CN112363058B - Lithium ion battery safety degree estimation method and device based on impedance spectrum and Markov characteristic - Google Patents
Lithium ion battery safety degree estimation method and device based on impedance spectrum and Markov characteristic Download PDFInfo
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Abstract
The invention discloses a lithium ion battery safety degree estimation method and device based on impedance spectrum Markov characteristics, and belongs to the technical field of battery safety degree estimation. The invention is used for solving the problem that the prior art does not carry out quantification and real-time display on the safety of the battery. Establishing a Markov chain model of each state of a lithium ion battery; establishing a second-order RC equivalent circuit model of the lithium ion battery; mapping electrochemical impedance spectrums of the lithium ion battery in different states; analyzing influence relations among different states; and solving the safety degree of the battery, establishing a battery safety degree corresponding table, predicting and evaluating the safety condition of the lithium ion power battery in real time, timely reminding a user to pay attention to the safety state of the battery, making corresponding safety early warning, and reducing or even avoiding unnecessary battery harm.
Description
Technical Field
The invention relates to the field of battery safety degree estimation, in particular to a lithium ion battery safety degree estimation method and device based on impedance spectrum and Markov characteristics.
Background
Electric vehicles have been rapidly developed due to environmental protection, energy conservation and government support, and the development of electric vehicles has driven the commercial development of lithium batteries. However, while the power and energy density of a commercial lithium ion battery are improved, the possibility of spontaneous combustion and explosion of the battery caused by charging and discharging and the power of explosion of the battery are also improved, the charging and discharging of the battery are often accompanied by heat generation, if the battery generates too much heat and cannot be timely dissipated in the charging and discharging process, the performance of the battery may be remarkably deteriorated and degenerated due to heat accumulation along with the charging and discharging, and when the temperature is increased to melt a diaphragm in the battery, the positive electrode and the negative electrode are in short circuit, the battery may be in danger of explosion and the like.
Therefore, the safety problem restricts the application of the battery in the high-energy and high-power field, and the safety problem becomes a problem which is not to be solved by the battery and related industries. Thermal runaway is not only a fundamental reason for safety problems, but also one of the reasons for restricting the performance of batteries in the field of new energy, and the potential safety problems of lithium ion batteries greatly influence the confidence of consumers. Although a Battery Management System (BMS) is expected to accurately monitor a safety state (SOS) and predict and prevent the occurrence of some faults, it is difficult to secure all safety states in a life cycle thereof by a technical system due to complicated and various conditions of thermal runaway. Whether all factors are combined or not can be achieved, and the safety degree of the lithium ion power battery can be quantized as much as possible, which plays an important role in preventing battery accidents and guaranteeing the life safety of users.
Disclosure of Invention
In order to solve the above problems, the present invention provides a lithium ion battery safety degree estimation method and apparatus based on impedance spectrum and markov characteristics, which can estimate the safety degree value of the battery in real time according to the state data of the battery.
The invention provides a lithium ion battery safety degree estimation method based on impedance spectrum and Markov characteristic, which comprises the following steps:
establishing and determining parameters influencing the safety state of the battery according to the battery data, determining a main state parameter X1 and a plurality of secondary state parameters X2 and X3 … Xn from the state parameters, and setting an out-of-control state as S;
establishing an equivalent circuit model of the lithium ion battery, mapping an electrochemical impedance spectrum, and obtaining a weight coefficient alpha of the main state parameter according to the electrochemical impedance spectrum12、α13…α1nAnd a weight coefficient alpha of the secondary state parameter21、…α2n、…、αn1、αn2…αnn-1；
Determining a safety component of the primary status parameter and a safety component of the secondary status parameter according to:
in the formula, SXComponent of safety level, X, representing different states of the batteryburnA value, X, representing the state at the time of thermal runaway of the batterynowA value, X, representing the current statenewA value representing the state when the battery is just out of the field or works normally;
establishing a Markov model, and establishing a transfer matrix by combining the weight coefficient of the primary state parameter, the weight coefficient of the secondary state parameter, the safety degree component of the primary state parameter and the safety degree component of the secondary state parameter;
and establishing stable distribution vectors of the main state and the secondary state to obtain the current safety degree value of the battery.
Further, the state parameters refer to causes for thermal runaway of the battery, and include internal resistance of the battery, charging and discharging times of the battery and nuclear power state of the battery.
Further, the method for obtaining the weight coefficient of the main state parameter comprises the following steps:
determining the average value K of the proportional relation of the main state parameter to each secondary state parameter according to the map12、K13…K1n；
According to K12:K13:…:K1n＝α12:α13:…:α1nAnd alpha12+α13+…+α1nObtaining the weight coefficient alpha of the main state parameter as 112、α13…α1n。
Further, the method for obtaining the weight coefficient of the secondary state parameter comprises the following steps:
determining a secondary state parameter relative to the primary state parameter and each of the remaining secondary state parameters from the mapAverage value K of proportional relation of numbers21…K2n、…Kn1、…、Kn(n-1)；
According to K21：…：K2n＝α21:…:α2n，…，Kn1：…：Kn(n-1)＝αn1:…:αn(n-1)；
α21+α23+…+α2n＝1，…，αn1+αn2+…+αn(n-1)Obtaining a weight factor α for the secondary state parameter at 121、…α2n、…、αn1、αn2…αn(n-1)。
Further, the transition matrix is:
where Xn is the state of the cell, SXnRepresenting the degree of influence of each state on battery runaway for the safety degree components of the battery in different non-runaway states; s is the out-of-control state of the battery; alpha is alphaijIs a weight coefficient of the degree of influence of the i-state on the j-state, and
further, the stable distribution vector of the primary state, the secondary state and the out-of-control state is as follows:
π＝(πX1,πX2,...,πXn,πS)；
wherein, piSIs a battery safety value;
substituting into a formula: pi P and pi e (n) 1 to obtain the safety of the battery piSThe numerical value of (c).
Further, the lithium ion battery safety degree estimation method based on the impedance spectrum and the Markov characteristic comprises the steps of establishing a safety degree comparison table, wherein the safety degree comparison table is composed of a plurality of safety intervals, and the safety intervals correspond to the battery safety conditions at the current moment; and matching the obtained safety degree value with the safety interval to obtain the battery safety condition at the current moment.
The invention provides a lithium ion battery safety degree estimation device based on impedance spectrum and Markov characteristic, comprising:
the estimation module is used for estimating the current safety value of the battery according to the lithium ion battery safety estimation method based on the impedance spectrum and the Markov characteristic in the first aspect of the invention;
and the display module is used for displaying the safety information of the battery in the current state.
The system further comprises an interval matching module used for establishing a safety degree comparison table, wherein the safety degree comparison table is composed of a plurality of safety intervals, and the safety intervals correspond to the safety condition of the battery at the current moment; and matching the safety degree value obtained by the estimation module with the safety interval to obtain the battery safety condition at the current moment.
As described above, the present invention has the following effects compared with the prior art:
1. according to the method, the main parameters and the secondary parameters causing battery runaway are selected through data, the relation between the main state parameters and the secondary state parameters is determined through the lithium ion battery equivalent circuit model, the weight coefficient between the states is further determined, the real-time safety degree value of the battery is obtained through the Markov chain, the real-time accurate estimation of the safety information of the battery is realized, and the problem that the safety performance of the lithium ion battery in the using process cannot be quantitatively expressed in the prior art is solved;
2. the method identifies parameters of the equivalent circuit model through electrochemical impedance, can complete the estimation of the safety degree of the battery under the condition of not damaging the internal structure of the battery, and has economical efficiency and practicability;
3. the invention is realized by the existing hardware carrying software, and can be applied to various lithium ion battery application occasions.
Drawings
FIG. 1 is a flow chart of steps of a method for estimating the safety of a lithium ion battery according to an embodiment of the present invention;
fig. 2 is a second order RC equivalent circuit of a lithium ion battery according to an embodiment of the present invention;
FIG. 3 is an electrochemical impedance spectrum of a lithium ion battery in different SOC states when the temperature T is 75 ℃ and the cycle of charging and discharging is 1 in accordance with an embodiment of the present invention;
FIG. 4 is a graph showing the relationship between the internal resistance and the ohmic resistance of the lithium ion battery in different SOC states at a temperature T of 75 ℃ and different charging and discharging times according to the embodiment of the present invention;
figure 5 is a schematic diagram of a markov chain in accordance with an embodiment of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
The safety of the battery refers to that the battery does not burn, explode, generate toxic and harmful gases and do not hurt the user in the using process, in order to prevent the battery accident and ensure the life safety of the user, the safety degree of the battery in the using process is quantitatively described by combining various factors in the embodiment, which is called as the safety degree of the battery.
As shown in fig. 1, a lithium ion battery safety degree estimation method based on impedance spectrum and markov characteristic in this embodiment includes the following steps:
s1, establishing and determining parameters affecting the safety state of the battery according to the battery data, determining a main state parameter X1 and a plurality of secondary state parameters X2 and X3 … Xn from the state parameters, and setting an out-of-control state as S;
in the embodiment, a specific power battery module is selected to adopt a 3.7V/1750mAh ternary material 18650 type lithium ion battery. According to the historical data of the battery and the combination of expert experience analysis, the most main reason for causing the out-of-control of the battery is the increase of the internal resistance of the battery, so the internal resistance of the battery is taken as a main state parameter; the charge and discharge times and the charge state of the battery are used as secondary state parameters, specifically as shown in an influence state table of the lithium ion battery, and in the actual application process, the primary state parameters and the secondary state parameters of the battery can be selected according to different battery historical data, the working environment of the battery and the like.
Table 1: lithium ion battery influence state table
In the table, SR、Scycle、SSOCSequentially representing safety degree components of the battery in three states of internal resistance, charging and discharging times and SOC (state of charge) of the battery, and reflecting the influence degree of the three states of the battery on the out-of-control of the battery; sSIndicating a battery runaway condition of 1; alpha is alphaijA weight coefficient representing the degree to which the i state affects the j state, each state having no effect on the state itself, so alpha when i equals jijIs equal to 0, and
namely alpha12+α13＝1、α21+α23＝1、α31+α32＝1，α41+α42+α 421 is ═ 1; the proportion of the influence degree of each non-runaway state on other non-self states can be analyzed through experiments and historical data to obtain the specific value of the weight coefficient, and the proportion of the influence degree of the runaway state on other states is the proportion of the safety degree component of the non-runaway stateAnd inversely proportional.
When the battery is out of control, the temperature rises, the voltage rises, the internal resistance becomes large, the current rises, and the probability of the battery having safety problems and each parameter form positive correlation, so that the definition formula of the battery SOH is subjected to analog reasoning and a large amount of data verification, and a safety degree component formula can be obtained:
in the formula, SXComponent of safety level, X, representing different states of the batteryburnA value, X, representing the state at the time of thermal runaway of the batterynowA value, X, representing the current statenewIndicating the value of the state when the battery is just out of service or in normal operation.
In this embodiment, the safety component S of the main state of the batteryRComprises the following steps:
wherein, R is the ohmic internal resistance of the battery in the current state; rnewOhmic internal resistance of the battery when leaving factory; rburnOhmic internal resistance when thermal runaway occurs in the battery; for lithium ion batteries, the ohmic internal resistance consisting of electrode materials, electrolyte, diaphragm resistance and contact resistance of parts can represent the main part of the internal resistance of the battery, and R can be used for further improving the precisionseiAnd RctParameters for the secondary state are included. In the embodiment, the ohmic internal resistance of the battery can be normally used after the battery is aged to be connected in parallel, and for the use of the battery in the echelon utilization and the extreme environment, the battery management historical data and a large number of damage experiments can be selected according to the actual situation to change the corresponding XburnThe value is obtained.
Battery minor state safety component:
in the formula, cycle and SOC are the current charge and discharge times and the current state of charge of the battery in sequence; cycleburn、SOCburnThe charging and discharging times and the charge state of the battery when the battery has safety problems such as thermal runaway and the like are sequentially set; SOCnewThe battery is the state of charge at the time of shipment. These parameters can be obtained based on battery management system history data of the battery, related expert experience, and parameters provided by the battery manufacturer.
S2, establishing a Markov model, and establishing a transfer matrix by combining the weight coefficient of the primary state parameter, the weight coefficient of the secondary state parameter, the safety degree component of the primary state parameter and the safety degree component of the secondary state parameter;
the markov model described in this embodiment is shown in fig. 5, and the transition matrix obtained according to the model is:
s3, establishing an equivalent circuit model of the lithium ion battery, mapping an electrochemical impedance spectrum, and obtaining a weight coefficient alpha of the main state parameter according to the electrochemical impedance spectrum12And alpha13The weight coefficient alpha of the secondary state parameter21、α23、α31、α32The method specifically comprises the following steps:
s31, establishing a lithium ion battery second-order RC equivalent circuit model as shown in figure 2, wherein the lithium ion battery can be equivalent to a circuit system comprising a resistor, an inductor and a capacitor so as to simulate the change process in an electrochemical system. Wherein R isohmExpressing ohmic internal resistance; r isseiAnd CseiRepresents the resistance and capacitance of the SEI film; rctAnd CdRespectively representing a charge transfer resistance and an electrical double-layer capacitance; z is a linear or branched memberωIs Warburg impedance, i.e. diffusion of lithium ions in the electrode materialImpedance, further the lithium ion battery impedance can be obtained:
s32, the above formula is modified to obtain:
i.e. one circle center is
Radius of
A circle of (c); wherein Re (Z) is real impedance part, im (Z) is imaginary impedance part, and RohmIs ohmic internal resistance, R, in equivalent circuit modelseiIs the SEI resistance in the equivalent circuit model; further, the abscissa of the intersection point of the first circle extension and the x axis in the impedance spectrum of the lithium ion battery is RohmValue of R is the diameterseiValue, similarly obtained RctThe value is obtained.
And S33, calculating the corresponding ohmic internal resistance value of the lithium ion battery in the electrochemical impedance spectrum in different SOC states when the mapping temperature T is 75 ℃ and the charging and discharging times cycle is 1 as shown in figure 3.
S34, repeating the step S33, plotting the electrochemical impedance spectrum of the lithium ion battery under different SOC states at the temperature T of 75 ℃ and different charging and discharging times, calculating the corresponding ohmic internal resistance value, and drawing a relation curve chart as shown in FIG. 4.
S35, according to the relation curve chart in the step S34, the ohmic internal resistance and the state of charge of the state of charge SOC are in a linear relation within the interval of 0.2-0.8, and corresponding to the part, the average value K of the proportional relation of the ohmic internal resistance and the state of charge under different charging and discharging times is taken13I.e. Δ Rohm(n)＝K13(n)×ΔSOC(n)，
The average value K of the proportional relation of the ohmic internal resistance to the charging and discharging times can be obtained in the same way12Further, K can be obtained12:K13＝α12:α13，α12+α13Can solve alpha 1ijA specific value; such as for K12The influence of the ohmic internal resistance on the charging times of the user can be analyzed according to the actual service condition of the battery by further improving the precision, and the method corresponds to the method for improving the accuracy of the battery12＝2.36％，α13＝97.64％。
S36, obtaining the weight coefficient of the secondary state of the battery according to the principle of the step S35, which corresponds to the weight coefficient of the secondary state of the battery alpha in the example21＝58.34％，
α23＝41.66％，α31＝94.34％，α32＝5.66％。
And S4, establishing a stable distribution vector of the primary state and the secondary state to obtain the current safety degree value of the battery.
The stable distribution vectors of the primary state, the secondary state and the out-of-control state are as follows:
π＝(πR,πcycle,πsoc,πS)；
wherein, piR、πcycle、πsocRepresenting the corresponding stable distribution (limit distribution) of the states of the internal resistance, the charging and discharging times, the charge and the like of the battery, piSIs a battery safety value;
substituting into a formula: pi P and pi e (n) 1 to obtain the safety of the battery piSThe numerical value of (c).
In this example, R is takennew＝15mΩ、Rburn＝100mΩ、cycleburn＝1000、SOCburn＝70％、SOCnewWhen the ohmic internal resistance of the battery is 36m Ω, the number of charging and discharging times is 400 times, and the state of charge is 80% in this example, the safety factor S is 0.76.
S5, establishing a safety degree comparison table, wherein the safety degree comparison table is composed of a plurality of safety intervals, and the safety intervals correspond to the battery safety conditions at the current moment; and matching the obtained safety degree value with the safety interval to obtain the battery safety condition at the current moment. The safety level comparison table of this embodiment is shown in table 2:
| interval of safety degree | Degree of safety |
| 0-0.2 | Serious danger |
| 0.2-0.4 | Danger of |
| 0.4-0.6 | Potential danger |
| 0.6-0.8 | In general |
| 0.8-1 | Good effect |
As can be seen from Table 2, the safety of the battery of this example was very high.
The invention provides a lithium ion battery safety degree estimation device based on impedance spectrum and Markov characteristic, comprising:
the estimation module is used for estimating the current safety value of the battery according to the lithium ion battery safety estimation method based on the impedance spectrum and the Markov characteristic in the first aspect of the invention;
and the display module is used for displaying the safety information of the current state of the battery, including a safety degree interval and/or the current use safety condition of the battery.
The interval matching module is used for establishing a safety degree comparison table, the safety degree comparison table is composed of a plurality of safety intervals, and the safety intervals correspond to the battery safety conditions at the current moment; and matching the safety degree value obtained by the estimation module with the safety interval to obtain the battery safety condition at the current moment.
The embodiment provides an electronic device, which includes a processor, a memory and a display, where the memory has an instruction for implementing the method for estimating the safety of a lithium-ion power battery according to the embodiment of the present disclosure, and the processor is configured to call the instruction to execute the method for estimating the safety of a battery according to the embodiment of the present disclosure, where the processor in this embodiment may be a DSP or a single chip microcomputer, and the like.
In addition, when the instructions in the memory are implemented in the form of software functional units and sold or used as a stand-alone product, the instructions may be stored in a computer-readable storage medium, that is, a part of the technical solution of the present invention or a part of the technical solution that contributes to the prior art may be embodied in the form of a software product, the computer software product is stored in a storage medium, and includes several instructions to enable a computer device (which may be a personal computer, a server, or a network device) to execute all or part of the steps of the method according to the embodiments of the present invention. And the aforementioned storage medium includes: u disk, removable hard disk, read only memory, random access memory, magnetic or optical disk, etc. for storing program codes.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (7)
1. A lithium ion battery safety degree estimation method based on impedance spectrum and Markov characteristic is characterized by comprising the following steps:
establishing and determining parameters influencing the safety state of the battery according to the battery data, determining a main state parameter X1 and a plurality of secondary state parameters X2 and X3 … Xn from the state parameters, and setting an out-of-control state as S;
establishing a Markov model, and establishing a transition matrix by combining the weight coefficient of the primary state parameter, the weight coefficient of the secondary state parameter, the safety degree component of the primary state parameter and the safety degree component of the secondary state parameter, wherein the transition matrix is as follows:
in the formula, SXnRepresenting the degree of influence of each state on battery runaway for the safety degree components of the battery in different non-runaway states; alpha is alphaijA weighting factor for the degree of influence of the i-state on the j-state, where α is when i equals jijWhen i is 0, i is 1,
when the utility model is used, the water is discharged,
when the temperature of the water is higher than the set temperature,
establishing an equivalent circuit model of the lithium ion battery, mapping an electrochemical impedance spectrum, and obtaining a weight coefficient alpha of the main state parameter according to the electrochemical impedance spectrum12、α13…α1nAnd a weight coefficient alpha of the secondary state parameter21、…α2n、…、αn1、αn2…αnn-1；
Determining a safety component of the primary status parameter and a safety component of the secondary status parameter according to:
in the formula, SXRepresenting the safety component, X, of each state parameter of the batteryburnShowing the value of each state parameter when the battery is in thermal runaway, X showing the current value of each state parameter, XnewThe numerical value of each state parameter when the battery is just delivered from a factory or works normally is represented;
establishing stable distribution vectors of a main state, a secondary state and an out-of-control state to obtain a current safety degree value of the battery, wherein the stable distribution vectors of the main state, the secondary state and the out-of-control state are as follows:
π＝(πX1,πX2,...,πXn,πS)；
wherein, piSThe value is the safety degree value of the battery;
substituting into a formula: pi P and pi e (n) 1 to obtain the safety of the battery piSThe numerical value of (c).
2. The lithium ion battery safety degree estimation method based on the impedance spectrum and the Markov characteristic as claimed in claim 1, wherein the state parameters refer to causes for battery thermal runaway, and comprise battery internal resistance, battery charge and discharge times and battery state of charge.
3. The lithium ion battery safety degree estimation method based on the impedance spectrum and the Markov characteristic as claimed in claim 1, wherein the method for obtaining the weight coefficient of the main state parameter comprises the following steps:
determining the mean value K of the proportional relationship of the primary state parameter to each secondary state parameter from the electrochemical impedance spectrum12、K13…K1n；
According to K12:K13:…:K1n＝α12:α13:…:α1nAnd alpha12+α13+…+α1nObtaining the weight coefficient alpha of the main state parameter as 112、α13…α1n。
4. The lithium ion battery safety degree estimation method based on the impedance spectrum and the Markov characteristic as claimed in claim 1, wherein the secondary state parameter weighting coefficient obtaining method comprises:
determining the average value K of the proportional relationship of the secondary state parameter to the primary state parameter and each of the remaining secondary state parameters from the electrochemical impedance spectroscopy21…K2n、…Kn1、…、Kn(n-1)；
According to K21：…：K2n＝α21:…:α2n，…，Kn1：…：Kn(n-1)＝αn1:…:αn(n-1)；
α21+α23+…+α2n＝1，…，αn1+αn2+…+αn(n-1)Obtaining a weight factor α for the secondary state parameter at 121、…α2n、…、αn1、αn2…αn(n-1)。
5. The lithium ion battery safety degree estimation method based on the impedance spectrum and the Markov characteristic as claimed in claim 1, wherein the lithium ion battery safety degree estimation method based on the impedance spectrum and the Markov characteristic comprises establishing a safety degree comparison table, wherein the safety degree comparison table is composed of a plurality of safety intervals, and the safety intervals correspond to the battery safety condition at the current moment; and matching the obtained safety degree value with the safety interval to obtain the battery safety condition at the current moment.
6. A lithium ion battery safety degree estimation device based on impedance spectrum and Markov characteristic is characterized by comprising the following components:
an estimation module, which is used for estimating the current safety value of the battery according to the lithium ion battery safety estimation method based on the impedance spectrum and the Markov characteristic in any one of claims 1 to 5;
and the display module is used for displaying the safety information of the battery in the current state.
7. The lithium ion battery safety estimation device based on the impedance spectrum and the Markov characteristic as recited in claim 6, further comprising an interval matching module for establishing a safety comparison table, wherein the safety comparison table is composed of a plurality of safety intervals, and the safety intervals correspond to the battery safety conditions at the current moment; and matching the safety degree value obtained by the estimation module with the safety interval to obtain the battery safety condition at the current moment.
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