CN110658469A - Method for evaluating exchange current density of lithium ion battery electrode - Google Patents
Method for evaluating exchange current density of lithium ion battery electrode Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 36
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 238000005056 compaction Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R19/00—Arrangements for measuring currents or voltages or for indicating presence or sign thereof
- G01R19/08—Measuring current density
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Abstract
The invention provides a method for evaluating the exchange current density of a lithium ion battery electrode, which comprises the following steps: placing the three-electrode batteries in a thermostat with a preset temperature value, and charging or discharging each three-electrode battery according to a preset current threshold value; standing the three-electrode battery for a preset time threshold, obtaining a U-t recovery curve of a test electrode of the three-electrode battery relative to a reference electrode within standing time, and performing first-order exponential fitting on the U-t recovery curve; the U-t recovery curve is a curve of voltage changing along with time in standing time; and solving according to the relation between the potential and the current density under the low overpotential to obtain the magnitude sequence of the electrode exchange current density of each three-electrode battery. The method for evaluating the exchange current density of the lithium ion battery electrodes can judge the exchange current density of the two battery electrodes only according to the voltage recovery curve in the charging and discharging process of the battery.
Description
Technical Field
The invention relates to the technical field of battery detection, in particular to a method for evaluating the exchange current density of a lithium ion battery electrode.
Background
Lithium ion batteries have been widely used as power sources for various portable electric appliances, and are an attractive power source for electric vehicles due to their advantages of high specific energy and long life. The charge and discharge capacity of the lithium ion battery is greatly related to the lithium desorption and insertion dynamic performance of the electrode material. The electrode exchange current density is an important parameter for representing the reversibility of electrode reaction and the dynamic performance of electrode lithium extraction, the physical meaning of the electrode exchange current density is the absolute value of the current density of anode reaction and cathode reaction which are carried out according to two reaction directions, the absolute value is mainly used for describing the electron gaining and losing capacity of an electrode material, and the size of the electrode exchange current density is influenced by temperature and is also related to the property of the electrode reaction and the electrode material. The larger the electrode exchange current density is, the stronger the current capacity participating in the redox reaction is, and the better the electrochemical reversible degree in the charging and discharging process is. Conversely, the weaker the current capability involved in the redox reaction, the poorer the degree of electrochemical reversibility during charging and discharging.
The current evaluation process of the electrode exchange current density of the battery is complex.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for evaluating the exchange current density of a lithium ion battery electrode.
The invention provides a method for evaluating the exchange current density of a lithium ion battery electrode, which comprises the following steps:
s1, arranging a battery to be tested on a reference electrode to form a three-electrode battery, and then placing the three-electrode battery in a thermostat with a preset temperature value, wherein each three-electrode battery is charged or discharged according to a preset current threshold value until the three-electrode battery reaches a preset charge threshold value;
s2, standing the three-electrode battery for a preset time threshold, obtaining a U-t recovery curve of a test electrode of the three-electrode battery relative to a reference electrode within standing time, and performing first-order exponential fitting on the U-t recovery curve; the U-t recovery curve is a curve of voltage changing along with time in standing time; the test electrode is the anode or the cathode of the battery to be tested;
s3, obtaining a J-t function of the electrode current density changing along with time according to a first-order exponential fitting formula of a U-t recovery curve, and obtaining the magnitude sequence of the electrode exchange current density of each three-electrode battery by solving the J-t function.
Preferably, in step S2, the first-order exponential fitting expression of the U-t recovery curve is:
y is a1 × exp (-x/t1) + y 0; wherein y is voltage, a1 is coefficient, x is time, t1 is time constant, and y0 is open circuit voltage;
in step S3, the J-t function is: J-J1 × exp (-x/t 1); j is the current density, J1Is the initial current density.
Preferably, step S3 specifically includes: calculating reference values J0/J1 of the current density of each electrode to be tested according to a first-order exponential fitting expression, and comparing the reference values J0/J1 to obtain the magnitude sequence of the electrode exchange current density of each three-electrode battery, wherein J is0The current density is exchanged for the electrodes.
Preferably, in step S3, the electrode sheet size, the particle type, the area density, the compaction, and the electrode exchange current density of the three-electrode battery with the corresponding current threshold and the preset temperature value all being consistent are compared according to the solution result.
Preferably, in step S1, the battery to be tested includes a capacity type battery cell and/or a power type battery cell.
Preferably, in step S1, the battery to be tested includes one or more of a pouch battery, a square battery, a cylindrical battery, a ternary battery and an iron-lithium battery.
Preferably, in step S1, the current threshold is X, and 0C < X < 1C.
Preferably, in step S2, voltage detection is performed once every interval t0 during the standing time of the three-electrode battery to obtain a U-t recovery curve, wherein 0.001S is less than or equal to t0 is less than or equal to 5S.
Preferably, in step S1, the preset temperature value is 25 degrees.
Preferably, in step S2, the time threshold is 1 h.
The method for evaluating the exchange current density of the lithium ion battery electrodes can judge the exchange current density of the two battery electrodes only according to the voltage recovery curve in the charging and discharging process of the battery.
Compared with the complexity of the traditional electrode exchange current density test method, the method is simple and easy to implement, and has good application prospect in the test of the battery electrode exchange current density.
Drawings
FIG. 1 is a flow chart of a method for evaluating the exchange current density of an electrode of a lithium ion battery according to the present invention;
FIG. 2 is a schematic diagram of a U-t recovery curve and a corresponding fitted curve for a power 43Ah cell;
FIG. 3 is a schematic diagram of a U-t recovery curve and corresponding fitted curve for a volumetric 50Ah cell;
fig. 4 is a schematic diagram of a U-t recovery curve and a corresponding fitted curve for a power type 10Ah cell.
Detailed Description
Referring to fig. 1, the method for evaluating the magnitude of the electrode exchange current density of the lithium ion battery according to the present invention includes.
And S1, arranging a reference electrode on the battery to be tested to form a three-electrode battery, then placing the three-electrode battery in a constant temperature box with a preset temperature value, and charging or discharging each three-electrode battery according to a preset current threshold until the three-electrode battery reaches a preset charge threshold.
Specifically, in the present embodiment, in order to further ensure the stability of the battery state, the battery may be charged to full charge and then recharged to a predetermined charge threshold.
Specifically, in the present embodiment, the charge threshold is a value in the interval [ 10% SOC, 90% SOC ]. In the present embodiment, the current threshold is X, and 0C < X < 1C.
S2, standing the three-electrode battery for a preset time threshold, obtaining a U-t recovery curve of a test electrode of the three-electrode battery relative to a reference electrode within standing time, and performing first-order exponential fitting on the U-t recovery curve; the U-t recovery curve is a curve of voltage changing along with time in standing time; the test electrode is the positive electrode or the negative electrode of the battery to be tested.
In step S2, voltage detection is carried out once every interval t0 within the standing time of the three-electrode battery to obtain a U-t recovery curve, wherein t0 is more than or equal to 0.001S and less than or equal to 5S.
Specifically, in the present embodiment, the time threshold is 1 h.
S3, obtaining a J-t function of the electrode current density changing along with time according to a first-order exponential fitting formula of a U-t recovery curve, and obtaining the magnitude sequence of the electrode exchange current density of each three-electrode battery by solving the J-t function.
Specifically, in step S2 of the present embodiment, the first-order exponential fitting expression of the U-t recovery curve is:
y is a1 × exp (-x/t1) + y 0; where y is voltage, a1 is coefficient, x is time, t1 is time constant, and y0 is open circuit voltage.
In step S3, the J-t function is: J-J1 × exp (-x/t 1); j is the current density, J1Is the initial current density.
Specifically, when the current density of the electrode is tested,
wherein: r is the gas constant, F is the Faraday constant, T is the temperature, J0The current density is exchanged for the electrodes. That is to say that the first and second electrodes,u-y-0; thus, the values of J0/J1 can be obtained according to the fitting coefficient A1. Since the charge/discharge rates are consistent and the polarization ratios are consistent, the magnitude of the electrode exchange current density of the three-electrode battery can be compared according to the magnitude of J0/J1.
Specifically, step S3 is: calculating the current density reference value J0/J1 of each electrode to be tested according to a first-order exponential fitting expression, and comparing the current density reference values J0/J1 to obtain the magnitude sequence of the electrode exchange current density of each three-electrode battery, wherein J is0The current density is exchanged for the electrodes.
In step S3 of the present embodiment, the electrode exchange current density of the three-electrode battery in which the size, the type, the area density, and the compaction of the electrode sheet, and the corresponding current threshold value and the preset temperature value are all consistent is compared according to the solution result. That is, for a three-electrode battery with electrode current exchange density comparison in the same batch, the size of the electrode piece, the type of particles, the area density, the compaction, and the corresponding current threshold and the preset temperature value must be kept consistent, so as to ensure the measurement accuracy of the electrode current exchange density.
The method for evaluating the electrode exchange current density of the lithium ion battery provided by the invention is classified according to the types of the batteries, and the battery to be tested comprises a capacity type battery cell and/or a power type battery cell; the battery to be tested comprises one or more of a soft package battery, a square battery, a cylindrical battery, a ternary battery and a lithium iron battery according to the classification of the battery core types.
The invention is further explained below with reference to two specific examples.
Example 1
In this embodiment, the preset temperature value is 25 degrees, and the battery to be tested includes a power type 43Ah battery cell and a capacity type 50Ah battery cell.
In this embodiment, the method specifically includes the following steps:
s1, arranging a battery to be tested on a reference electrode to form a three-electrode battery, placing the three-electrode battery in a constant temperature box at 25 ℃, connecting each three-electrode battery to a charging cabinet, and discharging the three-electrode battery to 50% SOC (state of charge) at 0.1C after charging to 4.2V;
s2, standing the three-electrode battery for 1h, obtaining a U-t recovery curve of the test electrode of the three-electrode battery relative to the reference electrode within standing time, and performing first-order exponential fitting on the U-t recovery curve. In this embodiment, the test electrode is the positive electrode of the battery to be tested.
The first order exponential fit expression of the U-t recovery curve is:
y is a1 × exp (-x/t1) + y 0; where y is voltage, a1 is coefficient, x is time, t1 is time constant, and y0 is open circuit voltage.
Specifically, in this embodiment, U-t recovery curves of the positive electrodes corresponding to the power type 43Ah cell and the capacity type 50Ah cell with respect to the reference electrode are respectively shown in fig. 2 and fig. 3.
S3, obtaining a J-t function of the electrode current density changing along with time according to a first-order exponential fitting formula of a U-t recovery curve, and obtaining the magnitude sequence of the electrode exchange current density of each three-electrode battery by solving the J-t function.
The J-t function is: J-J1 × exp (-x/t 1); j is the current density, J1Is the initial current density.
Specifically, in this embodiment, the parameters of the power type 43Ah cell and the capacity type 50Ah cell are shown in the following table:
table one: parameter Table shown in example 1
As can be seen, in this embodiment, the electrode exchange current density of the 43Ah power cell is greater than that of the 50Ah capacity cell, which indicates that the 43Ah power cell has stronger dynamic performance.
Example 2
In this embodiment, the preset temperature value is 25 degrees, and the battery to be tested includes a power type 43Ah battery cell and a power type 10Ah battery cell.
In this embodiment, the method specifically includes the following steps:
s1, arranging a battery to be tested on a reference electrode to form a three-electrode battery, placing the three-electrode battery in a constant temperature box at 25 ℃, connecting each three-electrode battery to a charging cabinet, and discharging the three-electrode battery to 50% SOC (state of charge) at 0.1C after charging to 4.2V;
s2, standing the three-electrode battery for 1h, obtaining a U-t recovery curve of the test electrode of the three-electrode battery relative to the reference electrode within standing time, and performing first-order exponential fitting on the U-t recovery curve. The test electrode is the anode of the battery to be tested.
The first order exponential fit expression of the U-t recovery curve is:
y is a1 × exp (-x/t1) + y 0; where y is voltage, a1 is coefficient, x is time, t1 is time constant, and y0 is open circuit voltage.
Specifically, in this embodiment, U-t recovery curves corresponding to the power type 10Ah cell are respectively shown in fig. 4.
S3, obtaining a J-t function of the electrode current density changing along with time according to a first-order exponential fitting formula of a U-t recovery curve, and obtaining the magnitude sequence of the electrode exchange current density of each three-electrode battery by solving the J-t function.
The J-t function is: J-J1 × exp (-x/t 1); j is the current density, J1Is the initial current density.
Specifically, in this embodiment, the parameters of the power type 43Ah cell and the power type 10Ah cell are shown in the following table:
table two: example 2 parameter Table
As can be seen, in this embodiment, the electrode exchange current density of the 43Ah power cell is greater than that of the 10Ah capacity cell, which indicates that the 43Ah power cell has stronger dynamic performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (10)
1. A method for evaluating the magnitude of the electrode exchange current density of a lithium ion battery is characterized by comprising the following steps:
s1, arranging a battery to be tested on a reference electrode to form a three-electrode battery, and then placing the three-electrode battery in a thermostat with a preset temperature value, wherein each three-electrode battery is charged or discharged according to a preset current threshold value until the three-electrode battery reaches a preset charge threshold value;
s2, standing the three-electrode battery for a preset time threshold, obtaining a U-t recovery curve of a test electrode of the three-electrode battery relative to a reference electrode within standing time, and performing first-order exponential fitting on the U-t recovery curve; the U-t recovery curve is a curve of voltage changing along with time in standing time; the test electrode is the anode or the cathode of the battery to be tested;
s3, obtaining a J-t function of the electrode current density changing along with time according to a first-order exponential fitting formula of a U-t recovery curve, and obtaining the magnitude sequence of the electrode exchange current density of each three-electrode battery by solving the J-t function.
2. The method for evaluating the magnitude of the electrode exchange current density of the lithium ion battery according to claim 1, wherein in step S2, the first-order exponential fitting expression of the U-t recovery curve is as follows:
y is a1 × exp (-x/t1) + y 0; wherein y is voltage, a1 is coefficient, x is time, t1 is time constant, and y0 is open circuit voltage;
in step S3, the J-t function is: J-J1 × exp (-x/t 1); j is the current density, J1Is the initial current density.
3. The method according to claim 2, wherein the step S3 is specifically as follows: calculating the current density reference value J0/J1 of each electrode to be tested according to a first-order exponential fitting expression, and comparing the current density reference values J0/J1 to obtain the magnitude sequence of the electrode exchange current density of each three-electrode battery, wherein J is0The current density is exchanged for the electrodes.
4. The method for evaluating the magnitude of the electrode exchange current density of the lithium ion battery according to claim 1, wherein in step S3, the electrode exchange current densities of the three-electrode battery with the same electrode piece size, particle type, area density, compaction and corresponding current threshold and preset temperature value are compared according to the solution result.
5. The method of claim 1, wherein in step S1, the battery to be tested includes capacity cells and/or power cells.
6. The method for evaluating the magnitude of the electrode exchange current density of the lithium ion battery according to claim 1, wherein in step S1, the battery to be tested comprises one or more of a pouch battery, a prismatic battery, a cylindrical battery, a ternary battery and an iron lithium battery.
7. The method for evaluating the magnitude of the electrode exchange current density of a lithium ion battery according to claim 1, wherein in step S1, the current threshold is X, and 0C < X < 1C.
8. The method of claim 1, wherein in step S2, voltage detection is performed at intervals of t0 during the standing time of the three-electrode battery to obtain a U-t recovery curve, wherein t0 is less than or equal to 0.001S and less than or equal to 5S.
9. The method according to claim 1, wherein the preset temperature value is 25 degrees in step S1.
10. The method for evaluating the magnitude of the electrode exchange current density of a lithium ion battery according to any one of claims 1 to 9, wherein in step S2, the time threshold is 1 h.
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