (J- kg.K) Copper foil weight Quantity (g) Specific heat capacity of copper foil (J/kg.K) Weight of aluminum plastic film Quantity (g) Specific heat capacity of aluminum plastic film (J/kg.K)
27.79 710 9.972 390 3.08 1000
4) According to the mass and specific heat capacity of each material in the table of the step 3), the temperature of the battery is calculated to rise from room temperature to T at 25 DEG C 2 Total energy E of temperature T 13042J;
5) According to E T And E, calculate E S =E-E T =170557J=47.37Wh,E S Voltage V corresponding to the discharge curve S Is 3V as shown in fig. 2. Therefore, it was confirmed that when the battery storage voltage was lower than 3V, the battery was a safe and thermally stable voltage, and the energy discharged by the internal micro-short circuit of the battery could not raise the battery temperature to T 2 The safety of the battery in the storage process is ensured. At the same time, the safety SOE of the battery can be determined S The range is 0% -7.1%.
Example 2:
lithium iron phosphate battery thermal stability voltage determination
1) The lithium iron phosphate battery was tested for the rated battery energy e=31wh (111600J) according to the method specified in GB/31486, and the discharge curve is shown in fig. 3;
2) ARC test is carried out on the battery tested in the step 1) to obtain a battery T 2 Temperature = 200 ℃;
3) The mass and specific heat capacity of each material in the lithium iron phosphate battery are obtained, and are shown in table 2;
TABLE 2
Positive electrode Weight of (E) (g) Specific heat of positive electrode Capacity (J- kg.K) Aluminum foil weight Quantity (g) Specific heat capacity of aluminum foil (J/kg.K) Negative electrode conduction Weight of agent (g) Negative electrode conductive agent ratio Heat capacity (J/kg.K) Negative electrode bonding Weight of agent (g) Binder ratio of negative electrode Heat capacity (J/kg.K)
62.42 13988 1 200 5.5 220 0.19 500 0.56 1800
Diaphragm Weight of (E) (g) Specific heat of diaphragm Capacity (J- kg.K) Electrolyte solution Weight (g) Specific heat of electrolyte Container (J/kg.K) Positive electrode conduction Weight of agent (g) Positive electrode conductive agent ratio Heat capacity (J/kg.K) Positive electrode bonding Weight of agent (g) Binder ratio of positive electrode Heat capacity (J/kg.K)
5.06 1900 23 1000 0.98 500 1.294 1000
Negative electrode Weight of (E) (g) Specific heat of negative electrode Capacity (J- kg.K) Copper foil weight Quantity (g) Specific heat capacity of copper foil (J/kg.K) Weight of aluminum plastic film Quantity (g) Specific heat capacity of aluminum plastic film (J/kg.K)
16.75 97546 710 9.972 390 3.08 1000
4) According to the mass and specific heat capacity of each material in the table of the step 3), the temperature of the battery is calculated to rise from room temperature to T at 25 DEG C 2 Total energy E of temperature T 48833J;
5) According to E T And E, calculate E S =E-E T =62766J=17.435Wh,E S Voltage V corresponding to the discharge curve S Is 3.36V as shown in fig. 4. Therefore, when the storage voltage of the battery is lower than 3.36V, the battery is a safe thermal stable voltage, and the energy released by the internal micro-short circuit of the battery can not raise the temperature of the battery to T 2 The safety of the battery in the storage process is ensured. At the same time can determine the safety SOE of the battery S The range is 0% -43.7%.
Example 1 and example 2 were performed in the procedure shown in fig. 5 to determine the thermal stability conditions of the lithium battery.
Comparative examples 1 and 2 were stored according to a conventional method.
Comparative example 1:
when the battery of example 1 is stored at half-electricity, the battery safety voltage range is exceeded, and there is a risk of ignition of the battery due to short-circuiting during storage of the battery.
Comparative example 2
When the battery of example 2 is stored at half-electricity, the battery safety voltage range is exceeded, and there is a risk of ignition of the battery due to short-circuiting during storage of the battery.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (8)

1. A method for determining a thermal stability condition of a battery, comprising the steps of:
1) Obtaining rated energy E and a discharge curve of a battery to be characterized, wherein the discharge curve is a discharge curve of energy and voltage;
2) Obtaining the thermal runaway trigger temperature T of the battery to be characterized 2
3) Obtaining the mass of each material of the battery to be characterized in the step 1) and the specific heat capacity of each material, and then calculating the temperature rise of the battery to be characterized from the storage temperature to T 2 Total energy E required for temperature T
4) According to the rated energy E and the total energy E T And the discharge curve is calculated to obtain the thermal stability voltage V range of the battery to be characterized, or according to the rated energy E and the total energy E T Calculating to obtain the heat stable residual energy SOE of the battery to be characterized S A range;
in step 4), the method for calculating the battery thermal stability voltage V comprises the following steps:
4a) Calculating to obtain the rated valueEnergy E and the total energy E T Is the difference E of (2) S
4b) Determining energy as E according to the discharge curve obtained in the step 1) S The corresponding critical safety voltage V on the discharge curve S
4c) Obtaining the battery to be characterized with the heat stable voltage V range of V less than or equal to V S
In step 4), the residual energy SOE of the battery heat stability is calculated S The method comprises the following steps:
4A) Calculating the total energy E T Ratio E to the nominal energy E w
4B) Obtaining the heat stable residual energy SOE of the battery to be characterized S SOE in the range of 0% to less than or equal to S <E w %。
2. The method for determining the thermal stability condition of a battery according to claim 1, wherein: in the step 1), the battery to be characterized is a ternary lithium battery, a lithium iron phosphate battery, a lithium cobalt oxide battery or a lithium titanate battery.
3. The method for determining the thermal stability condition of a battery according to claim 1, wherein: in the step 2), the battery to be characterized, which is tested in the step 1), is subjected to a battery adiabatic acceleration calorimeter test to obtain the thermal runaway trigger temperature T of the battery to be characterized 2
4. The method for determining the thermal stability condition of a battery according to claim 1, wherein: in step 3), the materials of the battery to be characterized include, but are not limited to: positive electrode material, negative electrode material, positive electrode foil, negative electrode foil, diaphragm, electrolyte, conductive agent, adhesive and aluminum plastic film.
5. The method for determining the thermal stability condition of a battery according to claim 1, wherein: in step 3), the total energy E is calculated according to the following formula T:
Wherein m is x C for each material mass x And the specific heat capacity corresponding to each material is T, the storage temperature is 0-50 ℃, and n is the number of the types of materials contained in the battery to be characterized.
6. The method for determining the thermal stability condition of a battery according to claim 5, wherein: the storage temperature T is 25 ℃.
7. A battery storage method, comprising the steps of:
1) Obtaining a battery thermal stability voltage V or obtaining a battery thermal stability residual energy SOE by adopting the method for determining the battery thermal stability conditions according to any one of claims 1 to 6 S
2) Regulating the battery to a voltage less than or equal to V or to an electric quantity less than or equal to SOE S And then stored.
8. The battery storage method according to claim 7, wherein: in step 2), the storage temperature is less than or equal to the storage temperature.
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