CN115267551A - Method for simultaneously measuring open circuit potential curve and entropy coefficient curve of lithium ion battery electrode material - Google Patents
Method for simultaneously measuring open circuit potential curve and entropy coefficient curve of lithium ion battery electrode material Download PDFInfo
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- CN115267551A CN115267551A CN202210893146.8A CN202210893146A CN115267551A CN 115267551 A CN115267551 A CN 115267551A CN 202210893146 A CN202210893146 A CN 202210893146A CN 115267551 A CN115267551 A CN 115267551A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 238000007600 charging Methods 0.000 claims abstract description 26
- 238000007599 discharging Methods 0.000 claims abstract description 25
- 230000004913 activation Effects 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 238000004088 simulation Methods 0.000 claims description 19
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000005259 measurement Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/367—Software therefor, e.g. for battery testing using modelling or look-up tables
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
A method for simultaneously measuring an open circuit potential curve and an entropy coefficient curve of an electrode material of a lithium ion battery belongs to the technical field of lithium ion batteries. The method comprises the following specific steps: disassembling a battery to be simulated, assembling the battery into a button half battery, performing a plurality of circles of charge-discharge cyclic activation at room temperature, then performing charge or discharge (anode charge and cathode discharge) until the battery is fully charged or fully discharged, then charging and discharging fixed capacity (anode discharge and cathode charge) at the same current at room temperature, then respectively standing at different temperatures, returning the battery to the fixed capacity at the same current at room temperature after standing, repeating the operation until the upper limit or the lower limit of the specified voltage is reached, and recording the voltage and the voltage difference at different temperatures. And then, the open-circuit potential curve fitting adopts the combination of a tangent function and an exponential function, and the entropy coefficient curve fitting adopts polynomial fitting, so that an open-circuit potential curve and an entropy coefficient curve are obtained.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for simultaneously measuring an open circuit potential curve and an entropy coefficient curve of an electrode material of a lithium ion battery.
Background
In the present society, problems such as environmental pollution and energy crisis become more serious, and the development and utilization of renewable energy sources become research hotspots of scientists in various countries, such as solar energy, tidal energy, geothermal energy and the like. However, these renewable energy sources generally cannot be directly used for social production, and chemical energy storage devices are required to be used as media, and the rise and development of new energy storage technologies and chemical energy storage devices provide a powerful guarantee for the practical application of new energy technologies. Among various chemical energy storage devices, lithium ion batteries have the advantages of high voltage platform, high energy density, high power density, small self-discharge rate, long cycle life, no memory effect, small environmental pollution and the like, and are widely applied to the fields of electronics, automobiles, communication, aerospace and the like.
The directions of life prediction, state diagnosis, thermal management and the like of lithium ion batteries are the research hotspots of current researchers in various countries, and most of the researches are established on the basis of a battery simulation model. The electrochemical model of the lithium ion battery can simulate the external characteristics of the battery such as voltage, current and the like, and can simulate some microcosmic physical quantities which are difficult to actually measure in the battery, so that the electrochemical model of the lithium ion battery is widely applied to the aspects of aging failure analysis, service life prediction and the like of the battery.
The electrode potential curve of the battery refers to the potential change curve of an electrode material caused by the change of the dissolution degree and the ion adsorption degree of the electrode surface when the electrode is in contact with electrolyte with different concentrations. The battery terminal voltage is equal to the battery open circuit voltage minus the battery polarization overpotential, so the acquisition of the electrode potential curve is particularly important for the simulation calculation of the electrochemical model. The entropy coefficient of the electrode is an important parameter in determining the reversible heat and the accurate thermal model. Therefore, the electrode entropy coefficient curve is determined, and the accurate description of the reversible heat has important significance for battery thermal modeling. Nowadays, most of electrode material open-circuit potential curves and entropy coefficient curves are the results in the references, and in specific use, electrode materials produced by different manufacturers may have individual differences. Therefore, it is necessary to accurately measure the open-circuit potential curve and the entropy coefficient curve of the battery electrode material.
Disclosure of Invention
The invention aims to solve the problem of poor battery simulation precision caused by inaccuracy of an open-circuit potential curve and an entropy coefficient curve of an electrode material, and provides a method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the electrode material of a lithium ion battery.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a method for simultaneously measuring an open-circuit potential curve and an entropy coefficient curve of an electrode material of a lithium ion battery comprises the following steps: disassembling a battery to be simulated, assembling the battery into a button type half battery, performing charge-discharge cyclic activation for 2-4 circles at room temperature, then performing charge or discharge (anode charge and cathode discharge) until the battery is fully charged or fully discharged, then charging and discharging fixed capacity (anode discharge and cathode charge) at the same current at room temperature, then sequentially standing at different temperatures, returning the battery to the fixed capacity at the same current at room temperature after standing, repeating the operation until the upper limit or the lower limit of specified voltage is reached, recording the voltage and the voltage difference at different temperatures, and then fitting an open-circuit potential curve and an entropy coefficient curve.
Further, the battery to be simulated is a 18650 battery, a pouch battery, a rectangular battery, or the like.
Further, the room temperature is 25 ℃, and the temperature error is controlled to be +/-1 ℃.
Further, the half-cell was charged or discharged at 25 ℃.
And further activating the half-cell in a charge-discharge cycle, wherein the number of cycles of the charge-discharge cycle is 2-4, and the charge-discharge current is 0.2-0.5C.
And further, charging and discharging (anode charging and cathode discharging) the half battery to full charge or full discharge, wherein the anode is charged by constant current and constant voltage, the upper voltage limit is larger than the upper limit of the simulation full battery, the charging current is 0.5-1C, the cut-off current is 0.02C, the lower voltage limit is 0.001V, and the discharging current is 0.02-0.05C.
Further, the half-cell is subjected to fixed charge and discharge capacity (positive electrode discharge and negative electrode charge), the SOC of the positive electrode per discharge is 10%, the SOC of the negative electrode per charging is 10%, and the charge and discharge current is 0.5-1C.
Further, standing the battery at different temperatures, and standing the battery from high to low according to the simulated temperature, wherein the standing time is more than 5 hours.
Further, the battery is repeatedly charged and discharged at normal temperature to fix the capacity (anode discharge and cathode charge), and stands at different temperatures until the anode discharge voltage is less than the simulation full voltage Chi Xiaxian and the cathode charge voltage reaches 1.5-2V, the operation is stopped, and the voltages and the voltage difference at different temperatures are recorded.
Further, for the voltages and voltage differences obtained by the battery at different temperatures, the open-circuit potential curve fitting adopts the combination of a tangent function and an exponential function, and the entropy coefficient curve fitting adopts polynomial fitting, so that an open-circuit potential curve and an entropy coefficient curve are obtained.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method can measure the open-circuit potential curve and the entropy coefficient curve of the anode and cathode materials of the battery under the condition that the battery material is unknown and only the upper and lower charge and discharge limits of the battery are known;
(2) The method is simple and convenient, does not need excessive equipment and operation, and can solve the entropy coefficient while measuring the open-circuit potential curve, thereby providing reliable information for the simulation and the thermal management of the battery;
(3) The open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material obtained by the invention are applied to an electrochemical model, and the battery simulation precision can be improved.
Drawings
Fig. 1 is a graph of open circuit potential of the lithium ion battery positive electrode material measured by the present invention.
Fig. 2 is a graph of open-circuit potential of the lithium ion battery negative electrode material measured by the present invention.
Fig. 3 is a graph of the entropy coefficient of the lithium ion battery positive electrode material measured by the present invention.
Fig. 4 is a graph of the entropy coefficient of the lithium ion battery negative electrode material measured by the present invention.
Fig. 5 is a comparison graph of time-voltage simulation data and measured values of constant current discharge of a lithium ion battery at 25 ℃ according to the present invention.
Fig. 6 is a comparison graph of time-voltage simulation data and an actual measurement value of constant current discharge of the lithium ion battery at 0 ℃ in the present invention.
Fig. 7 is a comparison graph of time-voltage simulation data and actual measurement values of constant current discharge of a lithium ion battery at-20 ℃ in accordance with the present invention.
Fig. 8 is a comparison graph of time-voltage simulation data and measured values of constant current discharge of a lithium ion battery at-40 ℃ in accordance with the present invention.
Fig. 9 is a comparison graph of temperature simulation data and actual measurement values of constant current discharge of the lithium ion battery at 25 ℃ according to the present invention.
Fig. 10 is a comparison graph of temperature simulation data and actual measurement values of constant current discharge of the lithium ion battery at 0 ℃ in the present invention.
Fig. 11 is a comparison graph of the temperature simulation data and the measured value of the constant current discharge of the lithium ion battery at-20 ℃ in the present invention.
Fig. 12 is a comparison graph of the temperature simulation data and the actual measurement value of the constant current discharge of the lithium ion battery at-40 ℃ in the invention.
Detailed Description
The present invention will be further described with reference to the following specific examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention applies the measured open-circuit curve and entropy coefficient curve of the battery material to an electrochemical model, and the applied model patent numbers are as follows: CN201510337596.9, name: the invention discloses a method for acquiring electrochemical and thermal coupling models of a lithium ion battery, and the method is proved by practical use and experimental verification that the open-circuit curve and the entropy coefficient curve measured by the method can well improve the precision of low-temperature simulation.
Example 1:
the 18650 lithium ion battery, the upper limit of charging is 4.4V, the lower limit of discharging is 3.0V, the rated capacity is 2400mAh, the battery positive pole is lithium cobaltate, the negative pole is graphite.
The method comprises the following steps: firstly, disassembling the battery, respectively assembling the disassembled positive and negative pole pieces into button half batteries, wherein the negative poles of the half batteries use lithium pieces, and each material is provided with five button half batteries.
Step two: and (2) standing the button half-cell at 25 ℃ for 8 hours, starting activation, and performing constant current charging and discharging on the positive electrode, wherein the upper limit is 4.5V, the lower limit is 3.0V, and the charging and discharging current is 0.5C, and the negative electrode is subjected to constant current charging and discharging, the upper limit is 1.5V, the lower limit is 0.001V, and the charging and discharging current is 0.5C.
Step three: and standing the battery after the cycle for 3 hours, and charging the positive electrode by adopting a constant current and a constant voltage, wherein the upper limit of the voltage is 4.5V, the charging current is 0.5C, and the cut-off current is 0.02C. The cathode adopts constant current discharge, the lower limit of voltage is 0.001V, and the discharge current is 0.05C.
Step four: and (3) standing the fully charged or fully discharged half battery for 5 hours at 25 ℃, then discharging the positive electrode by adopting a constant current, wherein the discharging current is 0.1 ℃ and the discharging time is 1 hour, charging the negative electrode by adopting a constant current, the charging current is 0.1 ℃ and the charging time is 1 hour.
Step five: the positive and negative electrodes were left at 25, 0, -20, -40 ℃ for 5 hours in turn, and the voltages at different temperatures were recorded.
Step six: and (3) repeatedly carrying out normal-temperature charging and discharging (anode discharging and cathode charging) on the half-cell, standing at different temperatures until the anode discharging voltage is less than 3.0V and the cathode charging voltage reaches 1.5V, stopping operation, and recording the open-circuit voltage at different discharging depths and the voltage difference at different temperatures.
Step seven: the open circuit voltages at different depths of discharge measured for the half cells were fitted using a combination of tangent and exponential functions (results are shown in figures 1-2).
Step eight: and fitting the voltage difference measured by the half cell at different temperatures by adopting a polynomial. (see FIGS. 3-4 for results).
Step nine: and applying the fitted positive and negative open-circuit potential curve and entropy coefficient curve to an electrochemical model. (the simulation results are shown in FIGS. 5-12).
Claims (10)
1. A method for simultaneously measuring an open circuit potential curve and an entropy coefficient curve of an electrode material of a lithium ion battery is characterized by comprising the following steps of: the method specifically comprises the following steps: disassembling a battery to be simulated, assembling the battery into a button type half battery, performing charge-discharge cyclic activation for 2-4 circles at room temperature, then performing charge or discharge (anode charge and cathode discharge) until the battery is fully charged or fully discharged, then charging and discharging fixed capacity (anode discharge and cathode charge) at the same current at room temperature, then sequentially standing at different temperatures, returning the battery to the fixed capacity at the same current at room temperature after standing, repeating the operation until the upper limit or the lower limit of specified voltage is reached, recording the voltage and the voltage difference at different temperatures, and then fitting an open-circuit potential curve and an entropy coefficient curve.
2. The method for simultaneously measuring an open-circuit potential curve and an entropy coefficient curve of an electrode material of a lithium ion battery according to claim 1, wherein the method comprises the following steps: the battery needing simulation is a 18650 battery, a soft package battery, a square battery and the like.
3. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: the room temperature is 25 ℃, and the temperature error is controlled to be +/-1 ℃.
4. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: and when the half battery is charged or discharged, the charging or discharging is carried out at 25 ℃.
5. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: and activating the half-cell in a charge-discharge cycle, wherein the number of cycles of the charge-discharge cycle is 2-4, and the charge-discharge current is 0.2-0.5C.
6. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: and (3) charging and discharging the half battery (charging the positive electrode and discharging the negative electrode) to full charge or full discharge, wherein the positive electrode is charged by constant current and constant voltage, the upper limit of the voltage is larger than the upper limit of the simulation full battery, the charging current is 0.5-1C, the cut-off current is 0.02C, the lower limit of the voltage is 0.001V, and the discharging current is 0.02-0.05C.
7. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: and (3) carrying out fixed charge-discharge capacity (positive electrode discharge and negative electrode charge) on the half-cell, wherein the SOC of the positive electrode at each discharge is 10%, the SOC of the negative electrode at each charging is 10%, and the charge-discharge current is 0.5-1C.
8. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: and standing the battery at different temperatures, and standing the battery from high temperature to low temperature according to the simulated temperature, wherein the standing time is more than 5 hours.
9. The method for simultaneously measuring the open-circuit potential curve and the entropy coefficient curve of the lithium ion battery electrode material according to claim 1, wherein the method comprises the following steps: and (3) repeatedly carrying out normal-temperature charging and discharging on the battery to fix the capacity (anode discharging and cathode charging), standing at different temperatures until the anode discharging voltage is less than the simulated full voltage Chi Xiaxian and the cathode charging voltage reaches 1.5-2V, stopping operation, and recording the voltages and voltage differences at different temperatures.
10. The method for simultaneously measuring an open-circuit potential curve and an entropy coefficient curve of an electrode material of a lithium ion battery according to claim 1, wherein the method comprises the following steps: for the voltages and voltage differences obtained by the battery at different temperatures, the open-circuit potential curve fitting adopts the combination of a tangent function and an exponential function, and the entropy coefficient curve fitting adopts polynomial fitting, so that an open-circuit potential curve and an entropy coefficient curve are obtained.
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Cited By (1)
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| CN116125310A (en) * | 2023-01-30 | 2023-05-16 | 上海玫克生储能科技有限公司 | Fitting method, fitting system, fitting equipment and fitting medium for lithium intercalation quantity of battery electrode |
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| CN116125310B (en) * | 2023-01-30 | 2023-10-20 | 上海玫克生储能科技有限公司 | Fitting method, fitting system, fitting equipment and fitting medium for lithium intercalation quantity of battery electrode |
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