# Patent

## Title
Method of charging a lithium-sulphur cell

## Abstract

A method for charging a lithium-sulphur cell, said method comprising: •determining the discharge capacity, Qn, of the cell during a charge-discharge cycle, n, •calculating the value of a*Q n, where a=1.05 to 1.4, and, •in a later charge-discharge cycle, n+x, where x is an integer of 1 to 5, charging the cell to a capacity Qn+x that is equal to a*Qn.

## Background
The present invention relates to a method of charging a lithium-sulphur battery. The present invention also relates to a battery management system for charging a lithium-sulphur battery.
BACKGROUND
A typical lithium-sulphur cell comprises an anode (negative electrode) formed from lithium metal or a lithium metal alloy, and a cathode (positive electrode) formed from elemental sulphur or other electroactive sulphur material. The sulphur or other electroactive sulphur-containing material may be mixed with an electrically conductive material, such as carbon, to improve its electrical conductivity. Typically, the carbon and sulphur are ground and then mixed with solvent and binder to form a slurry. The slurry is applied to a current collector and then dried to remove the solvent. The resulting structure is calendared to form a composite structure, which is cut into the desired shape to form a cathode. A separator is placed on the cathode and a lithium anode placed on the separator. Electrolyte is then introduced into the assembled cell to wet the cathode and separator.
Lithium-sulphur cells are secondary cells and may be recharged by applying an external current to the cell. Typically, the cell is charged to a fixed cut-off voltage of, for example, 2.45-2.8V. However, with repeated cycling over an extended period, the capacity of the cell may fade. Accordingly, by repeatedly charging the cell to the selected cut-off voltage, the cell may eventually be repeatedly over-charged. This can have a detrimental effect on the longevity of the cell, as undesirable chemical reactions may take lead to damage to, for example, the cell's electrodes and/or electrolytes.
A method for terminating the charging of a lithium-sulphur cell is described in WO 2007/111988. Specifically, this reference describes adding an N—O additive, such as lithium nitrate, to the electrolyte of the cell. According to the passage at page 16, lines 29 to 31, of this reference, the additive is effective in providing a charge profile with a sharp increase in voltage at the point of full charge. Accordingly, if the cell voltage during charge is monitored, charging can be terminated once a rapid increase in voltage is observed.
The method of WO 2007/111988 relies on the voltage of the cell increasing sharply as the cell reaches full capacity. Not all lithium-sulphur cells, however, exhibit such a charging profile.



BRIEF DESCRIPTION OF THE DRAWINGS
Advantages of the present invention will become apparent to those skilled in the art with the benefit of the following detailed description of embodiments and upon reference to the accompanying drawings in which:
FIG. 1 depicts a graph of the capacity of a lithium-sulphur cell charged to a fixed capacity for 100 cycles; and
FIG. 2 depicts a graph of the capacity of a lithium-sulphur cell charged at a variable capacity for 100 cycles.



SUMMARY OF THE INVENTION
According to the present invention, there is provided a method of charging of a lithium-sulphur electrochemical cell, said method comprising:
determining the discharge capacity, Qn, of the cell during a charge-discharge cycle n,
calculating the value of a·Qn, where a=1.1 to 1.3, and,
in a later charge-discharge cycle, n+x, where x is an integer of 1 to 5, charging the cell to a capacity, Qn+x, that is equal to a·Qn.
Preferably, x is 1, 2 or 3, more preferably, 1 or 2, and most preferably 1. In a preferred embodiment, therefore, the cell is charged to a capacity that is determined as a function of the discharge capacity of the preceding cycle.
Preferably, a is a value selected from 1.1 to 1.2.
In a preferred embodiment, x is 1 or 2, preferably 1, and a is 1.1 to 1.2.
In the method of the present invention, the charge capacity of the cell is determined on the basis of the discharge capacity of an earlier (preferably the preceding) cycle. Because the discharge capacity of the cell is monitored, the cell can be charged to a level dependent on the number of charge-discharge cycles that the cell has undergone. In this way, the cell can be charged in such a way as to avoid or reduce the risk of over-charging as a result of capacity fade. By reducing the risk of over-charging, the risk of capacity fade may also be reduced. Advantageously, this can improve the longevity of the overall cell. This contrasts with conventional methods of charging a lithium sulphur cell where the cell is charged to a pre-determined voltage or capacity irrespective of the extent to which the cell has experienced capacity fade.
In one embodiment, the method of the present invention is applied from the first discharge cycle of the cell. In other words, the discharge capacity Qn is the beginning of life discharge capacity (Qbol) of the cell. In an alternative embodiment, the method of the present invention is applied after the cell has been charged more than once. In one embodiment, the method may be applied after signs of capacity fade are observed, for example, after 5 or more cycles of the cell. In one embodiment, the method of the present invention is applied after 10 or more cycles of the cell. Prior to implementing the method of the present invention, the cell may be charged using a different method, for example, by charging the cell to a fixed, pre-determined voltage using a constant current.
In one embodiment, the method additionally comprises the step of determining a threshold discharge capacity, Qt, of the cell. This threshold discharge capacity may be the discharge capacity of the cell during an early cycle in the life of the cell, for example, before any appreciable signs of capacity fade are observed. This may be the discharge capacity at the 5th cycle or sooner, for example, at the 4th, 3rd, 2nd or 1st cycle. In one embodiment, this may be the capacity of the cell during its first discharge cycle following cell assembly (i.e. the beginning of life discharge capacity, Qbol, or the discharge capacity at the first cycle). In a preferred embodiment, the threshold discharge capacity is the discharge capacity of the cell at the 1st or 2nd cycle.
Once the threshold discharge capacity is determined, the discharge capacity, Q, of the cell in subsequent discharge cycles is monitored. When the discharge capacity of the cell, Qm, falls below 0.8 Qt (e.g. below 0.7 Qt or below 0.6 Qt), the cell may be charged to (i) b·Qt, where b is 1.05 to 1.3, or to (ii) 2.45V, whichever is lower. Where the cell is charged to b·Qt, b is preferably 1.1 to 1.2, more preferably about 1.1. By charging the cell according to steps (i) or (ii) above once the discharge capacity of the cell falls below 0.8 Qt, the cell may be given a charging boost, converting a greater proportion of the short chain polysulphides to longer chain polysulphides. This can reduce the rate of subsequent losses in capacity due to undercharging of the cell.
Once the cell is charged according to steps (i) or (ii) above, the discharge capacity of the subsequent cycle is Qm+1. The charge capacity for the Qm+2 cycle is preferably a·Qm+1, wherein a is 1.1 to 1.3, preferably 1.1 to 1.2. The charge capacity of subsequent cycles may be based on the discharge capacity of the preceding cycle in this way until the discharge capacity of the cell once again falls below 0.8 Qtl (e.g. below 0.7 Qt or 0.6 Qt). At this point, steps (i) or (ii) may be repeated.
The present invention also provides a battery management system for carrying out the method described above. In a further aspect, the present invention provides a battery management system for a lithium-sulphur battery, said system comprising:
means for determining the discharge capacity, Qn, of the cell during a charge-discharge cycle (n),
means for calculating the value of a·Qn, where a=1.1 to 1.3, and,
means for charging the cell to a capacity Qn+x, that is equal to a·Qn in a later charge-discharge cycle, n+x, where x is an integer of 1 to 5.
The system may additionally include means for coupling the system to a lithium-sulphur battery. In one embodiment, the system includes a lithium sulphur battery.
In a preferred embodiment, the lithium-sulphur cell is charged by supplying electric energy at constant current. The current may be supplied so as to charge the cell in a time ranging from 30 minutes to 12 hours, preferably 8 to 10 hours. The current may be supplied at a current density ranging from 0.1 to 3 mA/cm2, preferably 0.1 to 0.3 mA/cm2. As an alternative to charging at a constant current, it may also be possible to charge the lithium-sulphur cell to a constant voltage until the relevant capacity is reached. Suitable voltages range from 2.35V to 2.8V
The electrochemical cell may be any suitable lithium-sulphur cell. The cell typically includes an anode, a cathode, and an electrolyte. Advantageously, a porous separator may be positioned between the anode and cathode. The anode may be formed of lithium metal or a lithium metal alloy. Preferably, the anode is a metal foil electrode, such as a lithium foil electrode. The lithium foil may be formed of lithium metal or lithium metal alloy.
The cathode of the electrochemical cell includes a mixture of electroactive sulphur material and electroconductive material. This mixture forms an electroactive layer, which may be placed in contact with a current collector.
The mixture of electroactive sulphur material and electroconductive material may be applied to the current collector in the form of a slurry in an organic solvent (e.g. water or an organic solvent). The solvent may then be removed and the resulting structure calendared to form a composite structure, which may be cut into the desired shape to form a cathode. A separator may be placed on the cathode and a lithium anode placed on the separator. Electrolyte may then be introduced into the assembled cell to wet the cathode and separator.
The electroactive sulphur material may comprise elemental sulphur, sulphur-based organic compounds, sulphur-based inorganic compounds and sulphur-containing polymers. Preferably, elemental sulphur is used.
The solid electroconductive material may be any suitable conductive material. Preferably, this solid electroconductive material may be formed of carbon. Examples include carbon black, carbon fibre and carbon nanotubes. Other suitable materials include metal (e.g. flakes, filings and powders) and conductive polymers. Preferably, carbon black is employed.
The weight ratio of electroactive sulphur material (e.g. elemental sulphur) to electroconductive material (e.g. carbon) may be 1 to 30:1; preferably 2 to 8:1, more preferably 5 to 7:1.
The mixture of electroactive sulphur material and electroconductive material may be a particulate mixture. The mixture may have an average particle size of 50 nm to 20 microns, preferably 100 nm to 5 microns.
The mixture of electroactive sulphur material and electroconductive material (i.e. the electroactive layer) may optionally include a binder. Suitable binders may be formed from at least one of, for example, polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, ethylene-propylene-diene rubber, methacrylate (e.g. UV-curable methacrylate), and divinyl esters (e.g. heat curable divinyl esters).
As discussed above, the cathode of the electrochemical cell may further comprise a current collector in contact with the mixture of electroactive sulphur material and solid electroconductive material. For example, the mixture of electroactive sulphur material and solid electroconductive material is deposited on the current collector. A separator is also disposed between the anode and the cathode of the electrochemical cell. For example, the separator may be in contact with the mixture of electroactive sulphur material and solid electroconductive material, which, in turn, is in contact with the current collector.
Suitable current collectors include metal substrates, such as foil, sheet or mesh formed of a metal or metal alloy. In a preferred embodiment, the current collector is aluminium foil.
The separator may be any suitable porous substrate that allows ions to move between the electrodes of the cell. The porosity of the substrate should be at least 30%, preferably at least 50%, for example, above 60%. Suitable separators include a mesh formed of a polymeric material. Suitable polymers include polypropylene, nylon and polyethylene. Non-woven polypropylene is particularly preferred. It is possible for a multi-layered separator to be employed.
Preferably, the electrolyte comprises at least one lithium salt and at least one organic solvent. Suitable lithium salts include at least one of lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiClO4), lithium trifluoromethanesulfonimide (LiN(CF3SO2)2)), lithium borofluoride and lithium trifluoromethanesulphonate (CF3SO3Li). Preferably the lithium salt is lithium trifluoromethanesulphonate.
Suitable organic solvents are tetrahydrofurane, 2-methyltetrahydrofurane, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate, methylpropylpropionate, ethylpropylpropionate, methyl acetate, dimethoxyethane, 1, 3-dioxolane, diglyme (2-methoxyethyl ether), tetraglyme, ethylene carbonate, propylene carbonate, γ-butyrolactone, dioxolane, hexamethyl phosphoamide, pyridine, dimethyl sulfoxide, tributyl phosphate, trimethyl phosphate, N, N, N, N-tetraethyl sulfamide, and sulfone and their mixtures. Preferably, the organic solvent is a sulfone or a mixture of sulfones. Examples of sulfones are dimethyl sulfone and sulfolane. Sulfolane may be employed as the sole solvent or in combination, for example, with other sulfones.
The organic solvent used in the electrolyte should be capable of dissolving the polysulphide species, for example, of the formula Sn2−, where n=2 to 12, that are formed when the electroactive sulphur material is reduced during discharge of the cell.
The concentration of lithium salt in the electrolyte is preferably 0.1 to 5M, more preferably 0.5 to 3M, for example, 1M. The lithium salt is preferably present at a concentration that is at least 70%, preferably at least 80%, more preferably at least 90%, for example, 95 to 99% of saturation.
In one embodiment, the electrolyte comprises lithium trifluoromethanesulphonate and sulfolane.
The weight ratio of electrolyte to the total amount of electroactive sulphur material and electroconductive material is 1-15:1; preferably 2-9:1, more preferably 6-8:1.
Comparative Example 1
In this example, a lithium-sulphur cell is charged to a fixed voltage over 200+ cycles. FIG. 1 shows the charge and discharge capacity curves over the life of the cell. As can be seen from the Figure, capacity fades with increasing cycle life.
Example 2
In this Example, a lithium-sulphur cell is charged to a fixed voltage until initial signs of capacity fade are observed at the end of cycle 15. The discharge capacity at cycle 15, Q15 is determined and, at cycle 16, the cell is charged to a capacity that is a·Q15, where a=1.10. The discharge capacity at cycle 16, Q16, is then determined and, at cycle 17, the cell is charged to a·Q16 and so on. As can be seen in FIG. 2, the rate of capacity fade is reduced by using this charging method.

## Claims

1. A method for charging a lithium-sulphur cell, said method comprising:
coupling the lithium-sulphur cell to a battery management system, wherein the battery management system comprises a means for charging the cell, and a means for determining the discharge capacity,
wherein the discharge capacity is determined by:
determining the discharge capacity, Qn, of the lithium-sulphur cell during a charge-discharge cycle, n,
calculating the value of a*Qn, where a=1.05 to 1.4, and,
in a later charge-discharge cycle, n+x, where x is an integer of 1 to 5, charging the lithium-sulphur cell to a discharge capacity, Qn+x, that is equal to a*Qn 
determining a threshold discharge capacity, Qt, of the cell, wherein the threshold capacity is the discharge capacity at the 5th cycle or sooner, and
when the discharge capacity of the cell, Qm, falls below 0.8 Qt, charging the cell to (i) b*Qt, when b is 1.05 to 1.3, or to (ii) 2.45V, whichever is lower.

2. The method of claim 1, wherein x is an integer selected from 1, 2 or 3.

3. The method of claim 1, wherein x is 1.

4. The method of claim 1, wherein a is a value selected from 1.1 to 1.3.

5. The method of claim 1, wherein a is selected from 1.1 to 1.2.

6. The method of claim 1, wherein the threshold capacity of the lithium-sulphur cell is the capacity during its first discharge cycle.

7. The method of claim 1, wherein b is 1.1 to 1.2.