CN104347896B - Method for improving service life of lithium ion battery in low-temperature environment - Google Patents

Method for improving service life of lithium ion battery in low-temperature environment Download PDF

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CN104347896B
CN104347896B CN201310340827.2A CN201310340827A CN104347896B CN 104347896 B CN104347896 B CN 104347896B CN 201310340827 A CN201310340827 A CN 201310340827A CN 104347896 B CN104347896 B CN 104347896B
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CN104347896A (en
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吴宁宁
徐金龙
宋韶灵
李群
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RiseSun MGL New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/443—Methods for charging or discharging in response to temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a method for improving the service life of a lithium ion battery in a low-temperature environment, belonging to the technical field of batteries. The method is characterized in that before the battery is used in a low-temperature environment, the battery is pulsed to raise the temperature of the battery. Before the battery is used in a low-temperature environment, a certain amount of pulse electricity is applied to the battery to enable the battery to uniformly reach an appropriate temperature. The service life of the battery in a low-temperature environment is improved while the design cost of the battery is not increased. The method can improve the temperature of the battery in a short time, and the temperature rise uniformity of the battery is good, so that the temperature of the battery use environment is reduced, and the service life of the battery in a low-temperature environment is prolonged.

Description

Method for improving service life of lithium ion battery in low-temperature environment
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a method for improving the service life of a lithium ion battery in a low-temperature environment.
Background
With the gradual depletion of traditional energy and the gradual serious pollution caused by the traditional energy, governments of various countries have stronger expectations for new energy automobiles, and the emergence of the new energy automobiles is expected to relieve the increasingly severe energy and environmental stresses faced by people at present. The battery technology, which is a key technology for the development of new energy vehicles, is thus mentioned as an important place. Lithium ion power batteries are widely used due to their advantages in energy density, power performance, etc.
The application range of lithium ion batteries is continuously expanded, and the requirements on the application conditions are increasingly strict. What follows is what the lithium battery industry must solve, and how to improve the service life of the lithium battery at low temperature and improve the stability of the battery at low temperature is an opportunity and challenge facing the industry.
In order to solve the problems, lithium battery operators do a lot of work in the aspects of changing the active materials of the batteries, the thickness of a current collector, optimizing the components of electrolyte and the like, so that the high-temperature and low-temperature performance of the batteries is greatly improved. But also results in increased cost of the battery and more complicated associated processes. In addition, on the basis of not changing the original formula and structure of the lithium battery, the battery system is subjected to integral heating and heat preservation in an external heating mode, the service environment temperature of the battery is changed, and a certain optimization effect can be achieved. However, the external heating method is difficult to ensure the uniformity of the internal temperature of each battery and a single battery in the battery system, so that the stability of the battery is poor.
Disclosure of Invention
The invention aims to provide a method for reducing the temperature of the use environment of a lithium ion battery and improving the service life of the lithium ion battery in a low-temperature environment on the basis of the prior art, wherein a pre-charging mode is adopted, and the method is used for increasing the temperature of the battery by applying pulses to the battery before the lithium ion battery is used in the low-temperature environment. Before the battery is used in a low-temperature environment, a certain amount of pulse electricity is applied to the battery to enable the battery to uniformly reach an appropriate temperature. The service life of the battery in a low-temperature environment is improved while the design cost of the battery is not increased.
In order to achieve the purpose, the invention adopts the following technical scheme:
before the battery is used in a low-temperature environment, firstly, the open-circuit voltage (OCV) and the temperature (T) of the battery are detected, and then initial pulse parameters applied to the battery are determined according to the open-circuit voltage and the temperature (the battery parameters in different systems are slightly different, and the battery parameters refer to VCritical point ofR, K), when the temperature of the battery rises by 1-2 ℃, adjusting the pulse parameters again according to the open-circuit voltage and the temperature until the temperature of the battery reaches the proper use temperature. Although the definition range of the low temperature environment of the battery is different for different systems, the low temperature environment is generally defined below with 0 ℃ as a demarcation point, and the above is a suitable temperature.
The applied pulses may be constant current pulses or constant voltage pulses.
The applied pulses are stepped pulses.
When constant voltage pulses are used, the selected voltage is VCritical point of。
Constant current pulse method, selected current In＝[(VCritical n-OCVn)/Rn]*K，VCritical point ofIt is critical potential of lithium deposition when charging the battery at corresponding temperature, OCV is initial voltage of the battery, and R is initial voltage at corresponding temperatureThe impedance capability of the battery to cause polarization in the state, K is a current correction coefficient of 0.5-2.0, n is a natural number, wherein I1＜I2＜I3＜…＜In。
The individual pulses are carried out over a time of 1mS to 100S, preferably 1mS to 1S.
The pulses applied can be charge, discharge and charge-discharge pulses, preferably discharge when SOC (determined by OCV) > 70%; when the SOC is more than or equal to 30% and less than or equal to 70%, a charge-discharge type is adopted; when SOC is less than 30%, charging type is adopted.
The above method is suitable for a single battery and a battery system.
The invention has the beneficial effects that:
the invention increases the temperature of the battery to a proper use temperature by a stepping pulse charging and discharging method, and then carries out normal charging and discharging, wherein the method is to select pulse current according to the temperature of the battery, and the pulse current is correspondingly increased along with the increasing of the temperature of the battery; because the pulse width of the method is narrow, the performance of the battery cannot be deteriorated in the pulse process; the method can improve the temperature of the battery in a short time, and the temperature rise uniformity of the battery is good, so that the temperature of the battery use environment is reduced, and the service life of the battery in a low-temperature environment is prolonged.
Drawings
FIG. 1: pulse current, battery voltage and time variation simulation curve (I) in constant current charge-discharge type pulse1Pulse current, t1Single pulse time);
FIG. 2: when the pulse is charged and discharged by constant current, the change of the stepping current and the time is simulated by a curve;
FIG. 3: a constant-current charging type pulse current and time variation simulation curve;
FIG. 4: a constant-current discharge type pulse current and time variation simulation curve;
FIG. 5: simulating a curve of the temperature rise of the surface of the battery along with the change of time;
FIG. 6: when the charging type pulse is carried out at constant voltage, a pulse current, a battery voltage and time change simulation curve;
FIG. 7: cell impedance profiles before and after the pulse in example 1.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The lithium battery technology and the tool are basically the same as those used in the traditional technology, and only a pulse type pre-charging self-heating method is adopted before the battery is used at a low temperature, so that the battery reaches a proper use temperature, and the service life of the battery in a low-temperature environment is further improved.
Firstly, the manufacturing process of the lithium ion battery comprises the following steps:
① coating the positive electrode, mixing the positive electrode material, carbon black, KS-15 and polyvinylidene fluoride (PVDF) according to a certain proportion, stirring, and coating the positive electrode;
② coating negative electrode, mixing graphite, carbon black, LA-132, and carboxymethyl cellulose (CMC) at a certain ratio, stirring, and coating the negative electrode;
③ baking the ① and ② positive and negative plates, rolling, cutting, matching, laminating and packaging to obtain a battery core;
④ liquid injection process, injecting 1.0mol/LLIPF6(EC: DEC: DMC =1:1:1) type electrolyte, 1.0mol/LLIPF6(EC: DEC: DMC =1:1:1) means that LiPF6 is dissolved in a mixed solution of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) with a volume ratio of 1:1:1 to form 1mol/L electrolyte;
⑤ and pre-charging to obtain the final product.
The main implementation mode is as the following scheme:
examples
Example 1: constant current charging and discharging
The battery with the capacity of 20Ah is manufactured according to the method, the battery is subjected to a self-preheating test from-15 ℃ in a stepping constant-current charge-discharge pulse mode, the total pulse flow is 8 steps, the single-step pulse time is 0.6S, the temperature interval is 2 ℃, and the voltage is VCritical point ofIt was assumed that 4.2V, OCV was 3.7V,k is 1.0, RnKnown as In＝[(VCritical n-OCVn)/Rn]Calculating I by KnIn the process of I1During pulse, the battery temperature is detected, and when the temperature reaches-13 ℃, the temperature is converted into I2Pulsing, step-wise pulsing at the following table currents until the cell temperature was greater than 0 ℃.
The parameters are shown in the following table:
Figure BDA00003631531600051
from the above table, t1And pulse number calculation: the temperature of the battery is uniformly increased from minus 15 ℃ to more than 0 ℃ within 36 min. To verify whether the pulse was harmful to the battery, the impedance spectrum of the battery was tested at an OCV of 3.7V at 25 ℃ after repeating the above test 30 times. As can be seen from fig. 7, the application of a pulsed current to heat the battery for a short period of time, the impedance of the battery increases slightly, but the change is not significant, and it is considered that the battery is not damaged.
Example 2: constant current charging
The battery with the capacity of 25Ah is manufactured according to the method, a self-preheating test is carried out on the battery from-10 ℃ in a stepping constant-current charging pulse mode, 5 pulse flows are carried out, the single-step pulse time is 0.05S, the temperature interval is 2 ℃, and the voltage is VCritical point ofWas identified as 4.2V, OCVn3.5V, K1.0, RnKnown as In＝[(VCritical n-OCVn)/Rn]Calculating I by KnIn the process of I1During pulse, the battery temperature is detected, and when the temperature reaches-8 ℃, the temperature is converted into I2Pulsing, step-wise pulsing at the following table currents until the cell temperature was greater than 0 ℃.
The parameters are shown in the following table:
from the above table, t1And pulse number calculation: the temperature of the battery is uniformly increased from minus 10 ℃ to more than 0 ℃ within 13min, and the SOC of the battery is increased by 19.5%.
Example 3: constant voltage type charging
The battery with the capacity of 30Ah is manufactured according to the method, a self-preheating test is carried out on the battery from-10 ℃ in a stepping constant-voltage charging pulse mode, 5 pulse flows are carried out, the single-step pulse time is 0.1S, the temperature interval is 2 ℃, and V is carried outCritical 1 ofWas determined to be 4.25V, OCV1At 3.5V, V was performedCritical 1 ofDuring pulse, the battery temperature is detected and converted into V when the temperature reaches-8 DEG CCritical 2 ofPulsing, step-wise pulsing at the following table currents until the cell temperature was greater than 0 ℃.
The parameters are shown in the following table:
Figure BDA00003631531600061
from the above table, t1And pulse number calculation: the temperature of the battery is uniformly increased from minus 10 ℃ to more than 0 ℃ within 11min, and the SOC of the battery is increased by 15%.
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 changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (6)

1. A method for improving the service life of a lithium ion battery in a low-temperature environment is characterized by comprising the following steps: before the battery is used in a low-temperature environment, the method firstly applies pulses to the battery to raise the temperature of the battery; before the battery is used in a low-temperature environment, firstly detecting the open-circuit voltage (OCV) and the temperature (T) of the battery, then determining an initial pulse parameter applied to the battery according to the open-circuit voltage and the temperature, and adjusting the pulse parameter again according to the open-circuit voltage and the temperature when the temperature of the battery rises by 1-2 ℃ until the temperature of the battery reaches the proper use temperature;
when constant voltage pulses are used, the selected voltage is VCritical point of；
Constant flow type pulseMethod of punching, selected current In＝[(VCritical n-OCVn)/Rn]*K，VCritical point ofThe method is characterized in that the critical potential of lithium precipitation occurs when a battery is charged at a corresponding temperature, OCV is the initial voltage of the battery, R is the impedance capability of the battery for causing polarization at the initial state at the corresponding temperature, K is a current correction coefficient of 0.5-2.0, n is a natural number, wherein I is1＜I2＜I3＜…＜In。
2. The method of claim 1 for improving the service life of a lithium ion battery in a low temperature environment, wherein: the single pulse is applied for a time of 1mS to 100S.
3. The method for improving the service life of a lithium ion battery in a low temperature environment according to claim 2, wherein: the single pulse is applied for a time of 1mS to 1S.
4. The method of claim 1 for improving the service life of a lithium ion battery in a low temperature environment, wherein: the pulses applied are charging, discharging or charging and discharging pulses.
5. The method for improving the service life of a lithium ion battery in a low temperature environment according to claim 4, wherein: the pulses implemented are as follows: when the SOC is more than 70%, adopting a discharge type; when the SOC is more than or equal to 30% and less than or equal to 70%, a charge-discharge type is adopted; when SOC is less than 30%, charging type is adopted, wherein SOC is determined by OCV.
6. The method of claim 1 for improving the service life of a lithium ion battery in a low temperature environment, wherein: the method is suitable for single batteries and battery systems.
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CN106655407B (en) * 2017-01-19 2020-08-07 宁德新能源科技有限公司 Battery charging method and device, electronic equipment, adapter and charger
CN107064817B (en) * 2017-04-24 2020-02-14 哈尔滨理工大学 Method for detecting charge state of zinc-silver battery
CN109904533B (en) * 2017-12-11 2022-03-25 奥动新能源汽车科技有限公司 Battery life analysis system and method for battery pack for electric vehicle
CN110470992B (en) * 2019-08-29 2020-06-19 清华大学 Durability test method and system for pulse heating of battery and data table generation method
CN110890600B (en) * 2019-09-24 2021-06-29 北京理工大学 Charging method for 18650 type lithium ion battery in low-temperature environment
CN111211595B (en) * 2020-01-14 2021-11-09 北京小米移动软件有限公司 Charging method and device, electronic equipment and storage medium
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CN112670622A (en) * 2020-12-22 2021-04-16 山东大学 Low-temperature lithium ion battery alternating-current preheating method based on constant-current constant-voltage charging and discharging
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