CN110323506A - A kind of chemical conversion antihunt means before lithium ion battery storage - Google Patents
A kind of chemical conversion antihunt means before lithium ion battery storage Download PDFInfo
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- CN110323506A CN110323506A CN201910623541.2A CN201910623541A CN110323506A CN 110323506 A CN110323506 A CN 110323506A CN 201910623541 A CN201910623541 A CN 201910623541A CN 110323506 A CN110323506 A CN 110323506A
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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
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- 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
Abstract
The present invention provides the chemical conversion antihunt means before a kind of storage of lithium ion battery, the lithium ion battery is stored for a long time after antihunt means provided by the invention, capacity retention ratio after being able to maintain higher storage life and storage, the method includes by battery constant-current discharge to the first discharge cut-off voltage, then with low discharging current to the predetermined voltage for being lower than the first discharge cut-off voltage, low current constant current charge-discharge recycles under the predetermined voltage and the first discharge cut-off voltage, charge and discharge cycles are carried out between the first discharge cut-off voltage and the first charge cutoff voltage with the first electric current, described first, second, third discharge cut-off voltage successively increases, described first, second, third charge cutoff voltage successively reduces, described first, second, third electric current is sequentially reduced；Adjustment cell voltage carries out positive negative pulse stuffing charge and discharge near storage voltage, the positive negative impulse current is equal in magnitude, and action time is identical to voltage is stored.
Description
Technical field
The present invention relates to technical field of lithium ion, stablize more particularly to the chemical conversion before a kind of storage of lithium ion battery
Method.
Background technique
In the case where lithium ion battery enters the large-scale application stage, lithium battery industry development is also by the branch energetically of national governments
It holds.Compared with conventional batteries, lithium battery is high with energy density, operating voltage is high, light-weight, small in size, self discharge is small, without note
Recall effect, have extended cycle life, charge quickly etc. advantages, rapidly become the key player of energy storage technology.
But in lithium ion battery after storing for a long time, the decaying of Yi Fasheng battery life, battery capacity conservation rate
Decline, by inventor it is long-term the study found that it is exactly that electrolyte is being deposited that when storage, which influences one of the factor of battery storage life,
Abnormal response when storage in electrode surface causes, and battery carries out chemical conversion before storing and stablizes at certain in specific voltage section
When, what electrolyte can be relatively stable is kept, thus the storage performance of the battery improved.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of lithium ion battery storage before chemical conversion antihunt means, the lithium from
Sub- battery is stored for a long time after antihunt means provided by the invention, after being able to maintain higher storage life and storage
Capacity retention ratio, the method includes by battery constant-current discharge to the first discharge cut-off voltage, then extremely with low discharging current
Lower than the predetermined voltage of the first discharge cut-off voltage, low current constant current is filled under the predetermined voltage and the first discharge cut-off voltage
Discharge cycles carry out charge and discharge cycles with the first electric current between the first discharge cut-off voltage and the first charge cutoff voltage, with
Two electric currents carry out charge and discharge cycles between the second discharge cut-off voltage and the second charge cutoff voltage, are put with third electric current in third
Carry out charge and discharge cycles between electric blanking voltage and third charge cutoff voltage, first, second, third discharge cut-off voltage according to
Secondary raising, first, second, third charge cutoff voltage successively reduce, and first, second, third electric current is sequentially reduced；
Adjustment cell voltage carries out positive negative pulse stuffing charge and discharge, the positive negative impulse current size near storage voltage to voltage is stored
Equal, action time is identical.
Inventor by prolonged the study found that before battery stores for a long time, by specific chemical synthesizing method to battery
Internal SEI film is modified, and has large effect to the storage performance of battery, firstly, advantageous compared with the circulation under low potential
In the SEI film for eliminating battery cathode transition deposition, into electrolyte, then the lithium ion for making part form SEI film re-dissolves
By the charge and discharge cycles repeatedly under different voltages, gradually the voltage range of charge and discharge cycles is reduced, is leaned on to storage voltage
Hold together, finally carries out charge and discharge pulse cycle near storage voltage, formation process in this way, inventor's discovery is in storage electricity
Electrolyte near pressure is less to the side reaction of battery, holding that can be relatively stable, while gradually reducing by electric current,
Successive elimination stores the voltage polarizing near voltage, improves the stability of electrolyte at this voltage.
Long-term storage in the present invention is referred to by 6 months processes stored above.
Specific scheme is as follows:
A kind of chemical conversion antihunt means before lithium ion battery storage, which comprises
1), by battery constant-current discharge to the first discharge cut-off voltage；
2), with low discharging current to the predetermined voltage for being lower than the first discharge cut-off voltage；
3), with low current constant current charge-discharge circulation between the predetermined voltage and the first discharge cut-off voltage；
4) it is several that charge and discharge cycles, are carried out between the first discharge cut-off voltage and the first charge cutoff voltage with the first electric current
It is secondary；
5) it is several that charge and discharge cycles, are carried out between the second discharge cut-off voltage and the second charge cutoff voltage with the second electric current
It is secondary；
6) it is several that charge and discharge cycles, are carried out between third discharge cut-off voltage and third charge cutoff voltage with third electric current
Secondary, first, second, third discharge cut-off voltage successively increases, and first, second, third charge cutoff voltage is successively
It reduces, first, second, third electric current is sequentially reduced；
7), adjustment cell voltage is to storing voltage；
8), the positive negative pulse stuffing charge and discharge cycles predetermined time is carried out near storage voltage.
Further, constant-current discharge is carried out with the electric current of 0.1-0.3C in the step 1.
Further, first discharge cut-off voltage is 2.7-2.75V, and the predetermined voltage is 2.65-2.7V.
Further, the low current in the step 2 and 3 is independently 0.02-0.05C.
Further, the first charge cutoff voltage is 4.2-4.25V；Second charge cutoff voltage is 4.0-4.05V；Third
Charge cutoff voltage is 3.8-3.85V；Second discharge cut-off voltage is 3.0-3.05V；Third discharge cut-off voltage is
3.3-3.35V；Described first, second, third electric current is 0.1-0.5C.
Further, the storage voltage is 3.5-3.6V.
Further, alternately, pulse current magnitude is equal for the positive negative pulse stuffing, and action time is identical, pulse charge
Action time with electric discharge is 5-30s, is spaced 1-10s, pulse current 0.02-0.05C.
The invention has the following beneficial effects:
1), in the SEI film for being conducive to eliminate battery cathode transition deposition compared with the circulation under low potential, part is made to form SEI
The lithium ion of film is re-dissolved into electrolyte, reduces the internal resistance of cell；
2), by the charge and discharge cycles repeatedly under different voltages, gradually the voltage range of charge and discharge cycles is reduced, to
Storage voltage is drawn close, and finally carries out charge and discharge pulse cycle near storage voltage, and formation process in this way regenerates
SEI film, and the battery after inventor's discovery so chemical conversion, near storage voltage, electrolyte is less to the side reaction of battery, energy
It is enough relatively stable to be kept；
3), gradually reducing by charging and discharging currents, successive elimination store the voltage polarizing near voltage, improve electrolyte
Stability at this voltage；
4), by the battery of the method for the present invention, storage performance is preferable, and higher cycle life and appearance are able to maintain after storage
Measure retention property.
Specific embodiment
The present invention will be described in more detail below by specific embodiment, but protection scope of the present invention not by
It is limited to these embodiments.
The lithium cobaltate cathode lithium ion battery that the battery used of the invention is 2400mAh for commercially available rated capacity, with
After 1C is recycled 100 times, the stability before storing to it is at then room temperature stores 6 months.
Embodiment 1
1), by the battery with the electric current constant-current discharge of 0.1C to 2.7V；
2) 2.65V, is discharged to 0.02C；
3), 0.02C constant current charge-discharge recycles 5 times between 2.65V and 2.7V；
4) it, is carried out charge and discharge cycles 5 times between 2.7V and 4.2V with 0.5C；
5) it, is carried out charge and discharge cycles 5 times between 3.0V and 4.0V with 0.3C；
6) it, is carried out charge and discharge cycles 5 times between 3.3V and 3.8V with 0.1C；
7) cell voltage, is adjusted to 3.5V；
8) positive negative pulse stuffing charge and discharge cycles 20min, is carried out near 3.5V, alternately, pulse is electric for the positive negative pulse stuffing
Flow equal in magnitude, pulse current 0.02C, action time is identical, and the action time of pulse charge and electric discharge is 30s, interval
10s。
Embodiment 2
1), by the battery with the electric current constant-current discharge of 0.3C to 2.75V；
2) 2.7V, is discharged to 0.05C；
3), 0.05C constant current charge-discharge recycles 6 times between 2.7V and 2.75V；
4) it, is carried out charge and discharge cycles 6 times between 2.75V and 4.25V with 0.5C；
5) it, is carried out charge and discharge cycles 6 times between 3.05V and 4.05V with 0.3C；
6) it, is carried out charge and discharge cycles 6 times between 3.35V and 3.85V with 0.1C；
7) cell voltage, is adjusted to 3.6V；
8) positive negative pulse stuffing charge and discharge cycles 20min, is carried out near 3.6V, alternately, pulse is electric for the positive negative pulse stuffing
Flow equal in magnitude, pulse current 0.05C, action time is identical, and the action time of pulse charge and electric discharge is 5s, is spaced 1s.
Embodiment 3
1), by the battery with the electric current constant-current discharge of 0.2C to 2.7V；
2) 2.65V, is discharged to 0.02C；
3), 0.02C constant current charge-discharge recycles 5 times between 2.65V and 2.7V；
4) it, is carried out charge and discharge cycles 5 times between 2.7V and 4.2V with 0.5C；
5) it, is carried out charge and discharge cycles 5 times between 3.05V and 4.0V with 0.3C；
6) it, is carried out charge and discharge cycles 5 times between 3.35V and 3.8V with 0.1C；
7) cell voltage, is adjusted to 3.55V；
8) positive negative pulse stuffing charge and discharge cycles 20min, is carried out near 3.55V, alternately, pulse is electric for the positive negative pulse stuffing
Flow equal in magnitude, pulse current 0.03C, action time is identical, and the action time of pulse charge and electric discharge is 20s, is spaced 5s.
Comparative example 1
1), by the battery with the electric current constant-current discharge of 0.1C to 2.7V；
2) 2.65V, is discharged to 0.02C；
3), 0.02C constant current charge-discharge recycles 5 times between 2.65V and 2.7V；
4) cell voltage, is adjusted to 3.55V；
Comparative example 2
1) it, is carried out charge and discharge cycles 5 times between 2.7V and 4.2V with 0.5C；
5) it, is carried out charge and discharge cycles 5 times between 3.05V and 4.0V with 0.3C；
3) it, is carried out charge and discharge cycles 5 times between 3.35V and 3.8V with 0.1C；
4) cell voltage, is adjusted to 3.55V；
5) positive negative pulse stuffing charge and discharge cycles 20min, is carried out near 3.55V, alternately, pulse is electric for the positive negative pulse stuffing
Flow equal in magnitude, pulse current 0.03C, action time is identical, and the action time of pulse charge and electric discharge is 20s, is spaced 5s.
Comparative example 3
Cell voltage is adjusted to 3.55V.
Experiment and data
Capacity retention ratio is battery charging and discharging capacity/battery calibration rated capacity that test obtains, by embodiment 1-3 and
The battery of comparative example 1-3, the capacity retention ratio after being recycled 10 times and 100 times under the electric current of 0.1C respectively.Seen from table 1, it deposits
Progress low pressure recycle and the progressive formation process to storage voltage of step voltage have battery performance different degrees of before storage
It influences, and passes through the battery of activation method of the present invention, either from the point of view of the capacity retention ratio at initial stage or the cyclicity in later period
Can from the point of view of, better than not activated battery.
Table 1
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it would be recognized that above-mentioned
Description be not considered as limitation of the present invention.
Claims (7)
1. the chemical conversion antihunt means before a kind of lithium ion battery storage, which comprises
1), by battery constant-current discharge to the first discharge cut-off voltage；
2), with low discharging current to the predetermined voltage for being lower than the first discharge cut-off voltage；
3), with low current constant current charge-discharge circulation between the predetermined voltage and the first discharge cut-off voltage；
4) charge and discharge cycles, are carried out several times between the first discharge cut-off voltage and the first charge cutoff voltage with the first electric current；
5) charge and discharge cycles, are carried out several times between the second discharge cut-off voltage and the second charge cutoff voltage with the second electric current；
6) charge and discharge cycles, are carried out several times between third discharge cut-off voltage and third charge cutoff voltage with third electric current,
First, second, third discharge cut-off voltage successively increases, and first, second, third charge cutoff voltage successively drops
Low, first, second, third electric current is sequentially reduced；
7), adjustment cell voltage is to storing voltage；
8), the positive negative pulse stuffing charge and discharge cycles predetermined time is carried out near storage voltage.
2. carrying out constant-current discharge in the step 1 such as above-mentioned method described in claim 1 with the electric current of 0.1-0.3C.
3. the method as described in the claims, first discharge cut-off voltage is 2.7-2.75V, and the predetermined voltage is
2.65-2.7V。
4. the method as described in the claims, the low current in the step 2 and 3 is independently 0.02-0.05C.
5. the method as described in the claims, the first charge cutoff voltage is 4.2-4.25V；Second charge cutoff voltage is
4.0-4.05V；Third charge cutoff voltage is 3.8-3.85V；Second discharge cut-off voltage is 3.0-3.05V；Third is put
Electric blanking voltage is 3.3-3.35V；Described first, second, third electric current is 0.1-0.5C.
6. the method as described in the claims, the storage voltage is 3.5-3.6V.
7. the method as described in the claims, alternately, pulse current magnitude is equal for the positive negative pulse stuffing, action time
Identical, the action time of pulse charge and electric discharge is 5-30s, is spaced 1-10s, pulse current 0.02-0.05C.
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| CN111446514A (en) * | 2020-03-17 | 2020-07-24 | 上海理工大学 | Method for reasonably adjusting discharge cut-off voltage of lithium battery along with service life attenuation of battery |
| CN112117506A (en) * | 2020-10-22 | 2020-12-22 | 江苏卫健信息科技有限公司 | Storage method of power lithium ion battery |
| CN114361624A (en) * | 2021-12-09 | 2022-04-15 | 万向一二三股份公司 | Method for evaluating quick charging stability of lithium ion power battery |
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