CN109659641B - Improved safe charging method for power lithium battery - Google Patents

Improved safe charging method for power lithium battery Download PDF

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CN109659641B
CN109659641B CN201910056123.XA CN201910056123A CN109659641B CN 109659641 B CN109659641 B CN 109659641B CN 201910056123 A CN201910056123 A CN 201910056123A CN 109659641 B CN109659641 B CN 109659641B
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charging
lithium battery
battery
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peak value
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CN109659641A (en
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时玮
李丹勇
蔡文川
刘欢
康鑫
韩甜
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Beijing Jiaotong University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • H01M10/441Methods for charging or discharging for several batteries or cells simultaneously or sequentially
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Charge And Discharge Circuits For Batteries Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses an improved safe charging method for a power lithium battery, which comprises the following steps: s1, drawing a dQ/dV standard curve of a certain type of lithium battery; s2, normally charging the target lithium battery with the same type as the target lithium battery in the step S1, drawing a dQ/dV real-time curve and recording a dQ/dV extreme value; s3, when the first peak value of the dQ/dV appears in the step S2, comparing the corresponding voltage with the voltage corresponding to the first peak value of the dQ/dV on the standard curve in the step S1, and analyzing and judging whether the target lithium battery is in a safe state; s4, measuring and calculating the consistency of the internal resistance of each single battery or calculating the internal resistance of the battery pack, and entering a quick charging stage if the internal resistance meets the requirement; s5, in the quick charging stage, charging areas in adjacent peak and valley ranges are charged by adopting a method of changing current in a stepped mode; and S6, after the quick charging stage is finished, completing charging by using an electric automobile manufacturer or a national standard recommendation method. The invention has the advantages of rapidness, safety, convenience and good effect.

Description

Improved safe charging method for power lithium battery
Technical Field
The invention relates to the technical field of health management of power lithium batteries, in particular to an improved safe charging method of a power lithium battery.
Background
Common power lithium batteries include ternary batteries, L TO and L MO, wherein the ternary batteries are nominally 3.7V, L TO is nominally 2.4V, and L MO is nominally 3.7V.
Each battery cell overcharge or overdischarge can all lead to the safety problem in the power lithium cell, and prior art realizes safe charging through setting up protection system to the power lithium cell, nevertheless can not monitor each battery cell's state, will influence the live time of power lithium cell in case each battery cell energy is inconsistent to must appear a voltage slightly high or the battery cell that slightly hangs down frequently be in overcharge or overdischarge state, use very big possibility after the long time and cause the incident.
Therefore, there is an urgent need to develop an improved safe charging method for a lithium battery, which can perform charging safely and rapidly, and has a significant progress compared to the prior art.
Disclosure of Invention
The invention aims to provide an improved safe charging method for a power lithium battery, which aims to overcome the defects of the prior art, and the charging method monitors the charging process through a dQ/dV curve, can monitor the states of all single batteries to ensure the consistency of all the single batteries, avoids a certain single battery from being in an overcharged or overdischarged state for a long time, and enables the whole charging process to be carried out in a safe and rapid direction.
The invention achieves the purpose through the following technical scheme:
an improved safe charging method for a power lithium battery is characterized by comprising the following steps:
s1, drawing a dQ/dV standard curve of a certain type of lithium battery;
s2, normally charging the target lithium battery with the same type as the target lithium battery in the step S1, drawing a dQ/dV real-time curve and recording a dQ/dV extreme value;
s3, when the first peak value of the dQ/dV in the step S2 occurs, comparing the corresponding voltage with the voltage corresponding to the first peak value of the dQ/dV on the standard curve in the step S1, and when the deviation of the two is not more than the sum of the polarization voltage and the ohmic voltage drop of the current lithium battery charging, judging that the target lithium battery is in a safe charging state currently;
s4, measuring and calculating the consistency of the internal resistance of each single battery in the target lithium battery or calculating the internal resistance of the battery pack, and entering a quick charging stage when the internal resistance of each single battery of the target lithium battery is kept consistent or the internal resistance of the current target lithium battery is between 0.8 and 1.5 times of the normal internal resistance, wherein the quick charging stage is a charging area from a first dQ/dV peak value to a third dQ/dV peak value;
s5, in the quick charging stage, charging areas in adjacent peak and valley ranges are charged by adopting a method of changing current in a stepped mode;
and S6, after the quick charging stage is finished, adopting a method recommended by an electric vehicle manufacturer until the charging is finished, or continuously charging the target lithium battery by using constant current with the rate of 1.0C until the charging is finished, and then converting the constant current charging into constant voltage charging until the charging current is 0.05C to finish the charging.
Further, in step S1, the dQ/dV standard curve is plotted as follows:
s1.1, charging a certain type of lithium battery under a constant current condition with 0.05C multiplying power, enabling the voltage to change constantly in the charging and discharging direction, and obtaining a group of voltages dV at equal intervals;
s1.2, integrating the current in each dV time interval to obtain a group of dQ;
and S1.3, drawing a dQ/dV standard curve by taking the voltage value as an abscissa and the dQ/dV value as an ordinate to obtain a voltage value corresponding to the dQ/dV value at an extreme value.
Furthermore, the dV is the voltage acquisition precision which can be achieved by the machine under the current charging rate.
Further, in the step S4, the method for measuring and calculating the internal resistance consistency of each single battery specifically includes the following steps:
s4.1, charging the target lithium battery by a user-defined descending pulse current sequence within the range of 200A-0A, and carrying out pulse charging for a plurality of times;
s4.2, collecting the voltage of each single battery at the 100ms moment of each pulse, and sending the voltage to a data analysis system;
and S4.3, calculating the internal resistance of each single battery by the data analysis system, and judging the consistency.
Further, in step S4.1, the pulse current sequences are 200A, 150A, 100A, 50A and 0A.
Further, in step S4, the pulse interval is 10S, and each pulse current is maintained for 500ms and then made zero.
Further, in step S5, the fast charge stage includes a first fast charge interval and a second fast charge interval, where the first fast charge interval is a charge area from the first peak value of dQ/dV to the second peak value of dQ/dV, and the second fast charge interval is a charge area from the second peak value of dQ/dV to the third peak value of dQ/dV.
Further, in step S5, the charging regions in the range from the first peak value of dQ/dV to the first valley value of dQ/dV and the range from the second peak value of dQ/dV to the second valley value of dQ/dV are charged with stepwise increasing currents, and the charging regions in the range from the first valley value of dQ/dV to the second peak value of dQ/dV and the range from the second valley value of dQ/dV to the third peak value of dQ/dV are charged with stepwise decreasing currents. The charging mode can avoid the damage to the phase change crystal lattices of the positive and negative electrode active materials of the power lithium battery.
Further, in the step S5, the current magnification variation range of the stepwise variation current is 0.3C to 2.0C; when dQ/dV is at the trough, the current magnification is 2.0C.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. compared with the traditional method for realizing safe charging by arranging a protection system on a power lithium battery, the improved safe charging method for the power lithium battery adopts a dQ/dV curve to monitor the whole charging process, can judge the consistency of each single battery, effectively avoids a certain single battery from being in an over-charging or over-discharging state for a long time, and has the advantages of rapidness, safety, simple and convenient operation and ideal effect;
2. in the quick charging stage of the charging method of the power lithium battery, the charging areas in the adjacent peak value and valley value ranges are charged by adopting a method of changing current in a stepped manner, instead of adopting the charging current with the maximum multiplying power at the peak value, so that the damage to the phase change crystal lattices of the positive and negative electrode active materials of the power lithium battery is effectively avoided.
Drawings
Fig. 1 is a flowchart of a charging method according to a first embodiment.
FIG. 2 is a dQ/dV standard curve for the model number NCR18650B-MH12210 under the Song brand power lithium battery of example one;
fig. 3 is a diagram illustrating dQ/dv.vs. soc of a power lithium battery in the second embodiment during charging.
Fig. 4 is a partially enlarged view of stages 1-4 of fig. 3.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying drawings and specific examples. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example one
In the embodiment, a Songdahu dynamic lithium battery with the model number of NCR18650B-MH12210 is used as a charging object, the voltage range is 3.0-4.2V, and the capacity is 2900 mAh. As shown in fig. 1 and 2, the power lithium battery is charged by a safe and fast method, and the whole charging process is controlled and recorded by a battery intelligent management system, which specifically comprises the following steps:
s1, drawing a dQ/dV standard curve of a Song-brand power lithium battery with the model number of NCR18650B-MH 12210;
s2, charging the target lithium battery with the same type as the target lithium battery in the step S1 by adopting a 1.0C constant current, drawing a dQ/dV real-time curve and recording a dQ/dV extreme value;
s3, when the first peak value of the dQ/dV in the step S2 occurs, comparing the corresponding voltage with the voltage corresponding to the first peak value of the dQ/dV on the standard curve in the step S1, and when the deviation of the two is not more than the sum of the polarization voltage and the ohmic voltage drop of the current lithium battery charging, judging that the target lithium battery is in a safe charging state currently;
s4, measuring and calculating the consistency of the internal resistance of each single battery in the target lithium battery or calculating the internal resistance of the battery pack, and entering a quick charging stage when the internal resistance of each single battery of the target lithium battery is kept consistent or the internal resistance of the current target lithium battery is between 0.8 and 1.5 times of the normal internal resistance, wherein the quick charging stage is a charging area from a first dQ/dV peak value to a third dQ/dV peak value;
s5, in the quick charging stage, charging areas in adjacent peak and valley ranges are charged by adopting a method of changing current in a stepped mode;
and S6, after the quick charging stage is finished, continuously charging the target lithium battery by adopting the constant current with the rate of 1.0C until the rated voltage of the target lithium battery is reached, and finishing charging.
It should be noted that, in the step S1, the dQ/dV standard curve is plotted as follows:
s1.1, charging a Songdahu power lithium battery with the model number of NCR18650B-MH12210 under the condition of constant current with the magnification of 0.05C, enabling the voltage to be constantly changed in the charging and discharging direction, and obtaining a group of voltages dV at equal intervals, wherein the dV value is 0.0011V;
s1.2, integrating the current in each dV time interval to obtain a group of dQ;
and S1.3, drawing a dQ/dV standard curve by taking the voltage value as an abscissa and the dQ/dV value as an ordinate, and obtaining the voltage value corresponding to the dQ/dV value at an extreme value in detail by referring to the graph 2.
In step S4, the method for measuring and calculating the internal resistance consistency of each single battery specifically includes the following steps:
s4.1, charging the target lithium battery by a user-defined descending pulse current sequence within the range of 200A-0A, and carrying out pulse charging for a plurality of times;
s4.2, collecting the voltage of each single battery at the 100ms moment of each pulse, and sending the voltage to a data analysis system;
and S4.3, calculating the internal resistance of each single battery by the data analysis system, and judging the consistency.
In S4.1 to S4.3, the pulse current sequences are 200A, 150A, 100A, 50A, and 0A, and each pulse current is maintained for 500ms and then made zero, and the interval between adjacent pulses is 10S. In the step S4.2, the ADC chip of each cell is controlled to send the voltage of each cell to the charging pile in an array form, so as to calculate the consistency of the cells. If the battery intelligent management system does not have the function of uploading the voltage data of the single battery, the charger obtains the total voltage change of the battery pack according to the same current test sequence, and therefore the internal resistance of the battery pack is calculated. Step S4 is convenient for judging whether the lithium battery in the current charging state is in the safe charging state by analyzing the consistency condition of each single battery or the internal resistance range of the battery pack; and if the requirement of the safe charging state is met, entering a next quick charging stage, and if the requirement of the safe charging state is not met, stopping charging, detecting the lithium battery, and judging whether the anode and cathode materials of the lithium battery change or the diaphragm has a larger gap and the like.
The fast charging phase is composed of a first fast charging interval 101 and a second fast charging interval 102, wherein the first fast charging interval 101 refers to a charging area ranging from a first peak value of dQ/dV to a second peak value of dQ/dV, and the second fast charging interval 102 refers to a charging area ranging from the second peak value of dQ/dV to a third peak value of dQ/dV. Since the peak electromotive force corresponds to the point of phase change reaction at which the electrochemical reaction of the cell changes from one state to another, the electromotive force at the peak should correspond to the lowest current of the electrochemical reaction; in addition, the peak value of the dQ/dV curve represents that the anode and cathode materials of the battery are in a phase change process, so that the reduction of the charging current multiplying power at the peak value is beneficial to the stability of the anode and cathode reaction interfaces of the battery, and the anode and cathode active materials of the battery are effectively protected.
In the fast charging stage, the embodiment creatively provides that the charging area in the range of the adjacent peak value and valley value is charged by adopting a method of changing current in a stepped manner, which is beneficial to preventing the phase change crystal lattices of the positive and negative electrode active materials of the lithium battery from being damaged. Charging regions in the range from the first dQ/dV peak value to the first dQ/dV valley value and the second dQ/dV peak value to the second dQ/dV valley value are charged by adopting a mode of stepwise increasing current, and charging regions in the range from the first dQ/dV valley value to the second dQ/dV peak value and the second dQ/dV valley value to the third dQ/dV peak value are charged by adopting a mode of stepwise decreasing current. The current multiplying power change range of the step-type change current is 0.3C-2.0C; when the dQ/dV is at a low valley value, the current multiplying power is 2.0C; when dQ/dV is at the trough, the current magnification is 0.3C.
Example two
In this embodiment, based on the first embodiment, the charging region in the adjacent peak and valley ranges in the fast charging stage is charged by using a method of changing the current in a stepwise manner. Still adopt the power lithium cell of the card of making loose of model NCR18650B-MH12210 as the charging object, the voltage range is 3.0 ~ 4.2V, and the capacity is 2900 mAh.
As shown in fig. 3, the real-time dQ/dV curve in step S2 in the first embodiment is converted into a dQ/dv.vs. SOC curve, and between each peak and valley, the SOC interval is further divided into a plateau interval for step current charging according to the slope change of the curve, and each interval from the peak to the valley and from the valley to the peak can be divided into three segments according to the slope change, as shown in fig. 4, the curve is gentle at the peak top and the valley adjacent interval, the curve is fast in the middle area, and can be divided into three intervals of △ SOC1, △ SOC2 and △ SOC3 according to the slope change, and from the valley to the peak, the charging current magnification is reduced in a stepwise manner from 2C to 0.3C, the charging magnification corresponding to each step is determined by the slope and the SOC, the step size is determined by the length of the divided SOC interval, and the interval from the low 4 to the peak is divided into K45, K56 and K67 according to the slope change.
When the slope and the charging rate are specifically solved, charging is carried out until the SOC reaches a standard SOC value according to the SOC in the figure 3 as a reference standard. I isXFor a current value corresponding to a certain SOC, the specific formula of the corresponding current is as follows:
(1) in the stage from peak 1 to valley 4
IX=(SOCX-SOC1)/(SOC4-SOC1)*(2.0-0.3)+0.3
Wherein X =1, 2, 3, 4;
(2) in the stage of valley 4 to peak 7
IX=(SOCX-SOC4)/(SOC7-SOC4)*(0.3-2)+2.0
Wherein X =4, 5, 6, 7;
according to the above formula, in the present embodiment, SOC1、SOC2、SOC3、SOC4、SOC5、SOC6And SOC743%, 46%, 54%, 56%, 62%, 65% and 70%, respectively, I1、I2、I3、I4、I5、I6And I70.3C, 0.7C, 1.7C, 2.0C, 1.3C, 0.9C and 0.3C, respectively.
The above embodiments are merely preferred embodiments of the present invention, and the technical solutions of the present invention are described in further detail, but the scope and implementation of the present invention are not limited thereto, and any changes, combinations, deletions, substitutions or modifications that do not depart from the spirit and principle of the present invention are included in the scope of the present invention.

Claims (9)

1. An improved safe charging method for a power lithium battery is characterized by comprising the following steps:
s1, drawing a dQ/dV standard curve of a certain type of lithium battery;
s2, normally charging the target lithium battery with the same type as the target lithium battery in the step S1, drawing a dQ/dV real-time curve and recording a dQ/dV extreme value;
s3, when the first peak value of the dQ/dV in the step S2 occurs, comparing the corresponding voltage with the voltage corresponding to the first peak value of the dQ/dV on the standard curve in the step S1, and when the deviation of the two is not more than the sum of the polarization voltage and the ohmic voltage drop of the current lithium battery charging, judging that the target lithium battery is in a safe charging state currently;
s4, measuring and calculating the consistency of the internal resistance of each single battery in the target lithium battery or calculating the internal resistance of the battery pack, and entering a quick charging stage when the internal resistance of each single battery of the target lithium battery is kept consistent or the internal resistance of the current target lithium battery is between 0.8 and 1.5 times of the normal internal resistance, wherein the quick charging stage is a charging area from a first dQ/dV peak value to a third dQ/dV peak value;
s5, in the quick charging stage, charging areas in adjacent peak and valley ranges are charged by adopting a method of changing current in a stepped mode;
and S6, after the quick charging stage is finished, adopting a method recommended by an electric vehicle manufacturer until the charging is finished, or continuously charging the target lithium battery by using constant current with the rate of 1.0C until the charging is finished, and then converting the constant current charging into constant voltage charging until the charging current is 0.05C to finish the charging.
2. The improved safe charging method for lithium power battery as claimed in claim 1, wherein in step S1, the dQ/dV standard curve is plotted as follows:
s1.1, charging a certain type of lithium battery under a constant current condition with 0.05C multiplying power, enabling the voltage to change constantly in the charging and discharging direction, and obtaining a group of voltages dV at equal intervals;
s1.2, integrating the current in each dV time interval to obtain a group of dQ;
and S1.3, drawing a dQ/dV standard curve by taking the voltage value as an abscissa and the dQ/dV value as an ordinate to obtain a voltage value corresponding to the dQ/dV value at an extreme value.
3. The improved method of safely charging a lithium-ion battery as claimed in claim 2, wherein said dV is the voltage acquisition accuracy that can be achieved by the machine at the current charge rate.
4. The improved safe charging method for lithium power battery as claimed in claim 1, wherein in the step S4, the method for measuring the consistency of the internal resistances of the individual cells specifically comprises the following steps:
s4.1, charging the target lithium battery by a user-defined descending pulse current sequence within the range of 200A-0A, and carrying out pulse charging for a plurality of times;
s4.2, collecting the voltage of each single battery at the 100ms moment of each pulse, and sending the voltage to a data analysis system;
and S4.3, calculating the internal resistance of each single battery by the data analysis system, and judging the consistency.
5. The improved method of safely charging a lithium battery according to claim 4, wherein in step S4.1, the pulse current sequences are 200A, 150A, 100A, 50A and 0A.
6. The improved safe charging method for lithium battery as claimed in claim 4 or 5, wherein the pulse interval is 10s, and each pulse current is maintained for 500ms and then made zero.
7. The improved safe charging method for lithium power battery as claimed in claim 1, wherein in step S5, the fast charging phase comprises a first fast charging interval and a second fast charging interval, the first fast charging interval is a charging area from the first peak value of dQ/dV to the second peak value of dQ/dV, and the second fast charging interval is a charging area from the second peak value of dQ/dV to the third peak value of dQ/dV.
8. The improved method of safe charging for lithium power battery as claimed in claim 1, wherein in step S5, the charging regions from the first peak value of dQ/dV to the first valley value of dQ/dV and from the second peak value of dQ/dV to the second valley value of dQ/dV are charged with stepwise increasing currents, and the charging regions from the first valley value of dQ/dV to the second peak value of dQ/dV and from the second valley value of dQ/dV to the third peak value of dQ/dV are charged with stepwise decreasing currents.
9. The improved safe charging method for lithium power battery as claimed in any one of claims 1, 7 and 8, wherein in step S5, the current multiplying factor of the stepwise varying current ranges from 0.3C to 2.0C; when dQ/dV is at the trough, the current magnification is 2.0C.
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