CN115356641A - Lithium ion battery overcharge detection method based on ultrasonic characteristics - Google Patents
Lithium ion battery overcharge detection method based on ultrasonic characteristics Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 127
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- 230000008859 change Effects 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
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- 238000007600 charging Methods 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 20
- 230000005284 excitation Effects 0.000 claims description 9
- 238000010277 constant-current charging Methods 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 230000002427 irreversible effect Effects 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000009831 deintercalation Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 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]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/04—Analysing solids
- G01N29/11—Analysing solids by measuring attenuation of acoustic waves
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
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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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Abstract
The invention discloses a lithium ion battery overcharge detection method based on ultrasonic characteristics, which is characterized in that on the basis of representation of SOC by ultrasonic waves, ringing count is introduced into battery overcharge state evaluation, correlation between the ringing count and the SOC is determined, a relation equation set between the ultrasonic ringing count and stress, strain and damage variables in a battery circulation process is deduced, the change trend of the ultrasonic ringing count in the overcharge process is captured, the correlation between the ultrasonic ringing count and sound attenuation is utilized, the change of a microstructure in a material is reflected by measuring the ultrasonic ringing count, and the feasibility of detecting the overcharge state of the lithium ion battery by verifying the ringing count through an online measuring device.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery overcharge detection method based on ultrasonic characteristics.
Background
The development of the battery industry in the world at present has three characteristics, namely, the rapid development of green environment-friendly batteries including lithium ion storage batteries, nickel-hydrogen batteries and the like; secondly, the primary battery is converted into a storage battery, which accords with the strategy of sustainable development; thirdly, the battery is further developed to be small, light and thin. Among commercial rechargeable batteries, lithium ion batteries have the highest specific energy, and particularly polymer lithium ion batteries can be thinned. Lithium ion batteries have been rapidly growing in developed countries due to their high volumetric and mass specific energies, their rechargeable and non-polluting properties, and their three major characteristics of current battery industry development. The development of the markets of telecommunication, information and new energy, particularly the mass use of mobile phones, notebook computers and energy automobiles, brings market opportunity to lithium ion batteries. The polymer lithium ion battery in the lithium ion battery gradually replaces the liquid electrolyte lithium ion battery to become the mainstream of the lithium ion battery due to the unique advantage of the safety of the polymer lithium ion battery. Lithium ion batteries have been rapidly developed in recent years by virtue of their high energy density, long cycle life, and the like.
However, as lithium ion batteries are rapidly developed in various fields, the safety problems caused thereby are more serious, and overcharge is one of the main causes of battery failure and energy storage safety accidents. The accurate and timely identification of the overcharge of the battery is of great significance for improving the safety of the lithium ion battery. The existing detection technology cannot meet the requirements of precision and efficiency at the same time, and irreversible damage is caused to the battery per se to a certain extent. The ultrasonic detection technology is widely applied to nondestructive detection of the interior of a material, real-time and accurate evaluation on the internal damage and structural integrity of the material can be realized by analyzing and researching the sound propagation characteristics, and early warning information of battery faults can be provided by applying the ultrasonic technology to state detection of the material characteristics in a battery. Based on the statement, the invention provides a lithium ion battery overcharge real-time detection method based on ultrasonic characteristics.
Disclosure of Invention
The invention aims to solve the problems that the detection means in the prior art cannot meet the requirements on precision and efficiency at the same time and irreversible damage is generated to a battery to a certain extent, and provides an over-charge detection method of a lithium ion battery based on ultrasonic characteristics.
A lithium ion battery overcharge detection method based on ultrasonic characteristics comprises a lithium ion battery, a battery cycle tester, a transmitting circuit, a receiving circuit, a threshold circuit, a lower computer control circuit, an upper computer, a piezoelectric probe, a clamp, a temperature sensor, a voltage sensor and a current sensor, wherein the lithium ion battery, the battery cycle tester, the transmitting circuit, the receiving circuit, the threshold circuit, the lower computer control circuit, the upper computer, the piezoelectric probe and the clamp form a lithium ion battery overcharge detection system to realize ultrasonic ringing counting, the change of the charging state of the lithium ion battery is represented by ultrasonic ringing counting, the piezoelectric probes are clamped by a clamp and fixed on two sides of the lithium ion battery, a lower computer control circuit transmits excitation pulses to a transmitting circuit, the transmitting circuit controls the piezoelectric probe at a transmitting end to transmit ultrasonic waves to the lithium ion battery, the piezoelectric probe at a receiving end receives the ultrasonic waves passing through the lithium ion battery, the received signal is transmitted to the receiving circuit for processing and then transmitted to the threshold circuit, the threshold circuit extracts the characteristics of the ultrasonic wave and then transmits the characteristics to the lower computer control circuit for processing, the battery cycle tester is used for charging the lithium ion battery, the temperature sensor is arranged on the surface of the lithium ion battery, the device is used for detecting the temperature of the lithium ion battery and transmitting the detected information to a lower computer control circuit for processing, the voltage sensor is connected with the positive pole and the negative pole of the lithium ion battery, the current sensor is connected in series with the positive pole of the lithium ion battery, the voltage sensor and the current sensor respectively detect the voltage and the current of the lithium ion battery, and the detected information is transmitted to a lower computer control circuit for processing, and the lower computer control circuit transmits the received and processed information to an upper computer for state detection and fault analysis of the lithium ion battery.
The transmitting circuit is a multichannel narrow pulse generator and comprises an optical coupling isolation circuit, a MOSFET (metal oxide semiconductor field effect transistor) driving circuit, a unilateral pushing transmitting circuit, an impedance matching circuit and a high-voltage analog switch, excitation pulses sent by a lower computer control circuit are transmitted to the MOSFET driving circuit after passing through the optical coupling isolation circuit, the transmission performance of the excitation pulses is improved through the unilateral pushing transmitting circuit and the impedance matching circuit, and the excitation pulses are transmitted to a piezoelectric probe of a transmitting end by the high-voltage analog switch and then are converted into ultrasonic waves to be transmitted.
The receiving circuit comprises a detection circuit, a band-pass filter circuit, a program control gain amplifying circuit, a pre-amplifying circuit and a high-voltage analog switch, a piezoelectric probe of the receiving end receives an ultrasonic signal and converts the ultrasonic signal into an electric signal, the electric signal is transmitted to the pre-amplifying circuit and the program control gain amplifying circuit through the high-voltage analog switch to be amplified, the electric signal is filtered and de-noised through the band-pass filter circuit, the root mean square of the ultrasonic signal is calculated in the detection circuit, and the root mean square is transmitted to a threshold circuit to extract the characteristics of the ultrasonic wave.
The method for representing the change of the charging state of the lithium ion battery by the ultrasonic ringing count comprises the following specific operation steps: clamping the piezoelectric probes of the ultrasonic transmitting end and the ultrasonic receiving end by a clamp, and carrying out 0.5C constant current charging treatment on the lithium ion battery by adopting a battery cycle tester; during charging, the lower computer control circuit controls the transmitting circuit to transmit ultrasonic waves to the lithium ion battery, and controls the receiving circuit to receive the ultrasonic waves penetrating through the lithium ion battery, so that ultrasonic longitudinal waves received by the lithium ion battery in the longitudinal depth direction can be measured; the lithium ion battery and the clamp are placed in a constant temperature box to reduce experimental errors caused by the influence of external environment temperature difference; and analyzing and processing the acquired data in the upper computer to obtain the change relation between the ringing count and the charging state of the lithium ion battery, and carrying out real-time online detection on the overcharge fault of the lithium ion battery by combining voltage, current and temperature.
Preferably, the battery cycle tester is mainly provided bybase:Sub>A Xinwei high-precision battery performance system and comprisesbase:Sub>A lower computer (CT-4008-5V 20A-A) andbase:Sub>A middle computer (CT-ZWJ-4' S-T-1U).
Preferably, the upper computer is used for displaying voltage, current and temperature change in the charging process of the lithium ion battery in real time and controlling parameter setting and start-stop operation of the ultrasonic transmitting circuit and the ultrasonic receiving circuit.
Preferably, a pressure sensor is arranged on one side of the piezoelectric probe, so that the pressure on the lithium ion battery fixed on the clamp is constant in each experimental process.
Preferably, the piezoelectric probe selects a piezoelectric probe (a 405A-SB, olympus, japan) having a frequency of 5MHz to excite and receive the transmitted wave. An oily couplant (B2 glycerol couplant, japan Olilbus) is coated on the contact surface of the piezoelectric probe and the battery to enhance the wave transmission efficiency and maintain long-time online measurement.
The invention provides an ultrasonic characteristic-based lithium ion battery overcharge detection method, which has the following beneficial effects:
on the basis of representing the SOC by ultrasonic waves, the invention introduces the ringing count into the evaluation of the overcharge state of the battery, determines the correlation between the ringing count and the SOC, deduces a relational equation set between the ringing count of the ultrasonic waves and stress and damage variables in the circulation process of the battery, reflects the change of the microstructure in the material by measuring the ringing count of the ultrasonic waves and utilizing the correlation between the ringing count of the ultrasonic waves and sound attenuation in the overcharge process by capturing the change trend of the ringing count of the ultrasonic waves, and verifies the feasibility of detecting the overcharge state of the lithium ion battery by the ringing count through an online measuring device. The method can meet the requirements of the lithium ion battery on the precision and the efficiency of fault detection, and solves the problem that the existing internal flaw detection technology cannot realize on-line measurement.
Drawings
FIG. 1 is a schematic diagram of a lithium ion battery overcharge structure of a lithium ion battery overcharge detection method based on ultrasonic characteristics according to the present invention;
FIG. 2 is a diagram of a lithium ion battery overcharge detection system of a lithium ion battery overcharge detection method based on ultrasonic characteristics in accordance with the present invention;
FIG. 3 is an acoustic response diagram during the lithium ion battery overcharge process of a lithium ion battery overcharge detection method based on ultrasonic characteristics in accordance with the present invention;
FIG. 4 is a diagram showing the change of the ringing count during the overcharge of a lithium ion battery according to the method for detecting the overcharge of a lithium ion battery based on ultrasonic characteristics of the present invention;
FIG. 5 is a graph showing the voltage temperature change during the overcharge of a lithium ion battery according to one method of detecting the overcharge of a lithium ion battery based on ultrasonic characteristics of the present invention;
fig. 6 is a schematic diagram of ultrasonic ringing count extraction of a lithium ion battery overcharge detection method based on ultrasonic characteristics in the present invention.
The main elements are indicated with symbols.
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1 | |
2 |
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3 | |
4 |
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5 | Lower |
6 |
| Upper computer | 7 | |
8 |
| Clamp apparatus | 9 | |
10 |
| Voltage sensor | 11 | Current sensor | 12 |
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Referring to fig. 1 to 6, a method for detecting overcharge of a lithium ion battery 1 based on ultrasonic characteristics is shown.
A lithium ion battery 1 overcharge detection method based on ultrasonic characteristics comprises a lithium ion battery 1, a battery cycle tester 2, a transmitting circuit 3, a receiving circuit 4, a threshold circuit 5, a lower computer control circuit 6, an upper computer 7, a piezoelectric probe 8, a clamp 9, a temperature sensor 10, a voltage sensor 11 and a current sensor 12.
As shown in fig. 2, the lithium ion battery 1, the battery cycle tester 2, the transmitting circuit 3, the receiving circuit 4, the threshold circuit 5, the lower computer control circuit 6, the upper computer 7, the piezoelectric probe 8, and the clamp 9 form an overcharge detection system of the lithium ion battery 1 to realize ultrasonic ringing counting, the change of the charging state of the lithium ion battery 1 is represented by the ultrasonic ringing counting, the piezoelectric probe 8 is clamped by the clamp 9 and fixed on both sides of the lithium ion battery 1, the lower computer control circuit 6 transmits excitation pulses to the transmitting circuit 3, the transmitting circuit 3 controls the piezoelectric probe 8 at the transmitting end to transmit ultrasonic waves to the lithium ion battery 1, the piezoelectric probe 8 at the receiving end receives the ultrasonic waves passing through the lithium ion battery 1, transmits the received signals to the receiving circuit 4 to be processed and then transmitted to the threshold circuit 5, the characteristics of ultrasonic waves are extracted by the threshold circuit 5 and then transmitted to the lower computer control circuit 6 for processing, the battery cycle tester 2 is used for charging the lithium ion battery 1, the temperature sensor 10 is installed on the surface of the lithium ion battery 1 and used for detecting the temperature of the lithium ion battery 1 and transmitting the detected information to the lower computer control circuit 6 for processing, the voltage sensor 11 is connected to the positive electrode and the negative electrode of the lithium ion battery 1, the current sensor 12 is connected in series to the positive electrode of the lithium ion battery 1, the voltage sensor 11 and the current sensor 12 respectively detect the voltage and the current of the lithium ion battery 1 and transmit the detected information to the lower computer control circuit 6 for processing, and the lower computer control circuit 6 transmits the received and processed information to the upper computer 7 for state detection and fault analysis of the lithium ion battery 1.
As shown in fig. 2, the transmitting circuit 3 is a multichannel narrow pulse generator, and includes an optical coupling isolation circuit, a MOSFET driving circuit, a single-side driving transmitting circuit 3, an impedance matching circuit, and a high-voltage analog switch, an excitation pulse sent by the lower computer control circuit 6 is transmitted to the MOSFET driving circuit after passing through the optical coupling isolation circuit, and is transmitted to the transmitting circuit 3 and the impedance matching circuit through the single-side driving transmitting circuit to improve the transmission performance of the excitation pulse, and is transmitted to the piezoelectric probe 8 of the transmitting end by the high-voltage analog switch and then is converted into an ultrasonic wave to be transmitted.
As shown in fig. 2, the receiving circuit 4 includes a detection circuit, a band-pass filter circuit, a programmable gain amplifier circuit, a pre-amplifier circuit, and a high-voltage analog switch, wherein the piezoelectric probe 8 at the receiving end receives the ultrasonic signal and converts the ultrasonic signal into an electrical signal, the electrical signal is transmitted to the pre-amplifier circuit and the programmable gain amplifier circuit through the high-voltage analog switch for signal amplification, the signal is filtered and de-noised through the band-pass filter circuit, the root mean square of the ultrasonic signal is calculated in the detection circuit, and then the ultrasonic signal is transmitted to the threshold circuit 5 to extract the characteristics of the ultrasonic wave.
The method for representing the change of the charging state of the lithium ion battery 1 by the ultrasonic ringing count comprises the following specific operation steps: the piezoelectric probes 8 of the ultrasonic transmitting end and the ultrasonic receiving end are clamped by a clamp 9, and a battery cycle tester 2 is adopted to carry out 0.5C constant current charging treatment on the lithium ion battery 1; while charging, the lower computer control circuit 6 controls the transmitting circuit 3 to transmit ultrasonic waves to the lithium ion battery 1, and controls the receiving circuit 4 to receive the ultrasonic waves passing through the lithium ion battery 1, so that ultrasonic longitudinal waves received by the lithium ion battery 1 in the longitudinal depth direction can be measured; the lithium ion battery 1 and the clamp 9 are placed in a constant temperature box to reduce experimental errors caused by the influence of external environment temperature difference; and analyzing and processing the acquired data in the upper computer 7 to obtain the change relation between the ringing count and the charging state of the lithium ion battery 1, and carrying out real-time online detection on the overcharge fault of the lithium ion battery 1 by combining voltage, current and temperature.
The battery cycle tester 2 is mainly provided bybase:Sub>A Xinwei high-precision battery performance system and comprisesbase:Sub>A lower computer (CT-4008-5V 20A-A) andbase:Sub>A middle computer (CT-ZWJ-4' S-T-1U), and in order to prevent the battery from being broken down and influenced bybase:Sub>A lithium plating layer due to current change and overlarge current in the charging process of the battery,base:Sub>A 0.5C constant current charging mode is selected to perform overcharge detection test on the battery.
And the upper computer 7 is used for displaying voltage, current and temperature change in the charging process of the lithium ion battery in real time and controlling parameter setting and start-stop operation of the ultrasonic transmitting circuit 3 and the receiving circuit 4.
8 one side of piezoelectric probe be equipped with pressure sensor, guarantee that the pressure that fixes lithium ion battery 1 on anchor clamps 9 in the experimentation at every turn received is invariable, and pressure sensor has the digital display function, can audio-visually look over the pressure size that anchor clamps 9 applyed on lithium ion battery 1 to with operating personnel according to the clamp force of pressure value regulation anchor clamps 9.
In order to avoid the superposition of waves caused by overlarge wavelength and ensure the transmission efficiency of the waves, the piezoelectric probe 8 selects a piezoelectric probe (A405A-SB, nippon olympus) with the frequency of 5MHz to excite and receive the transmitted waves. An oily couplant (B2 glycerol couplant, japan olympus) is coated on the surface of the piezoelectric probe 8 in contact with the battery to enhance the wave transmission efficiency and maintain long-term online measurement.
The lithium ion battery 1 is a 3435mAh soft package lithium ion battery (SP 376080SI, tianjin Lishen), the positive electrode material is lithium cobaltate (LiCoO 2, LCO), the negative electrode material is graphite, and the size is 80 x 60 x 3.76mm.
The experimental data acquisition and processing steps of the invention are as follows:
s1, selecting a thermostat to set the constant temperature to 25 ℃, performing 0.5C constant current charging and discharging on a lithium ion battery 1, controlling a transmitting circuit 3 in a lower computer control circuit 6 to excite an ultrasonic signal every 30 seconds, acquiring the ultrasonic signal every 30 seconds corresponding to a receiving circuit 4, applying 5N pressure to a piezoelectric probe 8 by a clamp 9, acquiring and storing the ultrasonic signal excited every time by an upper computer 7, and extracting ultrasonic ringing count according to the condition that 10% of the amplitude of the ultrasonic signal under 100% SOC is used as a threshold voltage; as shown in fig. 6, after the ultrasonic signal is converted into a square wave signal and output by setting the threshold voltage Vr of the threshold circuit 5, the ultrasonic signal is received by the receiving circuit 4, and the ringing count characteristic is extracted by the lower computer control circuit 6;
s2, firstly carrying out Gaussian filtering processing on the acquired experimental data to filter out environmental noise signals caused by a constant temperature box and the battery cycle tester 2 in the experimental process, and then carrying out trend removing processing to eliminate the influence of the offset generated by the piezoelectric probe 8 when acquiring the data on the amplitude value and the selection of a ringing count threshold value;
s3, on the basis of representation of SOC by ultrasonic waves, introducing ringing counts into evaluation of the overcharge state of the battery, determining correlation between the ringing counts and the SOC, deducing a relational equation set between the ringing counts of the ultrasonic waves and stress and damage variables in the circulation process of the battery, researching the corresponding relationship between ultrasonic characteristics and the overcharge state by capturing the variation trend of the ringing counts of the ultrasonic waves in the overcharge process, and utilizing the correlation between the ringing counts of the ultrasonic waves and sound attenuation, wherein the relation between the ringing counts N and the sound attenuation beta is as follows:
f0 is probe frequency, vp is signal peak voltage, vr is threshold voltage, and beta is acoustic attenuation coefficient;
the change of the microstructure in the material is reflected by measuring the ultrasonic ringing count, and the feasibility of detecting the overcharge state of the lithium ion battery by using the ringing count is verified by an online measuring device;
s4, a relational equation set among ringing counting, stress and damage variables is as follows:
sigma is effective stress, D is a damage variable, E is elastic modulus, epsilon is strain, when the material is complete, D =0, when the material completely fails, D =1, m is a proportion parameter of the material, A1, B1 and C1 are fitting coefficients, experiments determine that the acoustic impedance of the material is changed due to the generation of internal bubbles and the loss of electrode layered oxide material in the overcharge process, so that the propagation speed of ultrasound and the degree of acoustic attenuation are influenced, and the change of acoustic attenuation can cause the change of ringing count, so that an acoustic signal is associated with the microstructure state of the battery, and the analysis can show that the change of the material in the overcharge process can be detected through ringing count, and the battery state can be more accurately represented by combining the acoustic wave amplitude and ToF.
Overcharge causes growth of lithium dendrites as shown in fig. 1, and when the lithium dendrites grow to a certain length, the separator is punctured, causing direct contact between the positive and negative electrodes of the battery, thereby forming a local short circuit. The overcharge causes decomposition of the electrolyte, and gases such as carbon dioxide, methane and ethylene are generated, and during the overcharge, excessive deintercalation of lithium causes collapse of the cathode structure, thereby causing huge heat and bubbles, and when the temperature rises to a certain value, the battery starts to expand to bulge, and when the maximum value is reached, the lithium ion battery 1 finally ruptures due to the nowhere release of the internal pressure.
As shown in fig. 3, during overcharge, the SOC increases with the insertion of lithium ions, the battery stiffness gradually increases, the ultrasonic signal gradually moves forward, the TOF becomes shorter, and the acoustic response waveform moves forward with the increase and decrease of the SOC of the lithium ion battery 1, indicating that the acoustic propagation speed increases.
As shown in figure 4, more and more gap bubbles exist between the positive electrode and the negative electrode, the distance between the electrodes is increased, the material is damaged, the sound attenuation is changed along with the change of the gap bubbles, the ringing count is changed and shows a descending trend according to a relational expression of the ringing count and the sound attenuation, the 0.5C constant-current charging is carried out, the theoretical full-current moment of the battery is 7200s, after the charging is continued, the descending trend of the ringing count shows that irreversible damage occurs in the battery to change the acoustic propagation characteristic, the descending of the ringing count can be used as an overcharge sign, the power supply is cut off at the moment of descending, and the danger of thermal runaway of the battery can be avoided.
As shown in fig. 5, as overcharge progresses, the surface temperature and the self voltage of the battery have no obvious fault signal, so that the safety state of the battery cannot be accurately reflected in time. The use of a ringing count feature to indicate the overcharge behaviour of a battery therefore has the advantage of higher sensitivity and more rapid response than conventional electrothermal parameters.
The principle of the ringing count is to count the number of times that a single ultrasonic excitation signal exceeds a threshold value by setting a threshold voltage to express the attenuation characteristic of the material, and the change of the ringing count is actually due to bubbles generated by decomposition reaction of an electrolyte during overcharge, so that the acoustic impedance of the material is increased, and the ringing count will begin to show a descending trend.
The working principle and the working process of the invention are as follows:
on the basis of representation of SOC by ultrasonic waves, ringing counts are introduced into evaluation of the overcharge state of the battery, correlation between the ringing counts and the SOC is determined, a relational equation set between the ultrasonic ringing counts and stress and damage variables in the battery circulation process is deduced, the change trend of the ultrasonic ringing counts in the overcharge process is captured, the correlation between the ultrasonic ringing counts and sound attenuation is utilized, the change of the microstructure in the material is reflected by measuring the ultrasonic ringing counts, and the feasibility of detecting the overcharge state of the lithium ion battery 1 by the ringing counts is verified by an online measuring device.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A lithium ion battery overcharge detection method based on ultrasonic characteristics is characterized by comprising a lithium ion battery, a battery cycle tester, a transmitting circuit, a receiving circuit, a threshold circuit, a lower computer control circuit, an upper computer, a piezoelectric probe, a clamp, a temperature sensor, a voltage sensor and a current sensor, wherein the lithium ion battery, the battery cycle tester, the transmitting circuit, the receiving circuit, the threshold circuit, the lower computer control circuit, the upper computer, the piezoelectric probe and the clamp form a lithium ion battery overcharge detection system to realize ultrasonic ringing counting, the change of the charging state of the lithium ion battery is represented by the ultrasonic ringing counting, the clamp clamps clamp the piezoelectric probes to be fixed on two sides of the lithium ion battery, the lower computer control circuit transmits excitation pulses to the transmitting circuit, and the transmitting circuit controls the piezoelectric probe at a transmitting end to transmit ultrasonic waves to the lithium ion battery, the ultrasonic wave passing through the lithium ion battery is received by a piezoelectric probe at a receiving end, the received signal is transmitted to a receiving circuit for processing and then transmitted to a threshold circuit, the characteristics of the ultrasonic wave are extracted by the threshold circuit and then transmitted to a lower computer control circuit for processing, a battery cycle tester is used for charging the lithium ion battery, a temperature sensor is arranged on the surface of the lithium ion battery and used for detecting the temperature of the lithium ion battery and transmitting the detected information to the lower computer control circuit for processing, a voltage sensor is connected to a positive electrode and a negative electrode of the lithium ion battery, a current sensor is connected to a positive electrode of the lithium ion battery in series, the voltage sensor and the current sensor respectively detect the voltage and the current of the lithium ion battery and transmit the detected information to the lower computer control circuit for processing, and the lower computer control circuit transmits the received and processed information to an upper computer for state detection and fault detection of the lithium ion battery And (6) analyzing.
2. The method for detecting the overcharge of the lithium ion battery based on the ultrasonic characteristics according to claim 1, wherein the specific operation steps of the method for characterizing the change of the charging state of the lithium ion battery by the ultrasonic ringing count are as follows: clamping the piezoelectric probes of the ultrasonic transmitting end and the ultrasonic receiving end by a clamp, and performing 0.5C constant current charging treatment on the lithium ion battery by adopting a battery cycle tester; when charging, the lower computer control circuit controls the transmitting circuit to transmit ultrasonic waves to the lithium ion battery, and controls the receiving circuit to receive the ultrasonic waves penetrating through the lithium ion battery, so that ultrasonic longitudinal waves received by the lithium ion battery in the longitudinal depth direction can be measured; the lithium ion battery and the clamp are placed in a constant temperature box to reduce experimental errors caused by the influence of external environment temperature difference; and analyzing and processing the acquired data in the upper computer to obtain the change relation between the ringing count and the charging state of the lithium ion battery, and carrying out real-time online detection on the overcharge fault of the lithium ion battery by combining voltage, current and temperature.
3. The method for detecting the overcharge of the lithium ion battery based on the ultrasonic characteristics as claimed in claim 1 and claim 2, wherein the experimental data acquisition and processing steps are as follows:
s1, selecting a thermostat to set the constant-current charging and discharging of 0.5C on a lithium ion battery under the condition of 25 ℃, controlling a transmitting circuit to excite an ultrasonic signal every 30 seconds in a lower computer control circuit, correspondingly acquiring the ultrasonic signal every 30 seconds in a receiving circuit, applying 5N pressure to a piezoelectric probe by a clamp, acquiring and storing the ultrasonic signal excited every time by an upper computer, and extracting the ringing count of ultrasonic waves by taking 10% of the amplitude of the ultrasonic signal under the condition of 100% SOC as a threshold voltage; as shown in fig. 6, after the ultrasonic signal is converted into a square wave signal and output by setting the threshold voltage Vr of the threshold circuit, the ultrasonic signal is received by the receiving circuit, and the ringing count characteristic is extracted by the lower computer control circuit;
s2, firstly carrying out Gaussian filtering processing on the acquired experimental data to filter out environmental noise signals caused by a constant temperature box and a battery cycle tester in the experimental process, and then carrying out trend removing processing to eliminate the influence of the offset generated by the piezoelectric probe when acquiring the data on the amplitude value and the selection of a ringing count threshold value;
s3, on the basis of representing the SOC by the ultrasonic waves, introducing ringing counts into a battery
In the state of charge evaluation, the correlation between the ringing count and the SOC is determined and the battery is derived
Relation equation between ultrasonic ringing count and stress and damage variables in circulation process
Group, by capturing the variation trend of ultrasonic ringing count during overcharge
Correspondence between ultrasonic characteristics and overcharge state, using ultrasonic ringing count and
the correlation between the sound attenuation, the ringing count N and the sound attenuation β is:
f 0 for probe frequency, vp is signal peak voltage, vr is threshold voltage, and β is acoustic
A wave attenuation coefficient;
the change of the microstructure inside the material is reflected by measuring the ultrasonic ringing count, and the feasibility of detecting the overcharge state of the lithium ion battery by the ringing count is verified by an online measuring device;
s4, a relation equation set among ringing counting, stress and damage variables is as follows:
sigma is effective stress, D is a damage variable, E is elastic modulus, epsilon is strain, when the material is complete, D =0, when the material completely fails, D =1, m is a proportion parameter of the material, A1, B1 and C1 are fitting coefficients, experiments determine that the acoustic impedance of the material is changed due to the generation of internal bubbles and the loss of electrode layered oxide material in the overcharge process, so that the propagation speed of ultrasound and the degree of acoustic attenuation are influenced, and the change of the acoustic attenuation can cause the change of ringing count, so that an acoustic signal is associated with the microstructure state of the battery, and the analysis can detect the change of the material in the overcharge process through ringing count, and the battery state can be more accurately represented by combining the acoustic wave amplitude and ToF.
4. The method for detecting overcharge of a lithium ion battery based on ultrasonic characteristics as claimed in claim 1 and claim 2, wherein overcharge causes decomposition of electrolyte, gas such as carbon dioxide, methane and ethylene is generated, excessive deintercalation of lithium during overcharge causes collapse of cathode structure, resulting in huge heat and bubbles, when temperature rises to a certain value, the battery begins to expand to bulge, and when the maximum value is reached, the lithium ion battery finally breaks due to the nowhere released internal pressure; along with the continuous embedding of lithium ions, the SOC is continuously increased, the battery rigidity is gradually increased, the ultrasonic signal gradually moves forwards, the TOF is shortened, and along with the continuous increase of the SOC of the lithium ion battery, the acoustic response waveform continuously moves forwards, which indicates that the sound propagation speed is continuously increased; the gap bubbles between the positive electrode and the negative electrode are more and more, the distance between the electrodes is increased, the material is damaged, the sound attenuation is changed along with the change, a formula 1 can be known from a relational expression of ringing counting and sound attenuation, the ringing counting is changed and shows a descending trend, the constant current charging at 0.5C is carried out, the theoretical full-current moment of the battery is 7200s, after the charging is continued, the descending trend of the ringing counting is shown, the irreversible damage is shown in the battery to change the acoustic propagation characteristic, the descending of the ringing counting can be used as an overcharge mark, the power supply is cut off at the descending moment, and the thermal runaway danger of the battery can be avoided.
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