CN113571790A - Charging method of lithium ion battery - Google Patents
Charging method of lithium ion battery Download PDFInfo
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- CN113571790A CN113571790A CN202110942287.XA CN202110942287A CN113571790A CN 113571790 A CN113571790 A CN 113571790A CN 202110942287 A CN202110942287 A CN 202110942287A CN 113571790 A CN113571790 A CN 113571790A
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- 238000007600 charging Methods 0.000 title claims abstract description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000010278 pulse charging Methods 0.000 claims abstract description 19
- 238000010277 constant-current charging Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010281 constant-current constant-voltage charging Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 230000010287 polarization Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000028161 membrane depolarization Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/448—End of discharge regulating measures
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a charging method of a lithium ion battery, wherein the ambient temperature of the lithium ion battery is-10 ℃ to-40 ℃, and the method sequentially comprises the following steps: step one, intermittent pulse charging is carried out until the capacity of the battery is 20-30 percent of that of the battery; step two, a constant current stage; the charging multiplying power is 0.5C-1C, and the cut-off condition is the upper limit voltage of the battery; step three, a constant pressure stage; the charge cut-off condition was 0.05C; in the charging process, intermittent pulse charging is matched with constant-current charging and constant-voltage charging, and the charging speed and the capacity are kept simultaneously.
Description
Technical Field
The invention relates to the field of lithium ion battery charging methods, in particular to a charging method of a lithium ion battery in a low-temperature environment.
Background
One charge and discharge of the secondary battery is regarded as one cycle, and when the discharge capacity is recorded every cycle and the discharge capacity decreases to a certain value, the battery life is regarded as the end, and the number of cycles is called the cycle life.
When the conventional secondary battery is used, the charging rate and the discharging rate set by each charging and discharging are the same, the lithium ion battery is subjected to constant-current charging to rated voltage according to the set charging rate, and then is subjected to constant-voltage charging according to the rated voltage, so that the current is reduced to cut-off current, the charging process is completed, the lithium ion battery is ensured to have larger capacity, and the problem that the stability of the anode material is poor due to more lithium ions removed from the anode material can be avoided.
Different environments can influence the internal impedance of the battery, especially at low temperature, because the rate of electrochemical reaction is slower under the low-temperature condition, and the migration speed of lithium ions in the electrolyte is slower, the concentration polarization is larger, the speed of the battery reaching the cut-off voltage and the cut-off current is faster, so that the charging capacity of the lithium ion battery in the low-temperature environment is smaller, and the energy density capable of being exerted is also lower. At this time, charging and discharging at the same rate as normal temperature is not proper, and irreparable damage is caused to the cycle life of the battery.
Disclosure of Invention
The invention aims to provide a charging method of a lithium ion battery, which combines the charging speed and the capacity maintenance through the cooperation of intermittent pulse charging with constant-current charging and constant-voltage charging in the charging process.
In order to solve the technical problem, the technical scheme of the invention is as follows: a charging method of a lithium ion battery is provided, the environment temperature of the lithium ion battery is-10 ℃ to-40 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging is carried out until the capacity of the battery is 20-30 percent of that of the battery;
step two, a constant current stage;
the charging multiplying power is 0.5C-1C, and the cut-off condition is the upper limit voltage of the battery;
step three, a constant pressure stage;
the charge cut-off condition was 0.05C.
Preferably, the intermittent pulse charging in the first step is performed according to a sequential cycle of forward pulse-stop charging for a period of time-reverse pulse to the pulse depth. The intermittent pulse charging function of the invention is depolarization and temperature rise, and reduces the internal resistance increase phenomenon of the battery caused by low-temperature environment, and the specific action mechanism is as follows: under continuous charging, lithium ions are accumulated on the surface of the negative electrode due to insufficient lithium embedding capacity of the negative electrode, intermittent pulse charging is that the sequence of positive pulse-charging stop for a period of time-reverse pulse is circulated to the pulse depth, the lithium ions migrate to the negative electrode during the positive pulse, and the lithium ions are embedded into the negative electrode; stopping charging for a period of time to allow the negative electrode to be embedded into the lithium ions remained in the positive pulse period, and relieving the phenomenon that the lithium ions which are not embedded into the negative electrode are accumulated on the surface of the negative electrode caused by the positive pulse, namely depolarization; the reverse pulse is a one-step rapid discharge process, and on one hand, the reverse pulse plays a role in guiding lithium ions still retained on the surface of the negative electrode back to the positive electrode and further depolarizing; on the other hand, the temperature rise of the system is large in the discharging process, the reverse pulse can improve the internal temperature of the battery, and the influence of low temperature on the internal resistance of the battery is reduced.
The preferred conditions for the forward pulse are: the forward constant-current charging multiplying power is 0.05C to 0.2C, and the single forward constant-current charging time is 1min to 10 min. The charging current of the forward pulse is too large, and lithium is easy to separate out; the single charge time of the positive pulse is too short, the charge capacity is less, the charge time is prolonged, and the single charge time of the positive pulse is too long, so that lithium ions are accumulated on the surface of the negative electrode to cause lithium precipitation.
Preferred conditions for the reverse pulse are: the reverse constant current discharge rate is 0.01C to 0.1C; the single reverse pulse time is 1s to 10 s. The single reverse pulse multiplying power is too large or the time is too long, so that the discharged electricity is large, and the charging time is prolonged.
The single stop charging time is 0.5s to 10 s. The single stop charging time is too short to buffer the lithium accumulation phenomenon caused by the C1 stage, and the single stop charging time is too long to prolong the charging time.
Preferably, the temperature of the battery is raised to-10 ℃ to 0 ℃ by intermittent pulse charging, the internal resistance of the battery is obviously reduced, the depolarization effect is obvious, and the lithium precipitation is effectively inhibited.
Preferably, the lithium ion battery is one of a lithium manganate battery, a lithium iron phosphate battery, a ternary battery, a cobalt acid lithium battery and a lithium ion secondary battery prepared from a composite material. The charging method provided by the invention is suitable for various battery systems and has remarkable universality.
The cutoff voltage in the constant current phase is preferably 3.65V. The constant current stage is used for increasing the overall charging speed, the internal resistance of a battery system is reduced and the temperature of the battery is increased after the gap pulse stage, at the moment, the battery can be charged by using a higher multiplying power relative to a low-temperature environment, the overall charging speed is increased, the charging and discharging multiplying power is 0.5C-1C in the constant current stage, and the cut-off condition is the upper limit voltage of the battery; the cut-off voltage does not influence the effect of the step, the multiplying power is set too small, the required time is too long, the multiplying power is set too large and exceeds the lithium intercalation capacity of the negative electrode under the environment, the lithium precipitation phenomenon occurs, and the battery is damaged. The constant voltage stage is used for eliminating polarization generated in the constant current stage, and the charge cut-off condition is 0.05C specified in GB/T31485.
By adopting the technical scheme, the invention has the beneficial effects that:
under the low-temperature environment, the ion conductivity of the internal electrolyte of the battery is poor, the steric hindrance for releasing and embedding lithium between the positive electrode and the negative electrode is large, the internal resistance of the battery is obviously larger than that of the battery at normal temperature, and if the battery is charged by continuously using the same charging rate as the normal temperature, the lithium ions cannot be embedded into the negative electrode, polarization is caused, and the phenomenon of lithium precipitation is generated. According to the design of a battery system, the invention provides a charge-discharge mode in a low-temperature environment, a pulse stage is added in the early stage of charging, at low temperature, pulse charging is utilized to reduce polarization, the multiplying power of each charging is reduced, the lithium ion is prevented from being deposited on the surface of a negative electrode to cause lithium precipitation, the front stage of the pulse is charged by using a low-current short-time wave band, the polarization phenomenon can be effectively reduced by the pulse, the temperature environment of the battery is improved, the internal resistance generated at low temperature is reduced, after the lithium ion is embedded into a certain amount, the internal environment of the battery is improved, and the current multiplying power and the charging time are subsequently improved, so that the integral charging speed is improved;
the pulse charging depth is 20-30%, the temperature rise of the battery is effectively guaranteed, the internal polarization of the battery is relieved, and the lithium separation phenomenon in the constant current charging stage is prevented; meanwhile, the charging time is considered, the charging efficiency is effectively improved, and the capacity retention rate is improved.
Thereby achieving the above object of the present invention.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
In this example, a 2000mAh lithium iron phosphate battery was selected and charged at-20 ℃ according to the following steps and conditions:
the environment temperature of the lithium ion battery is-20 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging;
positive pulse is 0.05C for 1 min; stopping charging for 0.5 s; reverse pulse 0.01C, 1 s;
recycling to 20% of the capacity;
step two, a constant current stage;
charging to 3.65V at a multiplying power of 0.5C;
step three, a constant pressure stage;
the voltage is 3.65V to 0.05C.
Example 2
In this example, a 2000mAh lithium iron phosphate battery was selected and charged at-20 ℃ according to the following steps and conditions:
the environment temperature of the lithium ion battery is-20 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging;
positive pulse is carried out for 0.1C and 3 min; stopping charging for 3 s; reverse pulse 0.03C, 3 s;
recycling to 23% of the capacity;
step two, a constant current stage;
charging to 3.65V at a multiplying power of 0.6C;
step three, a constant pressure stage;
the voltage is 3.65V to 0.05C.
Example 3
In this example, a 2000mAh lithium iron phosphate battery was selected and charged at-20 ℃ according to the following steps and conditions:
the environment temperature of the lithium ion battery is-20 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging;
positive pulse is carried out for 0.15C and 5 min; stopping charging for 5 s; reverse pulse 0.05C, 5 s;
c1 to C3 cycle to 25% of capacity;
step two, a constant current stage;
charging to 3.65V at the multiplying power of 0.7C;
step three, a constant pressure stage;
the voltage is 3.65V to 0.05C.
Example 4
In this example, a 2000mAh lithium iron phosphate battery was selected and charged at-20 ℃ according to the following steps and conditions:
the environment temperature of the lithium ion battery is-20 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging;
positive pulse is 0.2C for 7 min; stopping charging for 7 s; reverse pulse 0.07C, 7 s;
recycling to 27% of the capacity;
step two, a constant current stage;
charging to 3.65V at a multiplying power of 0.8C;
step three, a constant pressure stage;
the voltage is 3.65V to 0.05C.
Example 5
In this example, a 2000mAh lithium iron phosphate battery was selected and charged at-20 ℃ according to the following steps and conditions:
the environment temperature of the lithium ion battery is-20 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging;
positive pulse is 0.2C for 10 min; stopping charging for 10 s; reverse pulse 0.1C, 10 s;
c1 to C3 cycle to 30% of capacity;
step two, a constant current stage;
charging to 3.65V at the multiplying power of 1C;
step three, a constant pressure stage;
the voltage is 3.65V to 0.05C.
Comparative example 1
In the embodiment, a 2000mAh lithium iron phosphate battery is selected and charged at-20 ℃ according to the following conditions: the charge was charged to 3.65V at a rate of 0.2C and was constant voltage to 0.05C.
Comparative example 2
In the embodiment, a 2000mAh lithium iron phosphate battery is selected and charged at-20 ℃ according to the following conditions: the charge was charged to 3.65V at a rate of 0.5C and was constant voltage to 0.05C.
The specific performance index data after the batteries of examples 1 to 5 and comparative examples 1 and 2 were completely charged are shown in table 1.
Table 1 list of charging performance indexes of examples 1 to 5 and comparative examples 1 and 3 at-20 deg.c
| Group of | temperature/deg.C of battery | charge/mAh | Time/h for charging | Internal resistance/m omega |
| Comparative example 1 | -16 | 1680 | 5.3 | 12 |
| Comparative example 2 | -15 | 1359 | 2.5 | 27 |
| Example 1 | -8 | 1959 | 3.4 | 7 |
| Example 2 | -6 | 1946 | 3.2 | 9 |
| Example 3 | -5 | 1940 | 3.1 | 10 |
| Example 4 | -2 | 1934 | 2.9 | 10 |
| Example 5 | 0 | 1930 | 2.8 | 11 |
As can be seen from table 1, in the comparative example 1, the charging was performed in the low-rate mode at-20 ℃, the time spent for 5.3 hours was too long, and the charged amount of electricity was only 1680 mAh; comparative example 2 at a rate of 0.5C, although the time of use was short, the charge amount was only 1359mAh due to the increase of internal polarization; in both modes, the effect is not ideal; by adopting the charging method of the present invention, the battery capacity in examples 1 to 5 is more than 20% more than the battery capacity charged in the comparative mode, and it can be seen that the charging mode is helpful for increasing the charging capacity of the battery in the low temperature environment; compared with the temperature of the battery after the battery is charged, the scheme provided by the invention effectively improves the overall temperature of the battery, the battery is beneficial to charging more electric quantity after being heated, and the higher the charging multiplying power is, the higher the temperature rise of the battery is, so that a small part of capacity is correspondingly damaged; compared with the internal resistance of the battery after charging, the proposal provided by the invention effectively slows down the accumulation of lithium ions on the negative electrode caused by high-rate charging and reduces the internal resistance of the battery; the lower the charging multiplying power is, the lower the internal resistance is, the larger the charged electric quantity is, the larger the charging multiplying power is, the shorter the charging time is, the whole charging time is less than 3.5h, the charged electric quantity is greater than 1930mAh and is 96.5% of the original capacity 2000mAh, the whole data accords with the market demand, and the low-temperature charging mode provided by the invention is proved to be practical and effective.
The battery pack of example 5 was tested for charge performance at-30 ℃ and-40 ℃ as detailed in table 2.
TABLE 2 Charge Properties at-30 ℃ and-40 ℃ of the battery obtained in example 5
| Temperature of | temperature/deg.C of battery | charge/mAh | Time/h for charging | Internal resistance/m omega |
| -30℃ | -5℃ | 1837 | 2.6 | 11 |
| -40℃ | -17℃ | 1548 | 2.4 | 16 |
As can be seen from Table 2, as the ambient temperature decreases, the surface temperature of the battery decreases, the charging amount decreases, the charging time is shortened, the internal resistance increases, but the charging amount is still 92% at-30 ℃, and 77% at-40 ℃ is far higher than the same level.
Claims (8)
1. A charging method of a lithium ion battery is characterized in that:
the environment temperature of the lithium ion battery is-10 ℃ to-40 ℃, and the method sequentially comprises the following steps:
step one, intermittent pulse charging is carried out until the capacity of the battery is 20-30 percent of that of the battery;
step two, a constant current stage;
the charging multiplying power is 0.5C-1C, and the cut-off condition is the upper limit voltage of the battery;
step three, a constant pressure stage;
the charge cut-off condition was 0.05C.
2. The method of charging a lithium ion battery according to claim 1, wherein: the rule of intermittent pulse charging in the first step is that the sequence of forward pulse, stopping charging for a period of time and reverse pulse is cycled to the pulse depth.
3. The method of charging a lithium ion battery according to claim 2, wherein: the conditions for the forward pulse are: the forward constant-current charging multiplying power is 0.05C to 0.2C, and the single forward constant-current charging time is 1min to 10 min.
4. The method of charging a lithium ion battery according to claim 2, wherein: the conditions for the reverse pulse are: the reverse constant current discharge rate is 0.01C to 0.1C; the single reverse pulse time is 1s to 10 s.
5. A method of charging a lithium ion battery as claimed in claim 2, characterized in that: the single stop charging time is 0.5s to 10 s.
6. The method of charging a lithium ion battery according to claim 2, wherein: the temperature of the battery is raised to-10 ℃ to 0 ℃ by intermittent pulse charging.
7. The method of charging a lithium ion battery according to claim 1, wherein: the lithium ion battery is one of a lithium manganate battery, a lithium iron phosphate battery, a ternary battery, a cobalt acid lithium battery and a lithium ion secondary battery prepared from a composite material.
8. The method of charging a lithium ion battery according to claim 1, wherein: the cut-off voltage in the constant current phase was 3.65V.
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Application publication date: 20211029 |