CN113241482A - Charging technology of lithium-sulfur battery - Google Patents
Charging technology of lithium-sulfur battery Download PDFInfo
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- CN113241482A CN113241482A CN202110184673.7A CN202110184673A CN113241482A CN 113241482 A CN113241482 A CN 113241482A CN 202110184673 A CN202110184673 A CN 202110184673A CN 113241482 A CN113241482 A CN 113241482A
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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 charging technology of a lithium-sulfur battery, and belongs to the technical field of battery charging. The charging technology comprises two charging schemes: the charging current is gradually increased and matched with the pulse charging of the negative pulse current; the charging current is gradually increased and matched with the pulse standing time for pulse charging. Compared with constant-current charging, the charging technology can improve the charging speed of the battery, shorten the charging time and improve the electrochemical performance of the battery on the premise of the same charging electric quantity by reducing the charging polarization, particularly the polarization at the initial charging stage and excavating the charging potential.
Description
Technical Field
The invention belongs to the technical field of battery charging, and particularly relates to a charging technology of a lithium-sulfur battery.
Background
The lithium sulfur battery, as a secondary battery, has attracted researchers' extensive interest due to its ultra-high theoretical energy density of 2600 Wh/Kg. In addition, the sulfur is easy to obtain and low in cost, and is novelOne of the best choices of electrochemical energy storage systems. Unlike lithium batteries such as lithium iron phosphate, ternary nickel cobalt manganese, lithium cobaltate, and the like, which use the mechanism of insertion and extraction of lithium ions, lithium sulfur batteries use the chemical reaction between lithium ions and sulfur to realize energy conversion. A series of reversible chemical reactions occur in the charging and discharging processes of the lithium-sulfur battery, and S is respectively in a solid state in the discharging process8Conversion to liquid higher-order polysulphides Li2S8、Li2S6、Li2S4And then converted into low-order solid Li2S2And Li2S, and the charging process is reversed. Due to the characteristics of low conductivity of elemental sulfur, slow solid-phase conversion rate in the charging process, continuous dissolution of polysulfide in electrolyte and the like, high internal resistance is caused, and the performance of the battery is influenced. During cycling of lithium sulfur batteries, the accumulation of insoluble solid lithium sulfide results in the loss of more and more active lithium and sulfur, resulting in a decline in battery capacity.
One approach to solving these problems is to reduce the internal resistance of the lithium sulfur battery during charging and to slow the accumulation of insoluble solid lithium sulfide during cycling by developing new charging techniques to reduce the polarization of the charging process. Due to insoluble Li2S and Li2S2The polarization of the lithium-sulfur battery during the charging process shows a trend from big to small. The present invention provides various charging techniques for lithium sulfur batteries based on polarization characteristics of lithium sulfur battery charging.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery charging technology, which reduces the polarization in the charging process, slows down the accumulation of insoluble solid lithium sulfide, exploits the charging capacity of the battery and improves the cycle performance of the battery to a certain extent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a charging technology of a lithium sulfur battery is a pulse charging mode that the charging current is gradually increased and is matched with pulse standing time; or, the charging current is gradually increased and matched with a pulse charging mode of negative pulse current. The charging technique includes the following steps (S1) - (S2):
(S1) setting a set of gradually increasing charging current values Ic{Ic1,Ic2,Ic3,……,IcnA discharge current value IdA charging time value tcA discharge time value tdAnd a standing time trSetting a cut-off voltage Vmax；
(S2) the charging current for the first pulse charging of the battery is Ic1Charging time tcThen discharging the battery or standing, if discharging the battery, the discharging current is IdDischarge time tdThe standing time is t if the battery is kept standingr(ii) a Then carrying out second pulse charging on the battery with charging current Ic2Charging time tcDischarging the battery or standing, and if discharging the battery, the discharging current is IdDischarge time tdThe standing time is t if the battery is kept standingr(ii) a Sequentially charging the battery by the nth pulse charging with charging current of IcnCharging time tcFinally discharging or standing the battery with discharge current IdDischarge time tdOr a standing time tr(ii) a The operation is circulated until the battery voltage reaches a cut-off voltage Vmax。
In step (S2), the battery pulse charging current is increased from small to large, wherein Ic1Is the minimum value.
In step (S1), the charging current value Ic{Ic1,Ic2,Ic3,……,IcnThe rate is in the range of 0.05C-10C.
In step (S1), the charging time value tcIn the range of 0.1s to 30 s.
In step (S1), discharge current value IdIn the range of 0C to 0.2C.
In step (S1), discharge time value tdIn the range of 0.01s to 5 s.
In step (S1), the standing time value trIn the range of 0.01s to 30 s.
And (S2) after the battery is placed in an environment with the temperature of-80 to 60 ℃, the battery is charged.
In the charging process, the charging current is gradually increased, the pulse standing time is fixed, the pulse charging current is gradually increased, and each pulse charging time value and each pulse standing time value are constant values.
In the charging process of the invention, the charging current is gradually increased and pulse charging of the negative pulse current is fixed, the pulse charging current is gradually increased, and each pulse charging time value, each negative pulse current value and each negative pulse time value are constant values.
Drawings
Fig. 1 is a pulse charge with a gradually increasing charge current and a fixed pulse rest time.
Fig. 2 is a pulse charge with a gradually increasing charge current and a fixed negative pulse 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 ratio of 8: 1:1, and the components are uniformly mixed according to the weight ratio and are prepared by taking N-methyl pyrrolidone as a solvent. The isolating membrane is a microporous PP film, and the electrolyte is lithium salt IIILithium fluoromethylsulfonate was dissolved in 1, 3-dioxacycloalkane/1, 2-dimethoxyethane (DOL/DME, volume ratio: 1), and 2 wt% of LiNO was 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 gradually increasing charging current and fixed pulse rest time, referring to fig. 1, the technique is characterized in that the charging current I is in the pulse charging processcGradually increasing, while the remaining parameters (charging time t per pulse)cAnd rest time t of each pulser) Remain unchanged.
The specific procedure of example 1 is as follows:
setting a set of gradually increasing pulse charging current values Ic{Ic1,Ic2,Ic3,……,IcnIn which the first pulse charge current value Ic10.052mA, second pulse charging current value Ic20.057mA, namely the difference value of the charging current of the two pulses is 0.005mA, then each pulse charging current is increased gradually by taking 0.005mA as the amplification, and each pulse charging time t is setc10s, each pulse standing time trIs 1s, and is cycled, and is charged to the cut-off voltage of 2.8V.
Example 2
The charging current gradually increases and the pulse charging with the magnitude of the negative pulse current is fixed, referring to fig. 2, the technology is characterized in that the charging current I is in the pulse charging processcGradually increased, and the rest of the parameters (each negative pulse current I)dCharging time t of each pulsecAnd each negative pulse time td) Remain unchanged.
The specific procedure of example 2 is as follows:
set a groupGradually increasing pulse charging current value Ic{Ic1,Ic2,Ic3,……,IcnIn which the first pulse charge current value Ic10.052mA, second pulse charging current value Ic20.057mA, namely the difference value of the charging current of the two pulses is 0.005mA, then each pulse charging current is increased gradually by taking 0.005mA as the amplification, and each negative pulse current I is setd0.001mA, charging time t for each pulsec10s, each pulse standing time trIs 1s, and is cycled, and is charged to the cut-off voltage of 2.8V.
Fig. 3 and 4 are charging graphs of examples 1 and 2, respectively, at a normal temperature of 25 ℃, and it can be seen that both charging solutions of the present invention can reduce the polarization during the charging process of the battery, especially the polarization at the initial stage of charging the battery.
FIG. 5 is a graph showing cycle performance of examples 1 and 2 and a comparative example. As can be seen from the figure, all examples of the present invention can not only improve the charge rate of the battery but also maintain good cycle performance after 50 cycles, compared to the comparative example.
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 lithium-sulfur battery charging technology of the present invention is designed to gradually increase the pulse charging current and match with a constant pulse standing time or a constant negative pulse current, so as to slow the polarization accumulation during the charging process, reduce the polarization potential, especially the polarization at the initial charging stage, promote the conversion of different intermediate phases between sulfur and lithium, and improve the solid Li2S and Li2S2Slow the insoluble solid Li in the cycle2Accumulation of S to boost up electricityThe charge and discharge performance of the cell.
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 (9)
1. A charging technique for a lithium-sulfur battery, characterized by: the charging technology is a pulse charging mode that the charging current is gradually increased and is matched with pulse standing time; or, the charging technology is a pulse charging mode in which the charging current is gradually increased and matched with the negative pulse current.
2. The lithium sulfur battery charging technique as claimed in claim 1, wherein: the charging technique includes the following steps (S1) - (S2):
(S1) setting a set of gradually increasing charging current values Ic{Ic1,Ic2,Ic3,……,IcnA discharge current value IdA charging time value tcA discharge time value tdAnd a standing time trSetting a cut-off voltage Vmax；
(S2) the charging current for the first pulse charging of the battery is Ic1Charging time tcThen discharging the battery or standing, if discharging the battery, the discharging current is IdDischarge time tdThe standing time is t if the battery is kept standingr(ii) a Then carrying out second pulse charging on the battery with charging current Ic2Charging time tcDischarging the battery or standing, and if discharging the battery, the discharging current is IdDischarge time tdThe standing time is t if the battery is kept standingr(ii) a Sequentially charging the battery by the nth pulse charging with charging current of IcnCharging time tcFinally discharging the battery or standing stillDischarge current of IdDischarge time tdOr a standing time tr(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 pulse charging current is increased from small to large, wherein Ic1Is the minimum value.
4. The lithium sulfur battery charging technique as claimed in claim 2, wherein: in step (S1), the charging current value Ic{Ic1,Ic2,Ic3,……,IcnThe rate is in the range of 0.05C-10C.
5. The lithium sulfur battery charging technique as claimed in claim 2, wherein: in step (S1), the charging time value tcIn the range of 0.1s to 30 s.
6. The method of charging a lithium sulfur battery according to claim 2, characterized in that: in step (S1), discharge current value IdIn the range of 0C to 0.2C.
7. 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.
8. The lithium sulfur battery charging technique as claimed in claim 2, wherein: in step (S1), the standing time value trIn the range of 0.01s to 30 s.
9. The lithium sulfur battery charging technique as claimed in claim 2, wherein: and (S2) after the battery is placed in an environment with the temperature of-80 to 60 ℃, the battery is charged.
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Application publication date: 20210810 |