METHOD FOR AGEING ANALYSIS OF MIXED ELECTRODE LITHIUM ION CELL
20240103092 ยท 2024-03-28
Assignee
Inventors
- Niladri ROY CHOWDHURY (Hisings Backa, SE)
- Gustav GISKE (JOHANNESHOV, SE)
- Istaq AHMED (G?teborg, SE)
- Martin PETISME (G?teborg, SE)
- Carl-Robert FLOR?N (G?teborg, SE)
- Alice HAMRIN (G?teborg, SE)
- Masood TAMADONDAR (M?lndal, SE)
- Praveen Raju HASBAVI (G?teborg, SE)
Cpc classification
G01R31/392
PHYSICS
H01M10/48
ELECTRICITY
B60R16/033
PERFORMING OPERATIONS; TRANSPORTING
H01M2220/20
ELECTRICITY
H01M10/425
ELECTRICITY
B60L58/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
G01R31/392
PHYSICS
H01M10/0525
ELECTRICITY
H01M10/48
ELECTRICITY
Abstract
A method of determining ageing of a mixed electrode of a full cell lithium ion battery is presented. The method includes obtaining a voltage hysteresis of the full cell lithium ion battery by comparison of a charging voltage to a discharging voltage at a specific state of charge, SOC. The specific SOC is in a range from 0% to 20% of a maximum SOC. The method further includes determining ageing of a volume expanding component of the mixed electrode based on the obtained voltage hysteresis.
Claims
1. A method of determining ageing of a mixed electrode of a full cell lithium ion battery, the method comprising: obtaining a voltage hysteresis of the full cell lithium ion battery by comparison of a charging voltage to a discharging voltage at a specific state of charge, SOC, wherein the specific SOC is in a range from 0% to 20% of a maximum SOC, wherein the charging voltage and the discharging voltage are obtained at a respective discharging current and charging current configured such that a ratio between an initial capacity of the full cell lithium ion battery and a charging time is below 5%; and determining ageing of a volume expanding component of the mixed electrode based on a comparison of the obtained voltage hysteresis and a voltage hysteresis at the specific of a substantially uncycled corresponding full cell lithium ion battery.
2. The method of claim 1, wherein obtaining a voltage hysteresis of the full cell lithium ion battery comprises: charging the full cell lithium ion battery from a lower SOC region to an upper SOC region, and for the specific SOC, obtaining the charging voltage, and discharging the full cell lithium ion battery from the upper SOC region to the lower SOC region, and for the specific SOC, obtaining the discharging voltage.
3. The method of claim 1, wherein the volume expanding component of the mixed electrode is silicon.
4. The method of claim 1, further comprising, before obtaining a voltage hysteresis of the full cell lithium ion battery: fully charging the full cell lithium ion battery from a minimum SOC to the maximum SOC, and/or fully discharging the full cell lithium ion battery from the maximum SOC to the minimum SOC, and determining a current capacity of the full cell lithium ion battery based on energy provided to the full cell lithium ion battery during the fully charging and/or energy obtained from the full cell lithium ion battery during the fully discharging.
5. The method of claim 2, wherein the lower SOC region is a region from and including 0% to and including 10% of the maximum SOC of the full cell lithium ion battery.
6. The method of claim 2, wherein the upper SOC region is a region from and including 20% to and including 100% of the maximum SOC of the full cell lithium ion battery.
7. The method of claim 2, wherein the charging of the full cell lithium ion battery is performed prior to the discharging of the full cell lithium ion battery.
8. The method of claim 1, further comprising: obtaining a voltage hysteresis for the specific SOC from a substantially uncycled full cell lithium ion battery comprising a substantially identical mixed electrode as the full cell lithium ion battery, wherein determining ageing of the volume expanding component comprises comparing the obtained voltage hysteresis of the full cell lithium ion battery to the obtained voltage hysteresis of substantially uncycled full cell lithium ion battery.
9. The method of claim 1, wherein determining ageing of the volume expanding component comprises comparing the determined voltage hysteresis to a voltage hysteresis threshold, wherein the voltage hysteresis threshold is below 0.2 V.
10. The method of claim 1, further comprising: obtaining a voltage hysteresis for the specific SOC from a half cell battery comprising a substantially identical mixed electrode as the full cell lithium ion battery, wherein determining ageing of the volume expanding component comprises comparing the obtained voltage hysteresis of the full cell lithium ion battery to the obtained voltage hysteresis of the half cell battery.
11. The method of claim 1, wherein the ratio between the initial capacity of the full cell lithium ion battery and the charging time, is below 1%.
12. The method of claim 1, wherein the mixed electrode is an anode comprising silicon and graphite.
13. A vehicle, comprising a processor circuit and a full cell lithium ion battery having a mixed electrode, wherein the processor circuit is operatively connected to the full cell lithium ion battery and configured to determine ageing of the battery cell by causing the execution of the method according to claim 1.
14. The vehicle of claim 13, wherein the processor circuit is further configured to obtain an initial voltage hysteresis for the specific SOC during an early charge cycle of the full cell lithium ion battery and determining ageing of the volume expanding component of the mixed electrode based on comparing the obtained voltage hysteresis to the initial voltage hysteresis, wherein the early charge cycle is one of the first 1-20 charge cycles.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] These and other aspects, features and advantages will be apparent and elucidated from the following description of various embodiments; references being made to the appended diagrammatical drawings which illustrate non-limiting examples of how the concept can be reduced into practice.
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DETAILED DESCRIPTION OF EMBODIMENTS
[0049] Hereinafter, certain embodiments will be described more fully with reference to the accompanying drawings. The invention described throughout this disclosure may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided by way of example so that this disclosure will be thorough and complete, and will fully convey the scope of the invention, such as it is defined in the appended claims, to those skilled in the art.
[0050] The term coupled is defined as connected, although not necessarily directly, and not necessarily mechanically. Two or more items that are coupled may be integral with each other. The terms a and an are defined as one or more unless this disclosure explicitly requires otherwise. The terms substantially, approximately, and about are defined as largely, but not necessarily wholly what is specified, as understood by a person of ordinary skill in the art. The terms comprise (and any form thereof, such as comprises and comprising), have (and any form thereof, such as has and having), include (and any form thereof, such as includes and including) and contain (and any form thereof, such as contains and containing) are open-ended linking verbs. As a result, a method that comprises, has, includes or contains one or more steps possesses those one or more steps, but is not limited to possessing only those one or more steps.
[0051] With reference to
[0052] Generally, to cycle a battery cell 100 means that is fully discharged and then fully charged. In some embodiments, the opposite definition may apply, wherein to cycle a battery cell 100 means that it is fully charged and then fully discharged.
[0053] The charge current i.sub.c is generally specified in relation to a capacity C of the battery cell 100 to be charged. Or rather, an initial capacity C.sub.i of the battery cell 100 to be charged. The initial capacity C.sub.i may be described as the capacity C the battery cell 100 is expected to deliver when new, i.e. the capacity of a substantially uncycled battery cell 100. The capacity C is generally specified in ampere hours Ah and by putting this in relation to an estimated charging time T.sub.c in hours h, the charge current i.sub.c is commonly described as i.sub.c=C.sub.i/T.sub.c. Similarly, the charge current i.sub.d may be specified in relation to the initial capacity C.sub.i of the battery cell 100 to be discharged. The discharge current i.sub.d may be specified by putting the initial capacity C.sub.i of the battery cell 100 in relation to an estimated discharging time T.sub.d in hours h, the discharge current i.sub.d is commonly described as i.sub.d=C.sub.i/T.sub.d.
[0054] In
[0055] During the first lithiation cycle of the electrodes 110, 120 a protective insulating layer will form on their respective surfaces. The protective layer may be referred to as a solid electrolyte interphase (SEI). The SEI is an irreversibly formed surface layer comprised of compounds from the electrolyte 140. The SEI is, in other words, formed at surface areas of the electrodes 110, 120 when they are first exposed to the electrolyte 140. The formation of the SEI will cause a loss in capacity at the electrode 110, 120 due to e.g. lithium redox reactions, i.e. the formation of the SEI consumes lithium ions.
[0056] Historically, electrodes of battery cells have been based on graphite. However, graphite may experience significant irreversible loss due to large surface areas required to hold lithium ions. This will consume available lithium ions, and therefore reduce an energy density of the battery cell. In order to increase the energy density, i.e. the amount of energy a battery cell 100 of a given volume may store and later release, the materials of the electrodes 110, 120 may be changed. Silicon (Si) is one material having high capacity and low working potential. Silicon is commonly mixed with graphite to provide a mixed electrode 110, 120. This is most common for the anode 110, but similar embodiments may be envisioned also for the cathode 120.
[0057] One issue with silicon is that it will change in volume when depending on a state of charge of the battery cell 100, and as the volume expands, a surface area of the electrode 110, 120 will increase. The increase of surface area will expose more area of the electrode to the electrolyte 140 and the SEI will increase causing increased loss in capacity. As the electrode 110, 120 is delithiated, its volume decreases. Repeated lithiation and delithiation of the electrode 110, 120 will cause it to increase and decrease in volume which may cause the SEI to break, exposing more of the surface area of the electrode 110, 120 to the electrolyte. At these newly exposed surface areas, more SEI will be formed consuming further lithium ions causing even further decrease in capacity C. Formation of SEI will, in addition to consume lithium ions, also consume active components of the electrodes 110, 120. The repeated volume expansion and contraction put the volume expanding component of the electrode 110, 120 under stress. This generally leads to isolation and breakage of particles of the volume expanding component rendering them electrochemically inactive.
[0058] The above mentioned SEI is one reason for the capacity of a battery cell 100 being reduced. The capacity C of the battery cell is determined by the complex chemistry involving e.g. the electrolyte 140 and the electrodes 110, 120. Based on the components of the battery sell 100 causing the battery cell 100 to lose capacity, many facts regarding how the battery cell 100 has been used may be deduced. Further to this, knowing the reason for a capacity loss will increase the accuracy in estimating and modelling future behavior of the battery cell, i.e. remaining capacity C at a particular cell open voltage V.sub.O. It is also beneficial in predicting a remaining lifetime of a battery cell 100. Historically, obtaining such data required invasive method in order to obtain half-cell data. For instance, in order to track the loss of silicon in a mixed electrode 110, 120, differential voltage analysis (DVA) and incremental capacity analysis (ICA) may be employed, but both these methods require half-cell data in order to identify the peaks due to different components of the electrode materials. The present disclosure teaches of a method of tracking loss of silicon or another volume expanding components in a mixed electrode without the need for half-cell data.
[0059] In
[0060] In
[0061] As seen in
[0062] The inventors behind the present disclosure have discovered that the hysteresis voltage V.sub.H will differ between a new battery cell 100 and a battery cell 100 that has been cycled a number of times. This is shown in
[0063] The reduction in hysteresis voltage V.sub.H at the low SOC SOC.sub.L is an indication of a loss of the volume expanding component 115, 125 of the mixed electrode 110, 120. The loss of the volume expanding component 115, 125 causes a reduced change in volume during cycling; therefore the hysteresis voltage V.sub.H is reduced at comparably low SOC. In
[0064] The inventors have further concluded that the effect of the hysteresis is more visible at lower charging currents is and discharging currents i.sub.d. It has been shown that the effect is significantly increased at charging currents below C.sub.i/40, i.e. a ratio of 2.5% (the charging time T.sub.c is 40). The effect is even more significant at charging currents below C.sub.i/100, i.e. a ratio of 1% (the charging time T.sub.c is 100). Similarly, the effect is increased at discharging currents below C.sub.i/20 i.e. a ratio of 5% (the discharging time T.sub.d is 20). The effect is further increased at discharging currents below C.sub.i/40 i.e. a ratio of 2.5% (the discharging time T.sub.d is 40). The effect is even further increased at discharging currents below C.sub.i/100 i.e. a ratio of 1% (the discharging time T.sub.d is 100).
[0065] In
[0066] Ageing, i.e. loss of the active component 115, 125 of an electrode 110, 120 of the battery cell 100 may be determined in a number of different ways based on the voltage hysteresis V.sub.H at the specific SOCs. In one embodiment, ageing of a specific battery cell 100 may be determined by comparing the obtained voltage hysteresis V.sub.H at the specific SOCs, to a voltage hysteresis V.sub.H at the specific SOCs for a new battery cell 100 of a same model, or at least of a model having similar specification, as the specific battery cell 100. This is beneficial as the change in voltage hysteresis V.sub.H is proportional to the loss of the volume expanding component 115, 125 and a loss of the volume expanding component 115, 125 may be determined as a percentage loss of an initial amount of the volume expanding component 115, 125.
[0067] Alternatively, or additionally, the ageing may be determined by comparing the voltage hysteresis V.sub.H at the specific SOCs to a voltage hysteresis threshold V.sub.HT. If the voltage hysteresis V.sub.H at the specific SOCs to below the voltage hysteresis threshold V.sub.HT, the battery cell 100 may be determined to be aged. If the voltage hysteresis V.sub.H at the specific SOCs to above the voltage hysteresis threshold V.sub.HT, the battery cell 100 may be determined as not being aged.
[0068] In one embodiment, the voltage hysteresis threshold V.sub.HT may be set at 0.2 V. In another embodiment, the voltage hysteresis threshold V.sub.HT may be set at 0.15 V. In yet another embodiment, the voltage hysteresis threshold V.sub.HT may be set at 0.1 V.
[0069] This implementation of a voltage hysteresis threshold V.sub.HT is a rather digital approach and may be usable to determine if e.g. the battery cell 100 should be replaced or not. However, in some embodiments, a plurality of voltage hysteresis threshold V.sub.HT may be provided at different voltage hysteresis V.sub.H at the specific SOC SOCs. An upper voltage hysteresis threshold V.sub.HT may be set to indicate a limit for when the battery cell is to be considered new. Another voltage hysteresis threshold V.sub.HT may be set to indicate that the battery cell 100 should be replaced. Other voltage hysteresis thresholds V.sub.HT may be provided in between these voltage hysteresis thresholds V.sub.HT to provide granularity in the determining of the ageing of the battery cell 100.
[0070] In some embodiments, the ageing of the specific battery cell 100 may be determined by comparing the voltage hysteresis V.sub.H at the specific SOC SOCs to a corresponding voltage hysteresis V.sub.H at the specific SOC obtained from half-cell data of a battery half-cell having substantially the same specification as the specific battery cell 100. The half-cell data may be obtained using e.g. the previously mentioned DVA and/or ICA.
[0071] Based on the teaching presented herein, a method 200 of determining ageing of a mixed electrode 110, 120 as shown in
[0072] As shown in
[0073] With continued reference to
[0074] In some embodiments, the method may optionally comprise obtaining 260 a voltage hysteresis V.sub.H for the specific SOC SOCs from a substantially uncycled full cell battery 100. The uncycled full cell battery 100 may be a historic voltage hysteresis V.sub.H for the battery cell 100 for which ageing is determined obtained during one of the initial cycles of the battery cell 100. Alternatively, voltage hysteresis V.sub.H may be from any uncycled battery cell comprising a substantially identical mixed electrode 110, 120 as the full cell battery 100 under age determination. In such embodiments, the determining 250 ageing of the volume expanding component 115, 125 may optionally comprise comparing 252, see
[0075] It should be mentioned that the battery cell 100 may be operatively connected to or comprise a memory that stores voltage hysteresis V.sub.H at the specific SOC SOCs for the first, or first group of cycles of the battery cell 100. This data may be stored onto the memory during manufacturing of the battery cell 100 or stored during the first use of the battery cell 100. If the battery cell 100 is used in an electric vehicle EV 300, see
[0076] As seen in
[0077] Again in reference to
[0078] With reference to
[0079] Modifications and other variants of the described embodiments will come to mind to one skilled in the art having benefit of the teachings presented in the foregoing description and associated drawings. Therefore, it is to be understood that the embodiments are not limited to the specific example embodiments described in this disclosure and that modifications and other variants are intended to be included within the scope of this disclosure. For example, while embodiments of the invention have been described mainly with reference to a silicon and graphite anode, persons skilled in the art will appreciate that the embodiments of the invention can equivalently be applied to any combination of volume expanding components in an electrode, anode or cathode. Furthermore, although specific terms may be employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Therefore, a person skilled in the art would recognize numerous variations to the described embodiments that would still fall within the scope of the appended claims. Furthermore, although individual features may be included in different claims (or embodiments), these may possibly advantageously be combined, and the inclusion of different claims (or embodiments) does not imply that a combination of features is not feasible and/or advantageous. In addition, singular references do not exclude a plurality. Finally, reference signs in the claims are provided merely as a clarifying example and should not be construed as limiting the scope of the claims in any way.