CN112928351A - Pulse charging technology of lithium-sulfur battery - Google Patents
Pulse charging technology of lithium-sulfur battery Download PDFInfo
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- CN112928351A CN112928351A CN202110184565.XA CN202110184565A CN112928351A CN 112928351 A CN112928351 A CN 112928351A CN 202110184565 A CN202110184565 A CN 202110184565A CN 112928351 A CN112928351 A CN 112928351A
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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
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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 invention discloses a pulse charging technology of a lithium-sulfur battery, and belongs to the technical field of battery charging. The charging technology comprises two technical schemes: the negative pulse current is gradually reduced and the pulse charging of the charging current is fixed; the pulse standing time is gradually shortened and the pulse charging of the charging current is fixed. Compared with the prior art, the method has the advantages that the polarization influence caused by constant-current charging is obviously reduced, the polarization potential of the cathode of the battery is reduced, the charging speed of the battery is improved, and the charging potential of the lithium-sulfur battery is further developed by changing the pulse charging frequency.
Description
Technical Field
The invention belongs to the technical field of battery charging, and particularly relates to a pulse charging technology of a lithium-sulfur battery.
Background
With the increasingly prominent energy and environmental issues and the rapid development of the electric automobile industry, it is increasingly difficult for traditional lithium ion batteries to meet the needs of people for high energy density batteriesAnd (6) obtaining. The lithium-sulfur battery has the characteristics of high theoretical specific capacity, low cost, no pollution and the like, and is considered to be one of the most potential new generation high-energy density battery systems. However, there are still many problems that restrict the development and wide application of lithium sulfur batteries. These problems include sulfur and its reduction product Li2Poor electronic and ionic conductivity of S, insoluble Li in circulation process2The accumulation of S, uneven sulfur reaction in the positive electrode during charging and discharging, uneven reaction on the lithium negative electrode and even generation of lithium dendrites, etc., lead to poor cycle life of lithium-sulfur batteries, hindering their commercialization process.
To slow down insoluble Li during cycling2The accumulation of S, the reduction of non-uniform reactions on the electrodes and the inhibition of the growth of lithium dendrites, in addition to the optimization of the chemical system of the battery, is one of the ways to solve these problems by developing a pulse charging technique that conforms to the characteristics of lithium-sulfur batteries. Due to insoluble Li2S and Li2S2The polarization of the lithium-sulfur battery during the charging process shows a trend from big to small. The invention provides a pulse charging technology relating to a lithium-sulfur battery according to the change characteristics of polarization in the charging process of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a pulse charging technology of a lithium-sulfur battery, which can improve the charging speed of the battery by reducing the polarization of the battery in the charging process and simultaneously can slow down insoluble Li in the circulating process2The accumulation of S reduces the non-uniform reaction on the electrode and inhibits the growth of lithium dendrites on the negative electrode.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the pulse charging technology for lithium-sulfur battery is a pulse charging mode with gradually reduced pulse current and fixed charging current; alternatively, the pulse charging method is a pulse charging method in which the pulse rest time is gradually shortened and the charging current is fixed.
The specific charging technical scheme comprises the following steps (S1) - (S2):
(S1) setting a charging current value IcA charging time value tcA set of gradually reduced negative pulse current values Id{Id1,Id2,Id3,.....,IdnOr a set of progressively decreasing pulse rest time values tr{tr1,tr2,tr3,……,trnA discharge time value tdSetting a cut-off voltage Vmax；
(S2) the charging current for the first pulse charging of the battery is IcCharging time tcThen the battery is discharged or is kept still, and if the battery is discharged, the discharging current I is obtainedd1Discharge time tdThe standing time is t if the battery is kept standingr1(ii) a The charging current for the second pulse charging of the battery is IcCharging time tcThen the battery is discharged or is kept still, and if the battery is discharged, the discharging current I is obtainedd2Discharge time tdThe standing time is t if the battery is kept standingr2(ii) a Sequentially carrying out the nth pulse charging to the battery with the charging current of IcCharging time of tcThen the battery is discharged or is kept still, and if the battery is discharged, the current I is dischargeddnDischarge time tdIf the mixture is allowed to stand, the standing time is trn(ii) a The operation is circulated until the battery voltage reaches a cut-off voltage Vmax。
In step (S2), the battery negative pulse current is gradually decreased, wherein Id1The value is maximum.
In step (S2), the battery pulse rest time is gradually decreased, where tr1The value is maximum.
In step (S1), the charging current IcIs a fixed value and is in the range of 0.05C to 10C.
In step (S1), the charging time value tcIn the range of 0.1s to 30 s.
In step (S1), discharge current value { I }d1,Id2,Id3,.....,IdnThe value is in the range of 0C-0.2C.
In step (S1), discharge time value tdIn the range of 0.01s to 5 s.
In step (S1), the standing time value tr{tr1,tr2,tr3,……,trnWithin the range of 0.01s to 30 s.
And (S2) after the battery is placed in an environment with the temperature of-60 to 60 ℃, the battery is charged.
The pulse standing time is gradually reduced, the pulse charging of the charging current is fixed, the pulse standing time is gradually reduced, and the pulse charging current value and each pulse charging time value are fixed values.
The negative pulse current of the invention is gradually reduced and the pulse charging of the charging current is fixed, the negative pulse current value is gradually reduced, and the pulse charging current value, each pulse positive pulse charging time value and each negative pulse time value are all fixed values.
Drawings
Fig. 1 is a pulse charge with a gradually decreasing pulse rest time and a fixed charge current.
Fig. 2 is a pulse charge with a negative pulse current gradually decreasing and a fixed charge current.
FIG. 3 is a graph of the charging curves of example 1 and a comparative example.
FIG. 4 is a graph of the charging curves of example 2 and a comparative example.
FIG. 5 is a graph showing the cycle performance of examples and comparative examples.
Detailed Description
In order to better understand the technical solution of the present invention, the following further describes the content of the present invention with reference to specific implementation examples.
The battery systems adopted in all the examples and the comparative examples of the invention are consistent, and the actual capacities of all the batteries are in the range of 1.0-1.1 mAh. The cathode is a sulfur anode taking the ordered mesoporous carbon as a sulfur carrier, the cathode is metallic lithium, the button cell further comprises an isolating membrane and electrolyte, and the button cell is obtained through the processes of cell assembly, activation and the like. During the preparation process of the cathode, firstly, the ordered mesoporous carbon and sulfur powder are mixed in a proportion of 7: 3, then placing the mixed material in a reaction kettle at 155 ℃ for 12 hours, cooling, and mixing with PVDF and conductive carbon black in a weight ratio of 8: 1:1, mixing evenly according to the weight ratio of N-methylThe radical pyrrolidone is used as solvent. The isolating membrane is a microporous PP film, the electrolyte is lithium salt lithium trifluoromethanesulfonate imide dissolved in 1, 3-dioxane/1, 2-dimethoxyethane (DOL/DME, volume ratio is 1:1), and 2 wt% of LiNO is added3And (b) an additive, wherein the solubility of lithium salt is 1 mol/L. In addition, all tests are carried out in the environment of normal temperature 25 ℃, and the voltage test range is 1.7-2.8V.
The content of the embodiments of the invention and the comparative examples is as follows:
comparative example 1
And (4) constant current charging and discharging, wherein the charging current and the discharging current are both 0.5C.
Example 1
Pulse charging with a gradually decreasing pulse rest time and a fixed charging current magnitude, referring to fig. 1, the technique is characterized by a pulse rest time IrGradually decreases while the remaining parameters (each pulse charging current I)cAnd a charging time t of each pulsec) Remain unchanged.
The specific procedure of example 1 is as follows:
setting a set of gradually reduced pulse standing time values tr{tr1,tr2,tr3,……,trnIn which the first pulse has a rest time value tr1At 20s, the second pulse rest time value tr219.99s, namely the difference value of the charging current of the two pulses is 0.01s, then the standing time of each pulse is gradually reduced by taking 0.01s as the descending amplitude, and the charging current I of each pulse is setc0.588mA, and each pulse has charging time tcIt is 10s, and the charging is carried out until the cut-off voltage is 2.8V.
Example 2
The technique of pulse charging in which the magnitude of the negative pulse current is gradually reduced and fixed with reference to fig. 2 is characterized by the negative pulse current IdGradually decreases while the remaining parameters (each pulse charging current I)cCharging time t of each pulsecAnd each negative pulse time td) Remain unchanged.
The specific procedure of example 2 is as follows:
setting a set of gradually decreasing negative pulse current values Id{Id1,Id2,Id3,.....,IdnIn which the first negative pulse current value Id10.3mA, second negative pulse current value Id2Is 0.299mA, namely the difference value of the two negative pulse currents is 0.001mA, then each negative pulse current is reduced by taking 0.001mA as the amplitude reduction, and each pulse charging current I is setc0.588mA, and each pulse has charging time tcThe time of each negative pulse is 1s for 10s, and the cycle is repeated, and the charging is carried out until the cut-off voltage is 2.8V.
Fig. 3 and 4 are charging graphs of example 1 and example 2 in an ambient temperature of 25 deg.c, respectively. As can be seen from the figure, both charging solutions of the present invention can reduce the polarization during the charging process of the battery, particularly the polarization at the initial stage of the charging of the battery, compared to the comparative example.
FIG. 5 is a graph showing cycle performance of examples 1 and 2 and a comparative example. It can be seen from the figure that after nearly 50 cycles, all the examples of the present invention can not only increase the charging speed of the battery, but also maintain good cycle performance, compared with the comparative example, which indicates that the charging technology of the present invention does not adversely affect the performance of the battery.
In order to more clearly express the charging advantages of all the examples, table 1 briefly summarizes the charging parameters and the charging speeds of the examples and the comparative examples.
TABLE 1 table of Performance parameters for examples and comparative examples
In combination with the above-described embodiments, the charging technology for lithium-sulfur batteries according to the present invention, by designing to gradually increase the pulse charging frequency, slows down the polarization during the charging process of the batteries, and increases the conversion rate of different mesophases of sulfur and lithium, especially insoluble Li2S and Li2S2Slow the insoluble solid Li in the circulation2And (4) accumulating S. In addition, a pulse mode can also promote the electrolyte and the surface of the electrode to form a thin and more compact SEI film or CEI film, reduce uneven reaction on the electrode, promote uniform deposition of lithium ions on the negative electrode, and inhibit the growth of lithium dendrites so as to improve the comprehensive performance of the battery.
Finally, it should be noted that the above-described embodiments are only used for describing the technical solutions of the present invention, and are not limited thereto. The present invention may be suitably modified in the above-described embodiments, or some or all of the technical features may be equivalently replaced. Therefore, some modifications or changes to the present invention should also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A pulse charging technique for a lithium sulfur battery, characterized by: the charging technology is a pulse charging mode in which pulse current is gradually reduced and charging current is fixed; or, the charging technology is a pulse charging mode that the pulse standing time is gradually shortened and the charging current is fixed.
2. The charging technique for a lithium sulfur battery according to claim 1, characterized in that: the specific charging technical scheme comprises the following steps (S1) - (S2):
(S1) setting a charging current value IcA charging time value tcA set of gradually reduced negative pulse current values Id{Id1,Id2,Id3,.....,IdnOr a set of progressively decreasing pulse rest time values tr{tr1,tr2,tr3,……,trnA discharge time value tdSetting a cut-off voltage Vmax；
(S2) the charging current for the first pulse charging of the battery is IcCharging time tcThen the battery is discharged or is kept still, and if the battery is discharged, the discharging current I is obtainedd1Discharge time tdThe standing time is t if the battery is kept standingr1(ii) a The charging current for the second pulse charging of the battery isIcCharging time tcThen the battery is discharged or is kept still, and if the battery is discharged, the discharging current I is obtainedd2Discharge time tdThe standing time is t if the battery is kept standingr2(ii) a Sequentially carrying out the nth pulse charging to the battery with the charging current of IcCharging time of tcThen the battery is discharged or is kept still, and if the battery is discharged, the current I is dischargeddnDischarge time tdIf the mixture is allowed to stand, the standing time is trn(ii) a The operation is circulated until the battery voltage reaches a cut-off voltage Vmax。
3. The lithium sulfur battery charging technique as claimed in claim 2, wherein: in step (S2), the battery negative pulse current is gradually decreased, wherein Id1The value is maximum.
4. The lithium sulfur battery charging technique as claimed in claim 2, wherein: in step (S2), the battery pulse rest time is gradually decreased, where tr1The value is maximum.
5. The method of charging a lithium sulfur battery according to claim 2, characterized in that: in step (S1), the charging current IcIs a fixed value and is in the range of 0.05C to 10C.
6. The method of charging a lithium sulfur battery according to claim 2, characterized in that: in step (S1), the charging time value tcIn the range of 0.1s to 30 s.
7. The method of charging a lithium sulfur battery according to claim 2, characterized in that: in step (S1), discharge current value { I }d1,Id2,Id3,.....,IdnThe value is in the range of 0C-0.2C.
8. The method of charging a lithium sulfur battery according to claim 2, characterized in that: in step (S1), discharge time value tdIn the range of 0.01s to 5 s.
9. The method of charging a lithium sulfur battery according to claim 2, characterized in that: in step (S1), the standing time value tr{tr1,tr2,tr3,……,trnWithin the range of 0.01s to 30 s.
10. The lithium sulfur battery charging technique as claimed in claim 1, wherein: and (S2) after the battery is placed in an environment with the temperature of-60 to 60 ℃, the battery is charged.
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| US20130049673A1 (en) * | 2011-03-23 | 2013-02-28 | Indian Institute Of Technology | Photo-voltaic array fed switched capacitor dc-dc converter based battery charging for li-ion batteries |
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Application publication date: 20210608 |