CN113030743A - Valve-regulated lead-acid battery state evaluation method based on battery discharge behavior - Google Patents

Valve-regulated lead-acid battery state evaluation method based on battery discharge behavior Download PDF

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CN113030743A
CN113030743A CN202110165163.5A CN202110165163A CN113030743A CN 113030743 A CN113030743 A CN 113030743A CN 202110165163 A CN202110165163 A CN 202110165163A CN 113030743 A CN113030743 A CN 113030743A
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acid battery
single valve
lead
valve
controlled lead
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CN113030743B (en
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徐开仁
杜珂
覃剑
黎铭洪
黄晓明
黄厚鑫
唐静
张光资
鲍海波
苏淑敏
唐明峰
吴林恩
陶丁涛
覃云奕
何理国
肖远平
梁元清
耿昌易
罗喜
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Nanning Power Supply Bureau of Guangxi Power Grid Co Ltd
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Nanning Power Supply Bureau of Guangxi Power Grid Co Ltd
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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
    • G01R31/3842—Arrangements for monitoring battery or accumulator variables, e.g. SoC combining voltage and current measurements
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/392—Determining battery ageing or deterioration, e.g. state of health
    • 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]
    • G01R31/396—Acquisition or processing of data for testing or for monitoring individual cells or groups of cells within a battery
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Charge And Discharge Circuits For Batteries Or The Like (AREA)

Abstract

The invention relates to the technical field of state evaluation of valve-controlled lead-acid batteries, in particular to a method for evaluating the state of a valve-controlled lead-acid battery based on the discharge behavior of the battery. The invention considers the electricity, heat, nonlinear behavior and temperature estimation, obtains the open circuit voltage calculation method under different working conditions through the parameters of the nonlinear battery nuclear capacity during discharge, obtains the internal resistance and open circuit voltage of the battery according to the experiment, and estimates the battery life by the battery temperature, and more accurately realizes the service life evaluation of the lead-acid battery during the engineering application, and in the practical application, the calculated voltage of the first 2-3 hours can be adopted, and the discharge voltage within 10 hours can be deduced according to the valve-controlled lead-acid battery dynamic equivalent circuit model, thereby saving the discharge time, improving the nuclear capacity verification efficiency of the valve-controlled lead-acid battery, and the error judgment rate is low when the valve-controlled lead-acid battery is adopted for service life estimation.

Description

Valve-regulated lead-acid battery state evaluation method based on battery discharge behavior
Technical Field
The invention relates to the technical field of state evaluation of valve-controlled lead-acid batteries, in particular to a method for evaluating the state of a valve-controlled lead-acid battery based on the discharge behavior of the battery.
Background
The aging of the lead-acid valve-regulated battery is mainly manifested by capacity fading and power reduction. The direct causes of aging include loss of active material, loss of available lead, and increase in internal resistance. In the use process of the lead-acid valve-regulated storage battery, factors such as the running environment, the charging and discharging working conditions, the charging scheme of the battery and the like of the battery all affect the capacity decay rate of the battery, so that the voltage is abnormal.
In the actual production process, according to the operation and maintenance regulations of storage batteries, 0.1C current is mainly adopted for discharging for 10 hours (C is the capacity of the battery) at the temperature of 25 ℃, during discharging, the open-circuit voltage of the battery (the voltage of the storage battery without a load) is measured every 1 hour, if the voltage of a single battery is lower than 1.8V, the capacity of the battery is unqualified, the service life is expired, after discharging for 10 hours, the battery is charged for 10 hours according to the 0.1C current, the verification period of the whole nuclear capacity is long and the cost is high, meanwhile, the scheme does not consider the changes of parameters such as the temperature of the battery, the internal electrochemical reaction and the like, in the measurement process of the existing method, the battery is in a charging and discharging state, the actual measurement value is the open-circuit voltage (the storage battery with a load during discharging), and the error of the measurement value is.
Disclosure of Invention
In order to solve the problems, the invention provides a method for evaluating the state of a valve-regulated lead-acid battery based on the discharge behavior of the battery, which has the following specific technical scheme:
a method for evaluating the state of a valve-regulated lead-acid battery based on the discharge behavior of the battery comprises the following steps:
s1: acquiring the actual open-circuit voltage of the single valve-controlled lead-acid battery and the temperature of the single valve-controlled lead-acid battery, determining whether the single valve-controlled lead-acid battery is qualified or not according to the relationship between the open-circuit voltage of the single valve-controlled lead-acid battery and the temperature of the single valve-controlled lead-acid battery, and if the single valve-controlled lead-acid battery is judged to be unqualified, exiting the operation of the single valve-controlled lead; if the single valve-controlled lead-acid battery is judged to be qualified, the step S2 is carried out;
s2: measuring the internal resistance of the single valve-controlled lead-acid battery, calculating the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature, and if the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature is greater than a threshold value, judging that the single valve-controlled lead-acid battery is unqualified, and stopping the single valve-controlled lead-acid battery; if the single valve-controlled lead-acid battery is judged to be qualified, the step S3 is carried out;
s3: and evaluating the service life of the single valve-controlled lead-acid battery according to the functional relation between the actual open-circuit voltage and the discharge time of the single valve-controlled lead-acid battery.
Preferably, in step S1, the relationship between the open-circuit voltage of the single valve-regulated lead-acid battery and the temperature of the single valve-regulated lead-acid battery is as follows: and when the temperature is reduced by 1 ℃, the open-circuit voltage of the qualified single valve-controlled lead-acid battery is increased by 0-5 mV, when the temperature is increased by 1 ℃, the open-circuit voltage of the qualified single valve-controlled lead-acid battery is reduced by 0-5 mV, and if the open-circuit voltage of the single valve-controlled lead-acid battery is increased or reduced out of the range of 0-5 mV, the single valve-controlled lead-acid battery is judged to be unqualified.
Preferably, the step S2 includes the steps of:
s21: establishing a dynamic equivalent electrical model of the valve-regulated lead-acid battery, wherein the model consists of R capable of capturing dynamic behaviorsd1C1To composition, overvoltage resistance Rd1And an overvoltage capacitor C1After being connected in parallel, the internal resistance R in the discharge perioddIn series, the actual open circuit voltage of the valve-regulated lead-acid battery during discharge is calculated by the following equation (1):
Vter(n)＝OCV(n)-Rd(n)idis(n)-Vc1(n)； (1)
wherein, VterShows the actual open-circuit voltage, V, of the single valve-controlled lead-acid batteryter(n) shows the unit valve-controlled lead-acid battery of the nth dischargeThe actual open circuit voltage of; OCV represents the theoretical open-circuit voltage of the single valve-controlled lead-acid battery, and OCV (n) represents the theoretical open-circuit voltage of the single valve-controlled lead-acid battery discharged for the nth time; vc1As an overvoltage capacitor C1Voltage across, Vc1(n) overvoltage capacitor C for nth discharge1The voltage across; rd(n) represents the internal resistance during the nth discharge; i.e. idisIndicating the current at discharge, idis(n) represents a current at the time of the nth discharge;
s22: calculating the internal resistance R during the nth discharged(n)：
Figure BDA0002937586550000021
S23: calculating the overvoltage resistance R during the nth discharged1(n)：
Rd1(n)＝g(idis(n),OCV(n))＝g1(idis(n))·g2(OCV(n))； (3)
By quadratic function to overvoltage resistance Rd1(n) is fitted to the variation of the theoretical open circuit voltage ocv (n) to obtain the following equation:
g2(OCV(n))＝aRd1OCV(n)2+bRd1OCV(n)+cRd1； (4)
wherein, aRd1、bRd1、cRd1Is a constant;
by exponential function to overvoltage resistance Rd1(n) fitting to the change in current upon discharge to obtain the following equation:
Figure BDA0002937586550000022
wherein, ad1、bd1Is a constant;
then:
Figure BDA0002937586550000023
s24: calculating the total internal resistance during discharge:
Figure BDA0002937586550000031
s25: calculating the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature:
Figure BDA0002937586550000032
if Δ is not less than ΔmaxIf not, judging the single valve-controlled lead-acid battery to be qualified, wherein deltamaxThe threshold value of the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature is obtained; t isbat(n) is the temperature of the single valve-controlled lead-acid battery during the nth discharge; t isbat(n +1) is the temperature of the single valve-controlled lead-acid battery during the discharge of the (n +1) th time; t isbat(n+1)-Tbat(n) represents the temperature variation of the single valve-regulated lead-acid battery discharged twice adjacently; rint(n+1)-RintAnd (n) represents the internal resistance variation of the single valve-regulated lead-acid battery discharged twice in adjacent times.
Preferably, the theoretical open-circuit voltage ocv (n) of the nth discharged single valve-regulated lead-acid battery is calculated as follows: the state of charge SOC of a single valve regulated lead acid battery can be estimated in ampere hours and is expressed as:
Figure BDA0002937586550000033
wherein SOC (initial) is the initial charging state of the single valve-regulated lead-acid battery, CratedThe rated capacity of the single valve-controlled lead-acid battery is shown, and t is the charging time. By adopting a curve fitting method in a single valve-regulated lead-acid battery manufacturer data table, the SOC value of the charging state can be further applied to calculate the theoretical open-circuit voltage OCV (n) of the n-th discharged single valve-regulated lead-acid battery:
OCV(n)＝α×SOC(t)+β； (8)
wherein α and β are constants.
Preferably, the temperature variation T of the adjacent two-time discharge single valve-regulated lead-acid batterybat(n+1)-TbatThe calculation of (n) is as follows: the total heat generated in the single valve-controlled lead-acid battery is divided into two parts, namely joule heat and heat generated by convection loss;
the amount of heat generated inside the battery by joule heat is given by the following formula:
Hgen(n)＝∫idis(n)2Rint(n)； (9)
Hgen(n) represents the amount of heat generated by the nth discharge;
according to newton's law of cooling:
Figure BDA0002937586550000034
wherein, Tamb(n) is the environment temperature T of the single valve-controlled lead-acid battery during the nth dischargeambLambda is the cooling rate of the single valve-controlled lead-acid battery;
in order to be used as an estimator in a microcontroller, the formula (9) needs to be discretized:
Figure BDA0002937586550000041
Figure BDA0002937586550000042
Tbat(n)＝Trise(n)+Tamb； (13)
obtaining the temperature variation T of the single valve-regulated lead-acid battery with two adjacent discharges according to the formulas (10), (12) and (13)bat(n+1)-Tbat(n) is calculated as follows:
Figure BDA0002937586550000043
Trise(n) represents the temperature of the single valve-regulated lead-acid battery rising during the nth discharge; t isrise(n +1) represents the temperature of the single valve-controlled lead-acid battery rising during the discharge of the (n +1) th time; m is the mass of the single valve-controlled lead-acid battery; spIs a specific heat capacity; t is tsIs the sampling time; the cooling rate lambda of the single valve-regulated lead-acid battery is calculated in the following mode:
Figure BDA0002937586550000044
a is the area of the single valve-controlled lead-acid battery; and h is the heat transfer coefficient of the single valve-controlled lead-acid battery.
Preferably, the step S3 includes the steps of:
s31: the following equation is further derived from equation (1):
Figure BDA0002937586550000045
wherein, tau1For the time constant, the calculation is as follows:
Figure BDA0002937586550000046
wherein, aτd、bτdIs a constant of fit;
equation (16) then translates to the following:
Figure BDA0002937586550000047
when the actual open-circuit voltage V of the single valve-controlled lead-acid battery is calculated by the formula (18)terAnd (n) when the voltage is lower than 1.8V, the single valve-regulated lead-acid battery is considered to be unqualified, and the service life of the single valve-regulated lead-acid battery is expired.
The invention has the beneficial effects that: the invention provides a method for evaluating the state of a valve-controlled lead-acid battery based on the discharge behavior of the battery, which considers the electricity, heat and nonlinear behaviors and temperature estimation, obtains a calculation method of open-circuit voltage under the charge-discharge state of the battery under different working conditions by parameters during the discharge of the nuclear capacity of the nonlinear battery, obtains an evaluation method of internal resistance, open-circuit voltage and battery temperature of the battery on the service life of the battery according to experiments, more accurately realizes the service life evaluation of the lead-acid battery during engineering application, can adopt the calculated voltage of the first 2-3 hours during actual application, deduces the discharge voltage within 10 hours according to a dynamic equivalent circuit model of the valve-controlled lead-acid battery, saves the discharge time, improves the nuclear capacity verification efficiency of the valve-controlled lead-acid battery, and adopts the invention to evaluate the service life of the valve-controlled lead-acid battery, the occurring misjudgment rate is low.
Drawings
FIG. 1 is a schematic diagram of a dynamic equivalent electrical model of a valve-regulated lead-acid battery of the present invention;
FIG. 2 is RdThe result graph of exponential fitting of (1);
FIG. 3 shows R at different discharge current levelsd1A graph of results fitted to a theoretical open circuit voltage;
FIG. 4 is Rd1The result graph of exponential fitting of (1);
FIG. 5 shows τ at different discharge current levels1The result graph of exponential fitting of (1);
FIG. 6 is a graph showing the comparison result between the actual open-circuit voltage calculated by the experimental verification of the present invention and the actual open-circuit voltage actually measured;
FIG. 7 is a graph of open circuit voltage versus temperature for a valve-regulated lead acid battery;
FIG. 8 is a graph showing the relationship between the internal resistance change rate and the temperature of the valve-regulated lead-acid battery.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings in which:
a method for evaluating the state of a valve-regulated lead-acid battery based on the discharge behavior of the battery comprises the following steps:
s1: acquiring the actual open-circuit voltage of the single valve-controlled lead-acid battery and the temperature of the single valve-controlled lead-acid battery, determining whether the single valve-controlled lead-acid battery is qualified or not according to the relationship between the open-circuit voltage of the single valve-controlled lead-acid battery and the temperature of the single valve-controlled lead-acid battery, and if the single valve-controlled lead-acid battery is judged to be unqualified, exiting the operation of the single valve-controlled lead; if the single valve-controlled lead-acid battery is judged to be qualified, the step S2 is carried out;
in step S1, the relationship between the open-circuit voltage of the single valve-regulated lead-acid battery and the temperature of the single valve-regulated lead-acid battery is as follows: and when the temperature is reduced by 1 ℃, the open-circuit voltage of the qualified single valve-controlled lead-acid battery is increased by 0-5 mV, when the temperature is increased by 1 ℃, the open-circuit voltage of the qualified single valve-controlled lead-acid battery is reduced by 0-5 mV, and if the open-circuit voltage of the single valve-controlled lead-acid battery is increased or reduced out of the range of 0-5 mV, the single valve-controlled lead-acid battery is judged to be unqualified.
S2: measuring the internal resistance of the single valve-controlled lead-acid battery, calculating the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature, and if the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature is greater than a threshold value, judging that the single valve-controlled lead-acid battery is unqualified, and stopping the single valve-controlled lead-acid battery; and if the single valve-regulated lead-acid battery is judged to be qualified, performing step S3.
Step S2 includes the following steps:
s21: establishing a dynamic equivalent electrical model of the valve-regulated lead-acid battery, wherein the model consists of R capable of capturing dynamic behaviorsd1C1To composition, overvoltage resistance Rd1And an overvoltage capacitor C1After being connected in parallel, the internal resistance R in the discharge perioddSeries, diode Dd1、DdFor indicating the direction of current flow only, internal resistance R during dischargedReacting the concentration of electrolyte inside the battery; overvoltage resistor Rd1Reacting the state of activated materials in the storage battery; when the deviation between the calculated values of the parameters and the calculated values of the invention is larger, the problem exists in different parts in the battery.
The actual open-circuit voltage of the valve-regulated lead-acid battery during discharge is calculated by the following formula (1):
Vter(n)＝OCV(n)-Rd(n)idis(n)-Vc1(n)； (1)
wherein, VterShows the actual open-circuit voltage, V, of the single valve-controlled lead-acid batteryter(n) represents the actual open circuit voltage of the unit valve-regulated lead-acid battery discharged for the nth time; OCV represents the theoretical open-circuit voltage of the single valve-controlled lead-acid battery, and OCV (n) represents the theoretical open-circuit voltage of the single valve-controlled lead-acid battery discharged for the nth time; vc1As an overvoltage capacitor C1Voltage across, Vc1(n) overvoltage capacitor C for nth discharge1The voltage across; rd(n) represents the internal resistance during the nth discharge; i.e. idisIndicating the current at discharge, idis(n) represents a current at the time of the nth discharge.
The theoretical open-circuit voltage OCV (n) of the unit valve-regulated lead-acid battery discharged for the nth time is calculated as follows:
the state of charge SOC of a single valve regulated lead acid battery can be estimated in ampere hours and is expressed as:
Figure BDA0002937586550000061
wherein SOC (initial) is the initial charging state of the single valve-regulated lead-acid battery, CratedThe rated capacity of the single valve-controlled lead-acid battery is shown, and t is the charging time. By adopting a curve fitting method in a single valve-regulated lead-acid battery manufacturer data table, the SOC value of the charging state can be further applied to calculate the theoretical open-circuit voltage OCV (n) of the n-th discharged single valve-regulated lead-acid battery:
OCV(n)＝α×SOC(t)+β； (8)
where α and β are constants, α is 1.47, and β is 0.9. The linear approximation of OCV and SOC is effective between 10% and 90%. However, the relationship between the OCV and the SOC is not linear beyond the above range. Thus, in the present analysis, SOC is considered to be between 10% and 90%.
S22: calculating the internal resistance R during the nth discharged(n), experimental fit as shown in fig. 2:
Figure BDA0002937586550000062
s23: calculating the overvoltage resistance R during the nth discharged1(n)：
Rd1(n)＝g(idis(n),OCV(n))＝g1(idis(n))·g2(OCV(n))；(3)
By quadratic function to overvoltage resistance Rd1(n) is fitted to the variation of the theoretical open-circuit voltage OCV (n), as shown in FIG. 3, with a fitting error of + -1.5%, resulting in the following equation:
g2(OCV(n))＝aRd1OCV(n)2+bRd1OCV(n)+cRd1； (4)
wherein, aRd1、bRd1、cRd1Is a constant;
by exponential function to overvoltage resistance Rd1(n) is fitted to the change in current at the time of discharge, as shown in FIG. 4, to obtain the following equation:
Figure BDA0002937586550000071
wherein, ad1、bd1Is a constant;
then:
Figure BDA0002937586550000072
s24: calculating the total internal resistance during discharge:
Figure BDA0002937586550000073
s25: calculating the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature:
Figure BDA0002937586550000074
if Δ is not less than ΔmaxIf not, judging the single valve-controlled lead-acid battery to be qualified, wherein deltamaxThe threshold value of the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature is obtained; t isbat(n) is the temperature of the single valve-controlled lead-acid battery during the nth discharge; t isbat(n +1) is the temperature of the single valve-controlled lead-acid battery during the discharge of the (n +1) th time; t isbat(n+1)-Tbat(n) represents the temperature variation of the single valve-regulated lead-acid battery discharged twice adjacently; rint(n+1)-RintAnd (n) represents the internal resistance variation of the single valve-regulated lead-acid battery discharged twice in adjacent times.
Temperature variation T of adjacent twice-discharging single valve-controlled lead-acid batterybat(n+1)-TbatThe calculation of (n) is as follows:
the total heat generated in the single valve-controlled lead-acid battery is divided into two parts, namely joule heat and heat generated by convection loss;
the amount of heat generated inside the battery by joule heat is given by the following formula:
Hgen(n)＝∫idis(n)2Rint(n)； (9)
Hgen(n) represents the amount of heat generated by the nth discharge;
according to newton's law of cooling:
Figure BDA0002937586550000081
wherein, Tamb(n) is the environment temperature T of the single valve-controlled lead-acid battery during the nth dischargeambLambda is the cooling rate of the single valve-controlled lead-acid battery;
in order to be used as an estimator in a microcontroller, the formula (9) needs to be discretized:
Figure BDA0002937586550000082
Figure BDA0002937586550000083
Tbat(n)＝Trise(n)+Tamb； (13)
obtaining the temperature variation T of the single valve-regulated lead-acid battery with two adjacent discharges according to the formulas (10), (12) and (13)bat(n+1)-Tbat(n) is calculated as follows:
Figure BDA0002937586550000084
Trise(n) represents the temperature of the single valve-regulated lead-acid battery rising during the nth discharge; t isrise(n +1) represents the temperature of the single valve-controlled lead-acid battery rising during the discharge of the (n +1) th time; m is the mass of the single valve-controlled lead-acid battery; spIs a specific heat capacity; t is tsIs the sampling time; the cooling rate lambda of the single valve-regulated lead-acid battery is calculated in the following mode:
Figure BDA0002937586550000085
a is the area of the single valve-controlled lead-acid battery; and h is the heat transfer coefficient of the single valve-controlled lead-acid battery.
S3: and evaluating the service life of the single valve-controlled lead-acid battery according to the functional relation between the actual open-circuit voltage and the discharge time of the single valve-controlled lead-acid battery. Step S3 includes the following steps:
s31: the following equation is further derived from equation (1):
Figure BDA0002937586550000086
wherein, tau1For the time constant, the calculation is as follows:
Figure BDA0002937586550000087
wherein, aτd、bτdIs a constant of fit; the fit is shown in fig. 5.
Equation (16) then translates to the following:
Figure BDA0002937586550000091
when the actual open-circuit voltage V of the single valve-controlled lead-acid battery is calculated by the formula (18)terAnd (n) when the voltage is lower than 1.8V, the single valve-regulated lead-acid battery is considered to be unqualified, and the service life of the single valve-regulated lead-acid battery is expired.
The accuracy of the model was verified by comparing the actual open circuit voltage response estimated by equation (18) of the present invention with the voltage response measured in the experiment with a discharge current of 20A (C200 AH) for a discharge time of 10 hours. As is clear from fig. 6, the variation of the actual open circuit voltage obtained from the formula (18) and V obtained from the experimentterThe variation of (c) is very close, with an error of only 0.04%.
The parameters of the single valve-regulated lead acid battery in this example are shown in table 1 below:
table 1 specification of battery parameters for thermal modeling
(symbol) Means of Numerical value
m Quality of 9.6Kg
Tamb Ambient temperature 25℃
λ Rate of cooling 0.003/sec
A Area of 0.062m2
Sp Specific heat capacity 0.22Wh/Kg·K
h Coefficient of heat transfer 100W/m2·K
Table 1 table of discharge constants
Serial number Constant of discharge Numerical value
1 aod 0.1076
2 bod -0.343
3 ad1 0.18
4 bd1 -1.074
5 aRd1 0.097
6 bRd1 -2.325
7 cRd1 13.9
8 aτd 227
9 bτd -1.28
An application example of the present application is given below:
aiming at the operation and maintenance rules of the single valve-controlled lead-acid battery, in order to prevent the operation and maintenance modes that the single valve-controlled lead-acid battery needs to be charged for 10 hours and discharged for 10 hours, the service life evaluation flow of the single valve-controlled lead-acid battery is as follows:
and (3) temperature evaluation of the single valve-controlled lead-acid battery:
experiment: the method comprises the steps of selecting 104 qualified single valve-controlled lead-acid batteries and 104 unqualified single valve-controlled lead-acid batteries at a reference temperature of 25 ℃, changing the temperature between 20 ℃ and 30 ℃, keeping each temperature value for 1 hour, and measuring the open-circuit voltage of the single valve-controlled lead-acid batteries after ensuring the temperature of the single valve-controlled lead-acid batteries to be stable, wherein the maximum voltage change value is selected for the qualified single valve-controlled lead-acid batteries, the minimum voltage change value is selected for the unqualified single valve-controlled lead-acid batteries, the voltage of the qualified single valve-controlled lead-acid batteries is increased by (0-5) mV when the temperature is reduced by 1 ℃, and the voltage of the qualified single valve-. And when the voltage of the single valve-controlled lead-acid battery does not meet the condition, judging that the single valve-controlled lead-acid battery is unqualified, and exiting the operation.
Evaluating the internal resistance of the single valve-controlled lead-acid battery:
selecting 104 qualified single valve-controlled lead-acid batteries and 104 unqualified single valve-controlled lead-acid batteries, measuring the internal resistance of the single valve-controlled lead-acid batteries at each moment, wherein each temperature value lasts for 1 hour, and measuring the internal resistance of the single valve-controlled lead-acid batteries after the temperature of the single valve-controlled lead-acid batteries is stable, wherein the qualified single valve-controlled lead-acid batteries select the maximum internal resistance change value, the unqualified single valve-controlled lead-acid batteries select the minimum internal change rate, and the internal resistance change rate of the qualified single valve-controlled lead-acid batteries along with the temperature is less than 1.9%; the internal resistance change rate of the unqualified single valve-controlled lead-acid battery along with the temperature is more than 1.9 percent, and delta at the momentmaxThe setting is 1.9%, as shown in fig. 8.
And (3) evaluating the service life of the single valve-regulated lead-acid battery according to the function relation of the actual open-circuit voltage and the discharge time of the single valve-regulated lead-acid battery in the formula (18).
The present invention is not limited to the above-described embodiments, which are merely preferred embodiments of the present invention, and the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A method for evaluating the state of a valve-regulated lead-acid battery based on the discharge behavior of the battery is characterized in that: the method comprises the following steps:
s1: acquiring the actual open-circuit voltage of the single valve-controlled lead-acid battery and the temperature of the single valve-controlled lead-acid battery, determining whether the single valve-controlled lead-acid battery is qualified or not according to the relationship between the open-circuit voltage of the single valve-controlled lead-acid battery and the temperature of the single valve-controlled lead-acid battery, and if the single valve-controlled lead-acid battery is judged to be unqualified, exiting the operation of the single valve-controlled lead; if the single valve-controlled lead-acid battery is judged to be qualified, the step S2 is carried out;
s2: measuring the internal resistance of the single valve-controlled lead-acid battery, calculating the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature, and if the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature is greater than a threshold value, judging that the single valve-controlled lead-acid battery is unqualified, and stopping the single valve-controlled lead-acid battery; if the single valve-controlled lead-acid battery is judged to be qualified, the step S3 is carried out;
s3: and evaluating the service life of the single valve-controlled lead-acid battery according to the functional relation between the actual open-circuit voltage and the discharge time of the single valve-controlled lead-acid battery.
2. The method for evaluating the state of the valve-regulated lead-acid battery based on the discharge behavior of the battery according to claim 1, wherein the method comprises the following steps: in the step S1, the relationship between the open-circuit voltage of the single valve-regulated lead-acid battery and the temperature of the single valve-regulated lead-acid battery is as follows: and when the temperature is reduced by 1 ℃, the open-circuit voltage of the qualified single valve-controlled lead-acid battery is increased by 0-5 mV, when the temperature is increased by 1 ℃, the open-circuit voltage of the qualified single valve-controlled lead-acid battery is reduced by 0-5 mV, and if the open-circuit voltage of the single valve-controlled lead-acid battery is increased or reduced out of the range of 0-5 mV, the single valve-controlled lead-acid battery is judged to be unqualified.
3. The method for evaluating the state of the valve-regulated lead-acid battery based on the discharge behavior of the battery according to claim 1, wherein the method comprises the following steps: the step S2 includes the steps of:
s21: establishing a dynamic equivalent electrical model of the valve-regulated lead-acid battery, wherein the model consists of R capable of capturing dynamic behaviorsd1C1To composition, overvoltage resistance Rd1And an overvoltage capacitor C1After being connected in parallel, the internal resistance R in the discharge perioddIn series, the actual open circuit voltage of the valve-regulated lead-acid battery during discharge is calculated by the following equation (1):
Vter(n)＝OCV(n)-Rd(n)idis(n)-Vc1(n)； (1)
wherein, VterShows the actual open-circuit voltage, V, of the single valve-controlled lead-acid batteryter(n) represents the actual open circuit voltage of the unit valve-regulated lead-acid battery discharged for the nth time; OCV represents the theoretical open-circuit voltage of the single valve-controlled lead-acid battery, and OCV (n) represents the theoretical open-circuit voltage of the single valve-controlled lead-acid battery discharged for the nth time; vc1As an overvoltage capacitor C1Voltage across, Vc1(n) overvoltage capacitor C for nth discharge1The voltage across; rd(n) represents the internal resistance during the nth discharge; i.e. idisIndicating the current at discharge, idis(n) represents a current at the time of the nth discharge;
s22: calculating the internal resistance R during the nth discharged(n)：
Figure FDA0002937586540000011
S23: calculating the overvoltage resistance R during the nth discharged1(n)：
Rd1(n)＝g(idis(n),OCV(n))＝g1(idis(n))·g2(OCV(n))； (3)
By quadratic function to overvoltage resistance Rd1(n) is fitted to the variation of the theoretical open circuit voltage ocv (n) to obtain the following equation:
g2(OCV(n))＝aRd1OCV(n)2+bRd1OCV(n)+cRd1； (4)
wherein, aRd1、bRd1、cRd1Is a constant;
by exponential function to overvoltage resistance Rd1(n) fitting to the change in current upon discharge to obtain the following equation:
Figure FDA0002937586540000021
wherein, ad1、bd1Is a constant;
then:
Figure FDA0002937586540000022
s24: calculating the total internal resistance during discharge:
Figure FDA0002937586540000023
s25: calculating the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature:
Figure FDA0002937586540000024
if Δ is not less than ΔmaxIf not, judging the single valve-controlled lead-acid battery to be qualified, wherein deltamaxThe threshold value of the change rate of the internal resistance of the single valve-controlled lead-acid battery along with the temperature is obtained; t isbat(n) is the temperature of the single valve-controlled lead-acid battery during the nth discharge; t isbat(n +1) is the temperature of the single valve-controlled lead-acid battery during the discharge of the (n +1) th time; t isbat(n+1)-Tbat(n) represents the temperature variation of the single valve-regulated lead-acid battery discharged twice adjacently; rint(n+1)-RintAnd (n) represents the internal resistance variation of the single valve-regulated lead-acid battery discharged twice in adjacent times.
4. The method for evaluating the state of the valve-regulated lead-acid battery based on the discharge behavior of the battery according to claim 3, wherein the method comprises the following steps: the theoretical open-circuit voltage OCV (n) of the unit valve-regulated lead-acid battery discharged for the nth time is calculated as follows:
the state of charge SOC of a single valve regulated lead acid battery can be estimated in ampere hours and is expressed as:
Figure FDA0002937586540000025
wherein SOC (initial) is the initial charging state of the single valve-regulated lead-acid battery, CratedThe rated capacity of the single valve-controlled lead-acid battery is shown, and t is the charging time. By adopting a curve fitting method in a single valve-regulated lead-acid battery manufacturer data table, the SOC value of the charging state can be further applied to calculate the theoretical open-circuit voltage OCV (n) of the n-th discharged single valve-regulated lead-acid battery:
OCV(n)＝α×SOC(t)+β； (8)
wherein α and β are constants.
5. The method for evaluating the state of the valve-regulated lead-acid battery based on the discharge behavior of the battery according to claim 3, wherein the method comprises the following steps: temperature variation T of adjacent twice-discharging single valve-controlled lead-acid batterybat(n+1)-TbatThe calculation of (n) is as follows:
the total heat generated in the single valve-controlled lead-acid battery is divided into two parts, namely joule heat and heat generated by convection loss;
the amount of heat generated inside the battery by joule heat is given by the following formula:
Hgen(n)＝∫idis(n)2Rint(n)； (9)
Hgen(n) represents the amount of heat generated by the nth discharge;
according to newton's law of cooling:
Figure FDA0002937586540000031
wherein, Tamb(n) is the environment temperature T of the single valve-controlled lead-acid battery during the nth dischargeambLambda is the cooling rate of the single valve-controlled lead-acid battery;
in order to be used as an estimator in a microcontroller, the formula (9) needs to be discretized:
Figure FDA0002937586540000032
Figure FDA0002937586540000033
Tbat(n)＝Trise(n)+Tamb； (13)
obtaining the temperature variation T of the single valve-regulated lead-acid battery with two adjacent discharges according to the formulas (10), (12) and (13)bat(n+1)-Tbat(n) is calculated as follows:
Figure FDA0002937586540000034
Trise(n) represents the temperature of the single valve-regulated lead-acid battery rising during the nth discharge; t isrise(n +1) represents the temperature of the single valve-controlled lead-acid battery rising during the discharge of the (n +1) th time; m is the mass of the single valve-controlled lead-acid battery; spIs a specific heat capacity; t is tsIs the sampling time; the cooling rate lambda of the single valve-regulated lead-acid battery is calculated in the following mode:
Figure FDA0002937586540000041
a is the area of the single valve-controlled lead-acid battery; and h is the heat transfer coefficient of the single valve-controlled lead-acid battery.
6. The method for evaluating the state of the valve-regulated lead-acid battery based on the discharge behavior of the battery according to claim 3, wherein the method comprises the following steps: the step S3 includes the steps of:
s31: the following equation is further derived from equation (1):
Figure FDA0002937586540000042
wherein, tau1For the time constant, the calculation is as follows:
Figure FDA0002937586540000043
wherein, aτd、bτdIs a constant of fit;
equation (16) then translates to the following:
Figure FDA0002937586540000044
when the actual open-circuit voltage V of the single valve-controlled lead-acid battery is calculated by the formula (18)terAnd (n) when the voltage is lower than 1.8V, the single valve-regulated lead-acid battery is considered to be unqualified, and the service life of the single valve-regulated lead-acid battery is expired.
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