CN106855610B - Lithium titanate battery health state estimation method - Google Patents
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- 230000036541 health Effects 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000007600 charging Methods 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 6
- 230000003862 health status Effects 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 5
- 238000012937 correction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000007405 data analysis Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 206010016766 flatulence Diseases 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 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]
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Abstract
The invention provides a lithium titanate battery health state estimation system and a lithium titanate battery health state estimation method, wherein the method comprises the following steps: charging/discharging the battery with constant current, and recording the electric quantity discharged by charge-discharge circulation; calculating the specific heat capacity corresponding to the selected charge-discharge cycle; solving a relation curve between the battery health state and the specific heat capacity and verifying the accuracy; the trend of the state of health of the battery is estimated. The technical scheme provided by the application utilizes the change of the specific heat capacity of the lithium titanate battery in the attenuation process to correct the lithium titanate battery, not only reflects the influence of the traditional aging factor on the health state of the battery, but also adds the specific heat capacity correction factor, thereby leading a new battery health state prediction model to predict the health state of the lithium titanate battery more accurately and improving the accuracy of the model.
Description
Technical Field
The invention relates to the field of state of health estimation, in particular to a lithium titanate battery state of health estimation method.
Background
Due to the characteristics of intermittence, uncontrollable property and the like of renewable energy sources such as wind power, solar energy and the like when the renewable energy sources are converted into electric energy, the renewable energy sources can seriously affect the safety and stability of a power grid when the renewable energy sources are connected into the power grid on a large scale, and therefore an energy storage technology is needed to realize dynamic supply and demand balance and provide auxiliary services such as peak regulation, frequency regulation and the like. Among the existing energy storage technologies, lithium ion batteries are widely used due to their characteristics of high energy density, long cycle life, environmental friendliness, and the like. But at the same time, the safety problem of the lithium ion battery is increasingly highlighted. How to accurately estimate the State of Health (SOH) of the battery is a key to ensure the safe operation of the lithium ion battery.
The SOH of a lithium battery refers to the current capacity capability of the lithium battery, and represents the percentage of the amount of electricity that the lithium battery can charge or discharge to the nominal capacity of the battery under certain conditions. As defined by the formula shown in formula (r),
as the cycle number and storage time of the lithium battery are accumulated, the capacity of the battery is gradually decreased (aged), and thus the state of health of the lithium battery is gradually decreased.
The reduction of the battery SOH in the storage process refers to the battery aging phenomenon caused by battery self-discharge, battery material characteristic change and the like in the storage process of the battery; the decrease in SOH of the battery during the recycling is a battery aging phenomenon caused by electrochemical reaction and changes in characteristics of battery materials during the use (charge and discharge) of the battery. Therefore, according to different aging mechanisms of the battery, different modeling modes can be adopted to estimate the SOH of the battery. At present, the lithium battery SOH mainly has the following modeling modes: electrochemical models, empirical models, and circuit models. The electrochemical model is mainly measured according to the change of an electrochemical parameter inside the battery in the battery attenuation process, the precision is high, but the model is complex to construct, and the application range is small; the empirical model is mainly based on monitoring data (temperature, internal resistance, voltage, current and the like) in the battery operation process, and is simple, but the experimental period is long; the circuit model is equivalent to a lithium ion battery into a circuit model from the electrical engineering perspective, and although the model can realize real-time monitoring of the battery SOH, the accuracy is poor.
The lithium titanate battery is a lithium ion battery taking lithium titanate as a negative electrode material, and compared with the traditional graphite negative electrode material, the lithium titanate material has the characteristics of zero strain, high discharge platform and the like, so that the cycle performance and the safety performance of the lithium titanate battery are greatly improved.
However, lithium titanate batteries are easy to swell during charging, discharging and placing, and the main component of generated gas is H especially in high-temperature environment2、CO、CO2And alkane gases. After the lithium titanate battery expands, the volume of the battery is increased, and the anode, the cathode and the diaphragm are not in close contact with each other any more, so that the battery fails, and the service life of the battery is seriously influenced. The flatulence phenomenon is the specific phenomenon of the lithium titanate battery, and the flatulence phenomenon can not occur in the traditional carbon cathode battery, so that the influence of the flatulence is not considered in the traditional lithium battery SOH estimation technology, and the traditional lithium battery SOH estimation technology is applied to estimate a lithium titanate battery system to generate large errors.
Therefore, a lithium titanate battery health state estimation method is needed, so that the SOH of a lithium titanate battery can be more accurately predicted, and the defect of large estimation error of a lithium titanate battery system in the prior art is overcome.
Disclosure of Invention
In order to solve the above-mentioned deficiencies in the prior art, the present invention provides a lithium titanate battery health status estimation method, comprising the steps of:
(1) carrying out charge-discharge circulation on the battery by using constant current, and recording the electric quantity discharged by the charge-discharge circulation;
(2) calculating the specific heat capacity corresponding to the current actual battery capacity in the selected charge-discharge cycle;
(3) obtaining the current battery capacity by using a capacity attenuation curve model, and obtaining the state of health (SOH) of the battery and the SOH and the specific heat capacity C of the battery based on the current battery capacitypAnd verifying the accuracy;
(4) the trend of the state of health of the battery is estimated.
Preferably, the step (1) includes: charging the battery at constant current of 0.2-1C, discharging the battery at constant current of 0.02-0.1C, and recording the electric quantity discharged in each charge-discharge cycle.
Preferably, the specific heat capacity C of the step (2)pCalculated as follows:
Cp＝Q/(mΔT) (1)
in the formula, Q: calorific value, m: quality of battery, Δ T: temperature difference before and after cell experiment;
the dispersion point relation of the current actual battery capacity and the specific heat capacity corresponding to the charge-discharge cycle is shown as the following formula:
Cp＝g(Ci) (2)
in the formula, CiIs the current actual battery capacity.
Preferably, the relation between the state of health and the specific heat capacity of the battery in the step (3) is shown as the following formula:
SOH＝F(Cp) (3)
in the formula, Cp: specific heat capacity; SOH: battery state of health.
Preferably, the state of health SOH of the battery is represented by the following formula:
of formula (II) to C'i: the current battery capacity is calculated by using the model; c0: an initial rated capacity;
preferably, the accuracy of the model of step (3) is verified as follows:
in formula (II), SOH'j: the current battery health state is calculated by utilizing a relation curve of the battery health state and the specific heat capacity; SOHj: current actual battery health status; j: j th batteryAnd (5) performing secondary circulation.
Preferably, the capacity-attenuation curve model
As shown in the following formula:
in the formula, Ni: number of battery cycles.
Preferably, the estimating of the trend of the state of health of the battery in the step (3) includes:
A. measuring the specific heat capacity of the battery to be measured to obtain the health state of the battery;
B. comparing the relation curve with the relation curve of the battery health state and the specific heat capacity;
C. and estimating the trend of the health state of the battery according to the comparison result.
A lithium titanate battery state of health estimation system, the system comprising: the device comprises a singlechip control module, and an alternating current pulse output module, a battery module, a display module and a detection module which are respectively connected with the singlechip control module.
Preferably, the single chip microcomputer control module comprises a data receiving part, a data analyzing part and a data processing and result output part;
the data receiving part is connected with the battery module and used for receiving response signal data made by the battery module aiming at an alternating current pulse signal output by an alternating current pulse, the data analyzing part is connected with the data receiving part and used for analyzing the received response signal data, the data processing part is connected with the data analyzing part and used for processing the analyzed response signal data, and the result sending part is respectively connected with the data processing part and the display module and used for displaying the result of the data processing in the display module.
Compared with the closest prior art, the invention has the following excellent effects:
the lithium titanate battery health state estimation method provided by the invention depends on a capacity attenuation curve model of the lithium titanate battery, and the lithium titanate battery is corrected by using the change of the specific heat capacity in the attenuation process to generate a relation curve of the battery health state and the specific heat capacity, so that the influence of the traditional aging factor on the battery health state is reflected, and the specific heat capacity correction factor is added, so that the battery health state prediction model can predict the health state of the lithium titanate battery more accurately, and the model accuracy is improved.
Drawings
FIG. 1 is a graph showing the heat generation curve of a lithium titanate battery according to the present invention;
FIG. 2 is a graph of the capacity fade of a lithium titanate battery of the present invention;
FIG. 3 is a diagram showing the health status and specific heat capacity of a lithium titanate battery according to the present invention.
Detailed Description
For a better understanding of the present invention, reference is made to the following description taken in conjunction with the accompanying drawings and examples.
The method and the device aim at the specific heat capacity characteristic of the battery to estimate the state of health of the battery, so that the method and the device are only suitable for the battery with larger specific heat capacity change in the capacity fading process.
Fig. 2 is a capacity attenuation curve diagram of a lithium titanate battery, wherein a scattered point is the battery capacity recorded in the process that the battery undergoes 10000 cycles, a curve is a capacity attenuation curve obtained by fitting, and a capacity attenuation formula is as follows:
C＝C0-0.6234*exp[(x-1385.59)/3144.34]-0.6234*exp[(x-1385.59)/3144.2] (1)
wherein C is the fitted battery capacity, and x is the cycle number.
The technical scheme provided by the invention is further explained by using a specific embodiment, and the lithium titanate battery health state estimation method based on specific heat capacity detection comprises the following steps:
(1) the battery was charged/discharged at constant current and the amount of charge released was recorded over the charge-discharge cycle:
according to the embodiment of the invention, a lithium titanate soft package battery with the rated capacity of 50Ah is selected, the battery is charged at a constant current of 0.2-1C, and the cut-off voltage is 2.7V; discharging the battery at constant current of 0.02-0.1C, with cut-off voltage of 1.5V, and recording the amount of electricity discharged per charge-discharge cycle.
(2) Calculating the current actual battery capacity and specific heat capacity corresponding to a certain cycle:
recording the charge and discharge cycle number of the battery in real time, taking the battery off the charge and discharge instrument when the cycle number reaches 500,1000,1500, … … and 10000 times, recording the discharge capacity of the battery at the moment, and recording the cycle number N of the battery at the momenti. Placing the battery in ARC, testing the calorific value Q of the battery in the state by utilizing the heat insulation environment provided by ARC, and calculating the specific heat capacity C by utilizing a formulapThe dispersion point relationship between the specific heat capacity and the capacity retention rate is obtained.
As shown in FIG. 1, the specific heat capacity can be determined from the slope of the straight line:
Cp＝Q/(mΔT) (2)
the current scattering point relationship between the actual battery capacity and the specific heat capacity is as follows:
Cp＝g(Ci) (3)
in the formula, Q: calorific value, m: quality of battery, Δ T: temperature difference before and after cell experiment;
(3) and (3) solving a relation curve of the battery health state and the specific heat capacity, and verifying the accuracy:
A. calculating the relation curve of the battery health state and the specific heat capacity
According to recorded NiCorresponding to the capacity attenuation curve to obtain Ci', and using the formula to convert CiConverting the dispersion point relation between the specific heat capacity and the current actual battery capacity into the dispersion point relation between the battery health state and the specific heat capacity, fitting the dispersion points to obtain a relation curve between the battery health state and the specific heat capacity, wherein the relation is as follows:
the specific embodiment is shown in fig. 3, wherein the solid line is a battery SOH prediction curve, and the dotted line is a battery SOH true value. Wherein the true value is a fitting value obtained by combining the battery capacity and the battery capacity attenuation.
The relationship between the state of health and the specific heat capacity of the battery is shown as follows:
SOH＝F(Cp) (5)
in the formula, Cp: specific heat capacity; SOH: battery state of health.
The state of health SOH of the battery is shown by the following formula:
in the formula, Ci': the current battery capacity is calculated by using a capacity attenuation curve model; c0: an initial rated capacity;
capacity decay curve model
As shown in the following formula:
in the formula, Ni: number of battery cycles.
B. Verifying the accuracy of the model:
the predicted value is checked by the following formula.
In formula (II), SOH'j: the current battery health state is calculated by utilizing a relation curve of the battery health state and the specific heat capacity; SOHj: current actual battery health status; j: the j cycle of the cell. When the error between the current state of health of the battery and the actual state of health of the battery is within 5%, the model is relatively accurate.
(4) Estimating the trend of the battery state of health:
the value range of the battery state estimation model is used as the upper and lower limits of the state of health of the battery, and the value range can be set according to actual conditions. The health state of the battery to be tested can be obtained by measuring the specific heat capacity of the battery to be tested, and the trend of the health state of the battery can be predicted by comparing the health state with the relation curve in the graph 3.
Lithium titanate battery state of health estimation system based on specific heat capacity detects, the system includes: the device comprises a singlechip control module, and an alternating current pulse output module, a battery module, a display module and a detection module which are respectively connected with the singlechip control module.
The single chip microcomputer control module comprises a data receiving part, a data analyzing part and a data processing and result output part;
the data receiving part is connected with the battery module and used for receiving response signal data made by the battery module aiming at an alternating current pulse signal output by an alternating current pulse, the data analyzing part is connected with the data receiving part and used for analyzing the received response signal data, the data processing part is connected with the data analyzing part and used for processing the analyzed response signal data, and the result sending part is respectively connected with the data processing part and the display module and used for displaying the result of the data processing in the display module.
The detection module is electrically connected with the battery module and is used for detecting the voltage and the current in the circuit and recording the detected voltage and current values;
the battery module is a lithium ion power battery;
the alternating current pulse output module respectively outputs alternating current pulse signals with two frequencies to the battery modules connected with the alternating current pulse output module; the two frequencies of alternating current pulse signals are alternating current pulse signals with the frequencies of 5963Hz and 3Hz respectively.
And the data receiving part of the single chip microcomputer control module receives the voltage and current value information transmitted by the detection module, transmits the voltage and current value information to the data analysis part for data analysis, transmits a data analysis result to the data processing part, estimates the health state trend of the battery according to the data analysis result by the data processing part, and transmits the estimation result to the result output part.
The result output part of the single chip microcomputer control module is directly connected with the display part, and the result is displayed through the display part.
The present invention is not limited to the above embodiments, and any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are included in the scope of the claims of the present invention which are filed as the application.
Claims (8)
1. The lithium titanate battery health state estimation method is characterized by comprising the following steps:
(1) carrying out charge-discharge circulation on the battery by using constant current, and recording the electric quantity discharged by the charge-discharge circulation;
(2) calculating specific heat capacity C corresponding to current actual battery capacity in selected charge-discharge cyclep；
(3) Obtaining the current battery capacity by using a capacity attenuation curve model, and obtaining the state of health (SOH) of the battery and the SOH and the specific heat capacity C of the battery based on the current battery capacitypAnd verifying the accuracy;
(4) the trend of the state of health of the battery is estimated.
2. The lithium titanate battery state of health estimation method of claim 1, wherein the step (1) includes: charging the battery at constant current of 0.2-1C, discharging the battery at constant current of 0.02-0.1C, and recording the electric quantity discharged in each charge-discharge cycle.
3. The lithium titanate battery state of health estimation method of claim 1, in which step (2) C ispCalculated as follows:
Cp＝Q/(mΔT) (1)
in the formula, Q: calorific value, m: quality of battery, Δ T: temperature difference before and after cell experiment;
the dispersion point relation of the current actual battery capacity and the specific heat capacity corresponding to the charge-discharge cycle is shown as the following formula:
Cp＝g(Ci) (2)
in the formula, CiIs the current actual battery capacity.
4. The lithium titanate battery state of health estimation method of claim 1, characterized in that, the battery state of health SOH and specific heat capacity C of step (3) arepThe relationship of (A) is shown as follows:
SOH＝F(Cp) (3)
in the formula, Cp: specific heat capacity.
5. The lithium titanate battery state of health estimation method of claim 4, wherein the SOH is represented by the following formula:
of formula (II) to C'i: the current battery capacity is calculated by using a capacity attenuation curve model; c0: an initial rated capacity.
6. The lithium titanate battery state of health estimation method of claim 4, wherein the battery state of health SOH and specific heat capacity C are verified as followspThe accuracy of the relationship of (a) is shown by the following equation:
in formula (II), SOH'j: the current battery health state is calculated by utilizing a relation curve of the battery health state and the specific heat capacity; SOHj: current actual battery health status; j: the j cycle of the cell.
7. The lithium titanate battery state of health estimation method of claim 5 or 6, characterized in that the capacity decay curve model
As shown in the following formula:
in the formula, Ni: number of battery cycles.
8. The lithium titanate battery state of health estimation method of claim 1, wherein the estimating of the trend of battery state of health of step (4) comprises:
A. measuring the specific heat capacity of the battery to be measured to obtain the health state of the battery;
B. comparing the relation curve with the relation curve of the battery health state and the specific heat capacity;
C. and estimating the trend of the health state of the battery according to the comparison result.
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| CN111624493B (en) * | 2019-02-28 | 2022-03-22 | 北京新能源汽车股份有限公司 | Method and device for determining state of health (SOH) of battery and detection equipment |
| CN111157908A (en) * | 2020-01-09 | 2020-05-15 | 青岛特来电云科技有限公司 | Battery health degree prediction method based on big data machine learning |
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