CN113659245B - Electrochemical device heating method, electrochemical device and electric equipment - Google Patents
Electrochemical device heating method, electrochemical device and electric equipment Download PDFInfo
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- CN113659245B CN113659245B CN202110919695.3A CN202110919695A CN113659245B CN 113659245 B CN113659245 B CN 113659245B CN 202110919695 A CN202110919695 A CN 202110919695A CN 113659245 B CN113659245 B CN 113659245B
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
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- H01M10/615—Heating or keeping warm
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- H—ELECTRICITY
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The embodiment of the application provides an electrochemical device heating method, an electrochemical device and electric equipment, which comprise the following steps: obtaining an impedance-current frequency change relation of the electrochemical device at a first temperature, and determining a pulse current frequency based on the impedance-current frequency change relation; determining the lithium deposition rate and the lithium deposition potential of the negative electrode of the electrochemical device at a first temperature; obtaining a plurality of initial current amplitudes; the method comprises the steps of obtaining a plurality of cathode lowest potentials and a plurality of cathode impedances based on a first temperature, a first SOC, a pulse current frequency and a plurality of initial current amplitudes, determining a lithium precipitation potential difference and correcting the current amplitudes based on the cathode lowest potentials, the cathode impedances and the cathode lithium precipitation potentials, and improving the lithium precipitation phenomenon of the electrochemical device during self-heating.
Description
Technical Field
The present disclosure relates to the field of electrochemical technologies, and in particular, to a method for heating an electrochemical device, and an electrical apparatus.
Background
Lithium ion batteries have many advantages of high specific energy density, long cycle life, high nominal voltage, low self-discharge rate, small size, light weight, and the like, and are widely used in various fields including electric bicycles, electric vehicles, and the like. However, the lithium ion battery is sensitive to the temperature of the use environment, and when the temperature is low, the dischargeable capacity, the discharge power and other performances of the lithium ion battery are reduced, so that the lithium ion battery needs to be heated to be beneficial to use in the low-temperature environment.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for heating an electrochemical device, and an electric apparatus, which can improve a lithium deposition phenomenon during self-heating of the electrochemical device.
A first aspect of an embodiment of the present application provides a method for heating an electrochemical device, the method including obtaining an impedance-current frequency variation relationship of the electrochemical device at a first temperature, and determining a pulse current frequency based on the impedance-current frequency variation relationship; determining the lithium evolution rate and the lithium evolution potential of the negative electrode of the electrochemical device at the first temperature; obtaining a plurality of initial current amplitudes, wherein the charging multiplying power corresponding to the initial current amplitudes is larger than the lithium precipitation multiplying power; based on the first temperature, the first SOC, the pulse current frequency and a plurality of the initial current amplitude, obtaining a plurality of negative electrode minimum potentials and a plurality of negative electrode impedances, and based on the negative electrode minimum potentials, the negative electrode impedances and the negative electrode lithium-analyzing potential, determining a lithium-analyzing potential difference and correcting the current amplitude.
The embodiment of the application comprises the following technical effects: according to the embodiment of the application, the pulse current frequency is determined based on the obtained impedance-current frequency change relation at the first temperature, the lithium precipitation multiplying power and the negative lithium precipitation potential of the electrochemical device at the first temperature are determined, and then the lithium precipitation potential difference and the correction current amplitude are determined, so that the initial current amplitude is corrected by using the correction current amplitude, and the lithium precipitation phenomenon of the electrochemical device during self-heating is improved.
In one embodiment, after determining the lithium evolution potential difference and correcting the current amplitude, the method further comprises correcting the initial current amplitude by using the corrected current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude, so as to improve the lithium evolution phenomenon of the electrochemical device during self-heating.
In one embodiment, the step of determining the pulse current frequency based on the impedance-current frequency variation relationship includes determining a plurality of current frequencies having an impedance decreasing rate of 40% to 80% as the pulse current frequency based on the impedance-current frequency variation relationship, so that the heating power of the electrochemical device is increased to rapidly increase the temperature, thereby improving the heating efficiency.
In one embodiment, said determining a lithium evolution rate and a negative electrode lithium evolution potential of the electrochemical device at said first temperature comprises, at said first temperature, said electrochemical device performing a plurality of charge tests at different charge rates and acquiring a plurality of negative electrode potentials of said electrochemical device during said charge tests to determine said negative electrode lithium evolution potential and said lithium evolution rate at which lithium evolution of said electrochemical device occurs. According to the embodiment of the application, the lithium precipitation potential and the lithium precipitation rate of the negative electrode of the electrochemical device can be determined, and the risk of lithium precipitation of the electrochemical device in the self-heating process is favorably reduced.
In one embodiment, said step of obtaining a plurality of negative minimum potentials, a plurality of negative impedances based on said first temperature, first SOC, said pulse current frequency and a plurality of said initial current amplitudes comprises grouping a plurality of different initial current amplitudes and pulse current frequencies into a plurality of test sets; carrying out pulse charging heating test on the electrochemical device according to the pulse current frequency and the initial current amplitude of each test group to obtain the minimum negative potential, the negative potential drop and the pulse current amplitude of each test group; and obtaining the cathode impedance according to the cathode potential drop and the pulse current amplitude of each test group.
The method and the device can determine the cathode lowest potential, the cathode potential drop and the cathode impedance of the electrochemical device, and provide a basis for subsequently determining the corrected current amplitude.
In one embodiment, the determining a lithium evolution potential difference and the correcting the current magnitude based on the negative electrode minimum potential, the negative electrode impedance, and the negative electrode lithium evolution potential comprises determining the lithium evolution potential difference as a difference between the negative electrode minimum potential and the negative electrode lithium evolution potential; and determining the correction current amplitude according to the ratio of the lithium analysis potential difference to the negative impedance. The correction current amplitude can be obtained, the correction current amplitude can be used for correcting the initial current amplitude when correction is needed, and therefore the lithium precipitation phenomenon of the electrochemical device during self-heating is improved.
In one embodiment, the correcting the initial current amplitude by using the correction current amplitude and the pulse charging heating the electrochemical device by using the first current amplitude comprises adding the initial current amplitude and the correction current amplitude when the correction current amplitude is a positive value to obtain the first current amplitude, and performing the pulse charging heating on the electrochemical device by using the first current amplitude; and when the correction current amplitude is a negative value, subtracting the correction current amplitude from the initial current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude. According to the embodiment of the application, the initial current amplitude value is corrected through the correction current amplitude value, so that the lithium separation phenomenon of the electrochemical device during self-heating is improved.
In one embodiment, the first temperature comprises any one of-10 ℃, -20 ℃, or-30 ℃, and the first SOC comprises any one of 0-percent SOC, 50-percent SOC, or 100-percent SOC.
A second aspect of the present application provides an electrochemical device, including a pulse current frequency determining module, a lithium precipitation determining module, a current amplitude obtaining module, and a correction current amplitude determining module, where the pulse current frequency determining module is configured to obtain an impedance-current frequency variation relationship of the electrochemical device at a first temperature, and determine a pulse current frequency based on the impedance-current frequency variation relationship; the lithium evolution determining module is used for determining the lithium evolution multiplying power and the negative electrode lithium evolution potential of the electrochemical device at the first temperature; the current amplitude acquisition module is used for acquiring a plurality of initial current amplitudes, and the charging multiplying power corresponding to the initial current amplitudes is larger than the lithium precipitation multiplying power; the correction current amplitude determination module is configured to obtain a plurality of negative electrode minimum potentials and a plurality of negative electrode impedances based on the first temperature, the first SOC, the pulse current frequency, and the plurality of initial current amplitudes, and determine a lithium battery potential difference and a correction current amplitude based on the negative electrode minimum potentials, the negative electrode impedances, and the negative electrode lithium battery potential difference. According to the embodiment of the application, the pulse current frequency is determined based on the obtained impedance-current frequency change relation at the first temperature, the lithium precipitation multiplying power and the negative lithium precipitation potential of the electrochemical device at the first temperature are determined, and then the lithium precipitation potential difference and the correction current amplitude are determined, so that the initial current amplitude is corrected by using the correction current amplitude, and the lithium precipitation phenomenon of the electrochemical device during self-heating is improved.
In one embodiment, the device further comprises a heating module, which is used for correcting the initial current amplitude value by using the corrected current amplitude value to obtain a first current amplitude value, and performing pulse charging heating on the electrochemical device by using the first current amplitude value to improve the lithium separation phenomenon of the electrochemical device during self-heating.
In one embodiment, the pulse current frequency determining module is specifically configured to determine a plurality of current frequencies with impedance reduction rates of 40% to 80% as the pulse current frequency based on the impedance-current frequency variation relationship, so that the heating power of the electrochemical device can be increased, the temperature can be increased rapidly, and the heating efficiency can be improved.
In one embodiment, the lithium deposition determining module is specifically configured to perform a plurality of charging tests on the electrochemical device at the first temperature by using different charging rates, and obtain a plurality of negative electrode potentials of the electrochemical device during the charging tests to determine the negative electrode lithium deposition potential and the lithium deposition rate at which lithium deposition occurs in the electrochemical device, so as to reduce the risk of lithium deposition during self-heating of the electrochemical device.
In one embodiment, the correction current amplitude determination module is specifically configured to group a plurality of different initial current amplitudes and pulse current frequencies into a plurality of test groups; carrying out pulse charging heating test on the electrochemical device according to the pulse current frequency and the initial current amplitude of each test group to obtain the minimum negative potential, the negative potential drop and the pulse current amplitude of each test group; and obtaining the cathode impedance according to the cathode potential drop and the pulse current amplitude of each test group, and providing a basis for subsequently determining the correction current amplitude.
In one embodiment, the correction current magnitude determination module is specifically configured to: determining the lithium-analysis potential difference according to the difference value between the lowest potential of the negative electrode and the lithium-analysis potential of the negative electrode; and determining the correction current amplitude according to the ratio of the lithium-separation potential difference to the negative electrode impedance, and correcting the initial current amplitude by using the correction current amplitude when correction is needed, so that the lithium-separation phenomenon of the electrochemical device during self-heating is improved.
In one embodiment, the heating module is specifically configured to, when the correction current amplitude is a positive value, add an initial current amplitude to the correction current amplitude to obtain the first current amplitude, and perform pulse charging heating on the electrochemical device by using the first current amplitude; and when the correction current amplitude is a negative value, subtracting the correction current amplitude from the initial current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude. According to the embodiment of the application, the initial current amplitude value is corrected through the correction current amplitude value, so that the lithium separation phenomenon of the electrochemical device during self-heating is improved.
According to a third aspect of the embodiments of the present application, there is provided an electric device, comprising a processor and a machine-readable storage medium, wherein the electrochemical device according to the second aspect improves lithium deposition during self-heating of the electrochemical device.
The embodiment of the application provides an electrochemical device heating method, an electrochemical device and electric equipment, wherein pulse current frequency is determined based on an obtained impedance-current frequency change relation at a first temperature, lithium precipitation rate and negative lithium precipitation potential of the electrochemical device at the first temperature are determined, after a plurality of initial current amplitudes are obtained, a plurality of negative electrode minimum potentials and a plurality of negative electrode impedances are obtained based on the first temperature, a first SOC, the pulse current frequency and the plurality of initial current amplitudes, a lithium precipitation potential difference and a correction current amplitude are determined based on the negative electrode minimum potentials, the negative electrode impedances and the negative electrode lithium precipitation potential, and the initial current amplitude is corrected by using the correction current amplitude, so that the lithium precipitation phenomenon of the electrochemical device during self-heating is improved, the electrochemical device is enabled to be heated quickly and safely in a cold environment, and the electrochemical device is more beneficial to being used in the cold environment. Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Drawings
In order to illustrate the technical solutions of the present application and the prior art more clearly, the following briefly introduces examples and figures that need to be used in the prior art, it being obvious that the figures in the following description are only some examples of the present application.
FIG. 1 is a schematic flow chart of a method for heating an electrochemical device according to an embodiment of the present disclosure;
FIG. 2 is a graph of impedance versus current frequency for one embodiment of the present application;
FIG. 3a is a schematic view of another test set in one embodiment of the present application;
FIG. 3b is a schematic illustration of a test panel in one embodiment of the present application;
FIG. 4 is a schematic structural diagram of an electrochemical device provided in an embodiment of the present application;
fig. 5 is a schematic structural diagram of an electric device according to an embodiment of the present disclosure;
fig. 6 is a schematic structural diagram of a charger according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below with reference to the accompanying drawings and examples. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other technical solutions obtained by a person of ordinary skill in the art based on the embodiments in the present application belong to the scope of protection of the present application.
In the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery.
In the process of implementing the present application, the inventors of the present application found that, in the related art, lithium separation easily occurs in a self-heating method for a lithium ion battery, and a potential and a charging rate at which lithium separation does not occur in the lithium ion battery cannot be determined.
In view of the above, the present disclosure provides a method for heating an electrochemical device, as shown in fig. 1, the method including the steps of:
s101: acquiring an impedance-current frequency change relation of the electrochemical device at a first temperature, and determining a pulse current frequency based on the impedance-current frequency change relation;
the execution main body of the embodiment of the application can be an electrochemical device, and can also be electric equipment containing the electrochemical device, such as a two-wheel vehicle, an unmanned aerial vehicle and the like, and can also be an external charger or test equipment.
In the embodiment of the present application, for example, when the executing body is an electrochemical device, the electrochemical device may acquire a change relationship of impedance-current frequency thereof at a first temperature. In one example, the storage medium of the electrochemical device stores the impedance-current frequency variation relationship at a first temperature in advance, and the electrochemical device can read the impedance-current frequency variation relationship to determine the pulse current frequency.
The Impedance-current frequency variation relationship can be obtained based on Electrochemical Impedance Spectroscopy (EIS) tests. Specifically, electrochemical Impedance Spectroscopy (EIS) tests can be performed on various types of Electrochemical devices at a first temperature in advance, wherein the EIS tests are performed by applying an alternating current potential wave with different frequencies and small amplitude to the Electrochemical devices, and measuring the change of the ratio of the alternating current potential to the current signal along with the frequency of a sine wave, so that the electrode process dynamics of the Electrochemical devices are analyzed, and the Impedance-current frequency change relation of the various types of Electrochemical devices at the first temperature is obtained.
The obtained impedance-current frequency variation relationship may be stored in a storage medium of an electrochemical device, an electric device, an external charger, or a testing device, and may be embodied in a curve form or a table form, and the embodiment of the present application is not particularly limited. In one example, referring to fig. 2, the impedance-current frequency variation is represented by an impedance-current frequency variation curve in which the abscissa is the current frequency in Hz and the ordinate is the impedance in m Ω, reflecting the relationship between the impedance of the electrochemical device and the current frequency.
S102: determining the lithium precipitation rate and the lithium precipitation potential of the negative electrode of the electrochemical device at a first temperature;
the embodiment of the application can perform a charging test on the electrochemical device at the first temperature, so as to determine the lithium evolution rate and the lithium evolution potential of the negative electrode of the electrochemical device at the first temperature. In one example, the electrochemical device was subjected to a charge test at-30 ℃ at a charge rate of 1C (rate) and 2C, respectively, while the potential of the negative electrode of the electrochemical device was monitored. If no lithium is separated during the 1C charging test and lithium is separated during the 2C charging test, the lithium separation rate can be determined to be between 1C and 2C. At this time, the lithium deposition rate may be determined continuously according to a compromise search method, for example, the charging test is performed at a charging rate of 1.5C, and if lithium is not deposited during the 1.5C charging test, the charging test is performed continuously at 1.75C. If the 1.75C charging test is used for lithium precipitation, the 1.75C is determined as the lithium precipitation rate, and the corresponding lithium precipitation potential is the negative electrode lithium precipitation potential. If lithium is separated at a plurality of charge multiplying powers, the minimum charge multiplying power is the lithium separation multiplying power, and the corresponding negative electrode potential is the negative electrode lithium separation potential and is marked as Va0.
S103: acquiring a plurality of initial current amplitudes;
according to the embodiment of the application, a plurality of initial current amplitudes can be obtained, and the charging multiplying power corresponding to the initial current amplitudes is larger than the lithium precipitation multiplying power. The plurality of initial current magnitudes may be pre-generated at a first interval value, e.g., 1A (amperes), 1.5A, 2A. The first interval value may be 0.5, 1, 2, 3, or any point value in between. The lithium deposition rate may be a charging rate corresponding to the occurrence of lithium deposition in the electrochemical device, and is generally related to a temperature and an initial SOC (State of Charge) of the electrochemical device.
S104: obtaining a plurality of cathode lowest potentials and a plurality of cathode impedances based on the first temperature, the first SOC, the pulse current frequency and the plurality of initial current amplitudes, and determining a lithium-deposition potential difference and a correction current amplitude based on the cathode lowest potentials, the cathode impedances and the cathode lithium-deposition potential.
After obtaining a plurality of initial current amplitudes, determining the pulse current frequency, under first temperature and first SOC, can utilize a plurality of initial current amplitudes and a plurality of pulse current frequency to carry out pulse charging heating test to electrochemical device respectively to obtain a plurality of negative pole minimum potential and a plurality of negative pole impedance, wherein, negative pole minimum potential has a one-to-one corresponding relation with the negative pole impedance. The negative electrode lowest potential of the embodiment of the application can represent the negative electrode potential condition under the test condition, and is used for being compared with the negative electrode lithium precipitation potential, and the negative electrode impedance can represent the negative electrode impedance under the test condition and is used for calculating the adjustable current amplitude.
After obtaining the plurality of negative electrode minimum potentials and the plurality of negative electrode impedances, the lithium-analysis potential difference and the correction current amplitude can be calculated based on the negative electrode minimum potentials, the negative electrode impedances and the negative electrode lithium-analysis potentials. In the embodiment of the present application, if a plurality of negative minimum potentials exist in a first SOC, the minimum negative minimum potential may be selected, and the correction current amplitude may be calculated. Illustratively, if there are a plurality of negative electrode lowest potentials, negative electrode lowest potential a, negative electrode lowest potential B, negative electrode lowest potential C, respectively, at 0% soc, where negative electrode lowest potential a is the smallest, negative electrode lowest potential a is selected, and the correction current amplitude of negative electrode lowest potential a is calculated.
The lithium-separating potential difference represents a difference value between the lowest potential of the negative electrode and the lithium-separating potential of the negative electrode, and the initial current amplitude value is corrected by using the correction current amplitude value, so that the temperature of the electrochemical device can be increased at a high temperature-rising rate, and the lithium-separating phenomenon of the electrochemical device is improved.
In an alternative embodiment, after step S104, the method for heating an electrochemical device according to the embodiment of the present application may further include:
and correcting the initial current amplitude by using the correction current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude.
After the corrected current amplitude is obtained, the corrected current amplitude can be used for correcting the initial current amplitude to obtain a first current amplitude, namely the corrected current amplitude, and then the electrochemical device is subjected to pulse charging heating by using the first current amplitude, so that the lithium separation phenomenon of the electrochemical device during self-heating is improved.
The electrochemical device heating method provided by the embodiment of the application determines pulse current frequency based on the acquired impedance-current frequency change relationship at the first temperature, determines lithium precipitation multiplying power and a negative lithium precipitation potential of the electrochemical device at the first temperature, obtains a plurality of negative electrode minimum potentials and a plurality of negative electrode impedances based on the first temperature, the first SOC, the pulse current frequency and the plurality of initial current amplitudes after acquiring the plurality of initial current amplitudes, and determines a lithium precipitation potential difference and a correction current amplitude based on the negative electrode minimum potentials, the negative electrode impedances and the negative lithium precipitation potential, so that the initial current amplitude is corrected by using the correction current amplitude, the lithium precipitation phenomenon of the electrochemical device during self-heating is improved, the electrochemical device is enabled to be rapidly and safely heated in a cold environment, and the electrochemical device is more beneficial to being used in the cold environment.
In an optional embodiment, step S101 specifically includes:
a plurality of current frequencies having an impedance falling rate of 40% to 80% are determined as the pulse current frequencies based on the impedance-current frequency change relationship.
The inventors of the present application have found that, when an electrochemical device is charged using a current frequency having an impedance drop rate of 40% to 80% as a pulse current frequency, the heating power of the electrochemical device can be increased to rapidly increase the temperature, thereby improving the heating efficiency. For example, 0.5Hz and 1Hz may be selected as the pulse current frequency.
In an optional embodiment, step S102 specifically includes:
at a first temperature, the electrochemical device is tested for multiple times through different charging multiplying factors, and multiple negative electrode potentials of the electrochemical device in the charging test process are obtained, so that the lithium precipitation potential and the lithium precipitation multiplying factor of the negative electrode of the electrochemical device, at which lithium precipitation occurs, are determined.
The embodiment of the application can carry out multiple charging tests on the electrochemical device at a first temperature by adopting different charging rates. Illustratively, the electrochemical device was subjected to a charge test at-30 ℃ at a charge rate of 1C for 10 cycles; the electrochemical device was subjected to a charge test at-30 ℃ at a charge rate of 1.5C for 10 cycles. The negative electrode potential of the electrochemical device can be monitored in real time and recorded in the testing process, so that the negative electrode potentials of the electrochemical device in the charging testing process can be obtained.
Some of the electrochemical devices were subjected to a charge test and lithium evolution occurred. In this case, the negative electrode potential corresponding to the occurrence of lithium deposition in the electrochemical device in which lithium deposition occurs can be determined as the negative electrode lithium deposition potential, and the corresponding charge rate can be determined as the lithium deposition rate. When a plurality of electrochemical devices are used for lithium separation, the lithium separation rate is the minimum charging rate, and the negative electrode potential corresponding to the lithium separation rate is the negative electrode lithium separation potential. The method for detecting lithium deposition is not particularly limited, and any method commonly used in the art may be used as long as it can detect the occurrence of lithium deposition in an electrochemical device. According to the embodiment of the application, the lithium precipitation potential and the lithium precipitation rate of the negative electrode of the electrochemical device can be determined, and the risk of lithium precipitation of the electrochemical device in the self-heating process is favorably reduced.
In an alternative embodiment, the step of obtaining a plurality of negative minimum potentials and a plurality of negative impedances based on the first temperature, the first SOC, the pulse current frequency, and the plurality of initial current amplitudes may comprise:
A. forming a plurality of different initial current amplitudes and pulse current frequencies into a plurality of test groups;
for example, when the initial current amplitude is 3 and the pulse current frequency is 2, each pulse current frequency corresponds to 3 test groups, and 6 test groups can be formed.
FIG. 3a is a schematic diagram of test sets in an embodiment of the present application, referring to FIG. 3a, which records that the first temperature is-30 deg.C, the first SOC is 0% SOC and 100% SOC, respectively, the pulse current frequency is 1Hz and 0.5Hz, respectively, the initial current amplitude is 6A (corresponding to 1C), 9A (corresponding to 1.5C), 12A (corresponding to 2C), respectively, and each first SOC comprises 6 test sets. Also recorded in figure 3a are the temperature rise, rate of temperature rise, anode minimum potential, anode charge initiation potential, anode potential drop and anode impedance of the electrochemical devices in each test set, where the anode minimum potential, anode charge initiation potential and anode potential drop are the cathode minimum potential, cathode charge initiation potential and cathode potential drop, respectively, of the electrochemical devices. In the pulse charging self-heating test process, the temperature and the negative electrode potential of the electrochemical device can be monitored through sensors such as a temperature sensor or a voltage sensor to obtain the lowest potential of the negative electrode and the negative electrode potential drop, the terminal voltage of the electrochemical device can be monitored simultaneously to assist in judging whether the pulse charging self-heating test is abnormal or not, and the terminal voltage of the embodiment of the application can refer to the voltage between the positive electrode and the negative electrode of the electrochemical device.
B. Carrying out pulse charging heating test on the electrochemical device according to the pulse current frequency and the initial current amplitude of each test group to obtain the lowest negative potential, the negative potential drop and the pulse current amplitude of each test group;
the negative electrode lowest potential of each test group is recorded as Va and min, the negative electrode potential drop of each test group obtained in the pulse charging and heating test process is recorded as delta Va, and the pulse current amplitude is recorded as I.
C. And obtaining the cathode impedance according to the cathode potential drop and the pulse current amplitude of each test group.
In the embodiment of the present application, for each test group, a ratio between a negative potential drop of the test group and a pulse current amplitude may be calculated to obtain a negative impedance of the test group. Illustratively, the negative impedance of a single test set, denoted as Ra, ra = Δ Va/I, is obtained from the negative potential drop Δ Va and the corresponding pulse current amplitude I of the test set.
The method and the device provide a basis for subsequently determining the corrected current amplitude by determining the cathode lowest potential, the cathode potential drop and the cathode impedance of the electrochemical device.
In an alternative embodiment, the step of determining the lithium-evolving potential difference and correcting the current magnitude based on the negative minimum potential, the negative impedance and the negative lithium-evolving potential may comprise:
a. determining a lithium analysis potential difference according to a difference value between the lowest potential of the negative electrode and a lithium analysis potential of the negative electrode;
in the embodiment of the application, a difference value between the lowest potential of the negative electrode and the lithium analysis potential of the negative electrode can be calculated and is used as the lithium analysis potential difference and recorded as Δ V, wherein Δ V = Va and min-Va0.
b. And determining the correction current amplitude according to the ratio of the lithium analysis potential difference to the negative electrode impedance.
In the embodiment of the present application, a ratio between the lithium analysis potential difference and the negative impedance may be calculated as a correction current amplitude, which is recorded as Δ I = Δ V/Ra.
According to the embodiment of the application, the correction current amplitude can be obtained, and the initial current amplitude can be corrected by utilizing the correction current amplitude, so that the lithium separation phenomenon of the electrochemical device during self-heating is improved.
In an alternative embodiment, the step of correcting the initial current amplitude by using the corrected current amplitude to obtain the first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude may include:
when the correction current amplitude is a positive value, adding the initial current amplitude and the correction current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude;
and when the correction current amplitude is a negative value, subtracting the correction current amplitude from the initial current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude. Thereby determining the maximum pulse current amplitude capable of improving the lithium separation phenomenon of the electrochemical device at the current frequency.
According to the embodiment of the application, the initial current amplitude is corrected through the correction current amplitude, the first current amplitude, namely the corrected initial current amplitude, can be obtained, and self-heating is carried out by utilizing the first current amplitude, so that the lithium precipitation phenomenon of the electrochemical device during self-heating is improved.
The electrochemical device of the embodiment of the application may include at least one of a lithium iron phosphate system electrochemical device, a lithium nickel cobalt manganese oxide system electrochemical device, and a lithium cobalt oxide system electrochemical device. The electrochemical device according to the embodiment of the present application may include one lithium ion battery, or may include a plurality of lithium ion batteries.
The first temperature of the embodiment of the present application may comprise any point value between-10 ℃, -20 ℃, -30 ℃ or-10 ℃ to-30 ℃, the first SOC comprising 0% SOC, 50% SOC, 100% SOC or any point value between 0% SOC to 100% SOC, which may be selected according to the actual use of the electrochemical device.
In one embodiment of the present application, referring to fig. 3a, a lithium ion battery is tested to determine a first current amplitude under the following conditions:
1) After a pulse charging heating test is carried out on a lithium ion battery (model 6052C 9) at the temperature of-30 ℃ by using a 1C (6A) charging multiplying power and a 1Hz pulse current frequency, wherein the first SOC is 100%, the lowest potential Va, min = -0.17V of a negative electrode, and the negative electrode potential drop delta Va =0.68- (-0.17) = -0.85V in a single pulse charging process;
2) Calculating to obtain the negative impedance Ra = delta Va/I =0.85/6=0.142 omega;
3) After 10 cycles of charge and discharge cycle test is carried out on the lithium ion battery, the lithium separation potential of the negative electrode is 0.01V, and the lithium separation potential difference delta V between the lowest potential of the negative electrode and the lithium separation potential of the negative electrode is = -0.17V-0.01V = -0.18V;
4) Correction current amplitude Δ I = Δ V/Ra = -0.18/0.142= -1.27A;
5) The first current amplitude I' =6-1.27=4.73a, that is, the maximum current amplitude of the lithium ion battery, which does not separate lithium out under the conditions of-30 ℃ and 1Hz pulse current frequency, is 4.73A.
The lithium ion battery is charged by pulse with the current amplitude of 4.73A and the pulse current frequency of 1Hz and is self-heated at the temperature of minus 30 ℃, so that the lithium ion battery can be quickly and safely heated.
In another embodiment of the present application, referring to fig. 3b, a lithium ion battery is tested to determine a first current amplitude under the following conditions:
1) With a 1C (6A) charging rate and a 1Hz pulse current frequency, wherein the first SOC is 0%, after a pulse charging heating test is carried out on a lithium ion battery (model 6052C 9) in an environment at the temperature of-20 ℃, the lowest potential Va of a negative electrode is min =0.08V, and the negative electrode potential drop delta Va =0.67- (0.08) =0.59V in a single pulse charging process;
2) Calculating to obtain the impedance Ra = delta Va/I =0.59/6=0.098 omega of the negative electrode;
3) After 10 cycles of charge and discharge cycle test is carried out on the lithium ion battery, the lithium separation potential of the negative electrode is 0V, and the lithium separation potential difference delta V between the lowest potential of the negative electrode and the lithium separation potential of the negative electrode is =0.08V-0V =0.08V;
4) Correction current amplitude Δ I = Δ V/Ra =0.08/0.098=0.82a;
5) The first current amplitude I' =6+0.82=6.82A, namely the maximum current amplitude of the lithium ion battery without lithium separation under the conditions of-20 ℃ and 1Hz pulse current frequency is 6.82A.
The lithium ion battery adopts a current amplitude of 6.82A, pulse charging self-heating with the pulse current frequency of 1Hz is carried out at the temperature of minus 20 ℃, and the temperature of the lithium ion battery can be quickly and safely increased.
Corresponding to the above method embodiment, the embodiment of the present invention also provides a corresponding device embodiment.
As shown in fig. 4, an embodiment of the present application provides an electrochemical device including: a pulse current frequency determination module 401, a lithium analysis determination module 402, a current amplitude acquisition module 403, and a correction current amplitude determination module 404, wherein,
the pulse current frequency determining module 401 is configured to obtain an impedance-current frequency variation relationship of the electrochemical device at a first temperature, and determine a pulse current frequency based on the impedance-current frequency variation relationship.
And a lithium evolution determining module 402, configured to determine a lithium evolution rate and a negative lithium evolution potential of the electrochemical device at the first temperature.
A current amplitude obtaining module 403, configured to obtain multiple initial current amplitudes, where charging magnifications corresponding to the initial current amplitudes are all greater than the lithium deposition magnifications.
A correction current amplitude determination module 404 configured to obtain a plurality of negative minimum potentials and a plurality of negative impedances based on the first temperature, the first SOC, the pulse current frequency, and a plurality of the initial current amplitudes, and determine a lithium-extraction potential difference and a correction current amplitude based on the negative minimum potentials, the negative impedances, and the negative lithium-extraction potential.
In an alternative embodiment, the apparatus further comprises:
and the heating module is used for correcting the initial current amplitude value by using the corrected current amplitude value to obtain a first current amplitude value and performing pulse charging heating on the electrochemical device by using the first current amplitude value.
In an alternative embodiment, the pulse current frequency determination module is specifically configured to:
a plurality of current frequencies having an impedance falling rate of 40% to 80% are determined as the pulse current frequency based on the impedance-current frequency variation relationship.
In an alternative embodiment, the lithium analysis determination module is specifically configured to:
and at the first temperature, the electrochemical device carries out a plurality of charging tests through different charging multiplying factors, and a plurality of negative electrode potentials of the electrochemical device in the charging test process are obtained, so that the negative electrode lithium-separating potential and the lithium-separating multiplying factor of the electrochemical device with lithium separation are determined.
In an alternative embodiment, the correction current amplitude determination module is specifically configured to:
forming a plurality of different initial current amplitudes and pulse current frequencies into a plurality of test groups;
carrying out pulse charging heating test on the electrochemical device according to the pulse current frequency and the initial current amplitude of each test group to obtain the minimum negative potential, the negative potential drop and the pulse current amplitude of each test group;
and obtaining the cathode impedance according to the cathode potential drop and the pulse current amplitude of each test group.
In an alternative embodiment, the correction current magnitude determination module is specifically configured to:
determining the lithium-analysis potential difference according to the difference value between the lowest potential of the negative electrode and the lithium-analysis potential of the negative electrode;
and determining the correction current amplitude according to the ratio of the lithium analysis potential difference to the cathode impedance.
In an alternative embodiment, the heating module is used in particular for:
when the correction current amplitude is a positive value, adding an initial current amplitude to the correction current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude;
and when the correction current amplitude is a negative value, subtracting the correction current amplitude from the initial current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude.
In an alternative embodiment, the predetermined temperature comprises any one of-10 ℃, -20 ℃, -30 ℃ or-50 ℃, and the predetermined SOC comprises any one of 0% SOC, 50% SOC or 100% SOC.
The embodiment of the application provides an electrochemical device, pulse current frequency is determined based on the obtained impedance-current frequency change relation at a first temperature, lithium precipitation multiplying power and negative lithium precipitation potential of the electrochemical device at the first temperature are determined, after a plurality of initial current amplitudes are obtained, a plurality of negative electrode minimum potentials and a plurality of negative electrode impedances are obtained based on the first temperature, the first SOC, the pulse current frequency and the plurality of initial current amplitudes, and lithium precipitation potential and correction current amplitude are determined based on the negative electrode minimum potentials, the negative electrode impedances and the negative electrode lithium precipitation potential, so that the initial current amplitudes are corrected by using the correction current amplitudes, the lithium precipitation phenomenon of the electrochemical device during self-heating is improved, and the electrochemical device is more beneficial to being used in a cold environment.
The present example also provides a powered device, as shown in fig. 5, the powered device 500 includes a processor 501, a machine-readable storage medium 502, and an electrochemical apparatus 503 according to any of the above embodiments.
In one example, the powered device may be a two-wheeled vehicle or a drone that includes a processor and a machine-readable storage medium and is equipped with an electrochemical device that includes at least one lithium ion battery therein.
The embodiment of the present application further provides a charger, as shown in fig. 6, the charger 600 includes a processor 601 and a machine-readable storage medium 602, and the charger 600 further includes a detection circuit module 603, an interface 604, and a power interface 605. The detection circuit module 603 is configured to detect parameters of the electrochemical device, such as voltage, current, internal resistance, and the like; the interface 604 is used for electrically connecting with the lithium ion battery 701; power interface 605 is for connection to a power source; the machine-readable storage medium 602 stores machine-executable instructions that are executable by the processor 601 to perform the method steps described in any of the above embodiments when the processor executes the machine-executable instructions.
For the electrochemical device/consumer embodiments, since they are substantially similar to the method embodiments, the description is relatively simple, and reference may be made to the partial description of the method embodiments for relevant points.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the embodiment of the electric device, since it is substantially similar to the embodiment of the method, the description is simple, and for the relevant points, reference may be made to the partial description of the embodiment of the method.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (12)
1. A method of electrochemical device heating, wherein the method comprises:
acquiring an impedance-current frequency variation relation of the electrochemical device at a first temperature, and determining a plurality of current frequencies with impedance reduction rates of 40-80% as pulse current frequencies based on the impedance-current frequency variation relation;
determining the lithium precipitation rate and the lithium precipitation potential of the negative electrode of the electrochemical device at the first temperature;
obtaining a plurality of initial current amplitudes, wherein the charging multiplying power corresponding to the initial current amplitudes is larger than the lithium precipitation multiplying power;
obtaining a plurality of cathode minimum potentials and a plurality of cathode impedances based on the first temperature, the first SOC, the pulse current frequency and the plurality of initial current amplitudes, and determining a lithium-deposition potential difference and a correction current amplitude based on the cathode minimum potentials, the cathode impedances and the cathode lithium-deposition potential;
and correcting the initial current amplitude by using the correction current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude.
2. The electrochemical device heating method of claim 1, wherein the determining the lithium evolution rate and the negative lithium evolution potential of the electrochemical device at the first temperature comprises:
and at the first temperature, the electrochemical device carries out a plurality of charging tests through different charging multiplying factors, and a plurality of negative electrode potentials of the electrochemical device in the charging test process are obtained, so that the negative electrode lithium-separating potential and the lithium-separating multiplying factor of the electrochemical device with lithium separation are determined.
3. The electrochemical device heating method of claim 1, wherein the step of obtaining a plurality of negative minimum potentials, a plurality of negative impedances based on the first temperature, the first SOC, the pulse current frequency, and the plurality of initial current amplitudes comprises:
forming a plurality of different initial current amplitudes and pulse current frequencies into a plurality of test groups;
carrying out pulse charging heating test on the electrochemical device according to the pulse current frequency and the initial current amplitude of each test group to obtain the minimum negative potential, the negative potential drop and the pulse current amplitude of each test group;
and obtaining the cathode impedance according to the cathode potential drop and the pulse current amplitude of each test group.
4. The electrochemical device heating method of claim 1, wherein the determining a lithium evolution potential difference and correcting a current magnitude based on the negative minimum potential, the negative impedance, and the negative lithium evolution potential comprises:
determining the lithium-separating potential difference according to the difference value between the lowest potential of the negative electrode and the lithium-separating potential of the negative electrode;
and determining the correction current amplitude according to the ratio of the lithium analysis potential difference to the cathode impedance.
5. The electrochemical device heating method of claim 1, wherein the correcting the initial current amplitude with the corrected current amplitude and the pulsed charge heating the electrochemical device with the first current amplitude comprises:
when the correction current amplitude is a positive value, adding an initial current amplitude and the correction current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude;
and when the correction current amplitude is a negative value, subtracting the correction current amplitude from the initial current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude.
6. The electrochemical device heating method of claim 1, wherein the first temperature comprises any one of-10 ℃, -20 ℃, or-30 ℃, the first SOC comprising any one of 0%, 50%, or 100%.
7. An electrochemical device, wherein the device comprises: a pulse current frequency determining module, a lithium analysis determining module, a current amplitude obtaining module, a correction current amplitude determining module and a heating module, wherein,
the pulse current frequency determining module is used for acquiring an impedance-current frequency change relation of the electrochemical device at a first temperature, and determining a plurality of current frequencies with impedance reduction rates of 40-80% as pulse current frequencies based on the impedance-current frequency change relation;
the lithium evolution determining module is used for determining the lithium evolution multiplying power and the negative electrode lithium evolution potential of the electrochemical device at the first temperature;
the current amplitude acquisition module is used for acquiring a plurality of initial current amplitudes, and the charging multiplying power corresponding to the initial current amplitudes is larger than the lithium precipitation multiplying power;
the correction current amplitude determination module is configured to obtain a plurality of negative minimum potentials and a plurality of negative impedances based on the first temperature, the first SOC, the pulse current frequency, and the plurality of initial current amplitudes, and determine a lithium-deposition potential difference and a correction current amplitude based on the negative minimum potentials, the negative impedances, and the negative lithium-deposition potential;
the heating module is used for correcting the initial current amplitude value by using the corrected current amplitude value to obtain a first current amplitude value, and performing pulse charging heating on the electrochemical device by using the first current amplitude value.
8. The electrochemical device of claim 7, wherein the lithium analysis determination module is specifically configured to:
and at the first temperature, the electrochemical device carries out a plurality of charging tests through different charging multiplying factors, and a plurality of negative electrode potentials of the electrochemical device in the charging test process are obtained, so that the negative electrode lithium-separating potential and the lithium-separating multiplying factor of the electrochemical device with lithium separation are determined.
9. The electrochemical device of claim 7, wherein the correction current magnitude determination module is specifically configured to:
forming a plurality of different initial current amplitudes and pulse current frequencies into a plurality of test groups;
carrying out pulse charging heating test on the electrochemical device according to the pulse current frequency and the initial current amplitude of each test group to obtain the minimum negative potential, the negative potential drop and the pulse current amplitude of each test group;
and obtaining the cathode impedance according to the cathode potential drop and the pulse current amplitude of each test group.
10. The electrochemical device of claim 7, wherein the correction current magnitude determination module is specifically configured to:
determining the lithium-analysis potential difference according to the difference value between the lowest potential of the negative electrode and the lithium-analysis potential of the negative electrode;
and determining the correction current amplitude according to the ratio of the lithium analysis potential difference to the negative impedance.
11. The electrochemical device of claim 7, wherein the heating module is specifically configured to:
when the correction current amplitude is a positive value, adding an initial current amplitude and the correction current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude;
and when the correction current amplitude is a negative value, subtracting the correction current amplitude from the initial current amplitude to obtain a first current amplitude, and performing pulse charging heating on the electrochemical device by using the first current amplitude.
12. An electrical device comprising a processor, a machine-readable storage medium, and the electrochemical apparatus of any one of claims 7-11.
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