A Study on the Influence of Lithium Plating on Battery Degradation
Abstract
:1. Introduction
- To improve the degradation diagnostics model presented in [9] to simplify the quantification procedure of LLI, LAMNE and LAMPE;
- To identify the degradation modes of a commercial cell aged under a fast charge regime and analyze the underlying degradation mechanisms.
2. Experimental Setup and Data Acquisition
2.1. Full-Cell Experiments
2.2. Half-Cell Experiments
3. Quantification Procedure of LAM and LLI
3.1. Cell OCV Fitting
3.1.1. Identify the Cell OCV Fitting Range
3.1.2. Identification of Electrode OCV Use Range
3.2. Quantification of LAM and LLI
3.2.1. LLI Calculation
3.2.2. LAM Calculation
4. Degradation Analysis: Results and Discussion
4.1. Identification of Electrode Utilization Range
4.2. Application of the Degradation Diagnostics
- Higher levels of LLI (circa 19.4%) are observed for set A cells compared to set B cells (circa 7.3%) as shown in Figure 11. This could be explained through the following reasons. First, set A cells had higher levels of lithium plating (see Figure 3). Part of the plated lithium becomes irreversible, leading to LLI. Second, the increased LAM could raise the LLI level since LAM could occur in the lithiated state. Third, the plated lithium could crack the SEI layer, resulting in further growth of the SEI layer consuming cyclable lithium [40].
- Increased levels of LAM at the NE are observed under lithium plating. The LAM levels at NE of set A cells are significantly higher (an average of 16.2%, Figure 11) than those of set B cells (an average of 6.1%, Figure 11b). However, relatively low, the LAM levels in set B indicates that there could be some amount of lithium plating that is below the detectable level. As discussed within [29], the VRP method fails to detect lithium plating levels lower than 2.5%. Visual inspection of the electrodes (Figure 3) as detailed in Section 2.1 as well indicate relatively lower levels of lithium metal depositions in set B cells compared to that of set A cells.The LAM difference between the two sets as seen from Figure 11 indicates that higher the capacity fade under the influence of lithium plating, larger the LAM for two reasons. First, set A cells are charged with an aggressive current profile and found with much higher levels of lithium depositions and capacity fade compared to set B cells (see Figure 3). Second, other possible aging mechanisms such as binder decomposition and graphite exfoliation at the NE [41,42] that cause LAM may not induce such high levels of LAM given these cells are only tested for 52 cycles [4].In addition to the quantification of degradation modes using the proposed electrodes OCV profiles, IC–DV curves are also compared for degradation analysis. Figure 12a,b shows the evolution of IC and DV curves, respectively for the cell A1. In the DV curves, the cell capacity delivered between the peaks C2 and C3 is equal to the capacity delivered by the NE electrode between the peaks N1 and N2. Therefore, the percentage of capacity reduction between these peaks can be used to indicate the percentage of LAMNE. As seen from figure, the capacity between the peaks C2 and C3 has dropped by 15.6% (1.086 Ah compared to 1.285 Ah) which suggests that LAMNE is 15.6%. On the other hand, LAMNE estimated for the same cell using the electrode OCV profiles is 17.8%. The large levels of LAMNE calculated from both techniques highlights that mechanical stress has increased under lithium plating.Increased levels of LAM under the influence of lithium plating can originate from two possible sources. One, as discussed earlier, volume expansion due to the lithium metal depositions in the early cycles can raise the mechanical stresses within the cell and lead to LAM in the first moment. Second, as discussed within [43], formation of localized layers due to passivated lithium depositions or electrically isolated LAM in the early cycles may further increase the mechanical stresses locally which in turn can raise the LAM further.
- LAMNE is higher than LAMPE for each cell in set A (as per Figure 11) and the average LAMNE across the set A cells is 16.2% while the average LAMPE is only 8.9%. Since lithium plating occurs at the NE and metal depositions could stay between the NE and the separator, it can be reasonably assumed that the NE experiences higher levels of mechanical stresses compared to the PE ([3,12]). Therefore, it follows that mechanical stresses impact on the NE could be higher than the PE.
- The results also highlight that LAMNE levels are comparable to the LLI levels in the aged cells. For example, cell number one from set A lost 17.8% LAMNE and 19.4% LLI. LAM can occur in lithiated condition, which means LLI along with it or in the delithiated state. Since lithium plating occurs towards the end of charging or near to full lithiation of the electrode, mechanical stresses could rise remarkably in the lithiated state of NE. This could result in higher levels of LAM in the lithiated state (LAMliNE). As discussed within [44], the shift of valley points in the IC curve (*C2 and *C3) that correspond to the peaks C2 and C3 in the DV curve (or the peaks N1 and N2 of the NE) towards higher cell voltages (as seen from Figure 12a) as well indicates the dominance of LAMliNE. Therefore, significant levels of LLI may come from LAMliNE and the contribution of irreversible lithium plating to the total LLI can be much lower than the LLI from the LAM. This analysis indicates that most lithium plating can become reversible and LAMliNE can be a major result of lithium plating. However, this initial conclusion needs further study to quantify the LLI from LAM.
4.3. Research Challenges and Future Work
4.3.1. Impact of Electrode Degradation
4.3.2. Impact of Lithium Metal Depositions
4.3.3. Loading Ration Mismatch
5. Conclusions
Author Contributions
Funding
Conflicts of Interest
Abbreviations
BMS | Battery management system |
CC–CV | Constant current followed by constant voltage |
DV | Differential voltage |
EV | Electric vehicle |
IC | Incremental capacity |
LAM | Loss of active material |
LFP | Lithium iron phosphate |
LI | Lithium inventory |
LLI | Loss of lithium inventory |
NCA | Lithium nickel cobalt aluminum oxide |
NE | Negative electrode |
NEP | Negative electrode potential |
NMC | Nickel manganese cobalt oxide |
OCV | Open circuit voltage |
SEI | Solid electrolyte interface |
SOH | State of health |
SOC | State of charge |
VRP | Voltage relaxation profile |
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Test Case | Cells Used (Group: Cell Marking) |
---|---|
Case 1: Cells aged under fast charging regime | Three new cells (set A: A1, A2, A3) |
Case 2: Cells aged under less aggressive charging regime | Three new cells (set B: B1, B2, B3) |
Test Sequence | Sub-Step No. | Exp. Setup | Current/Voltage | Control Limits |
---|---|---|---|---|
Step 1: Preconditioning tests | 1.1 | Soak to 25 °C | – | t > 4 h |
1.2 | Constant current charge | C/3 current | V > 4.2 V | |
1.3 | Constant voltage charge | 4.2 V | I < C/60 | |
1.4 | Rest | – | t > 1 h | |
1.5 | Constant current discharge | C/3 current | V < 2.5 V | |
1.6 | Constant voltage discharge | 2.5 V | I < C/60 | |
1.7 | Rest | – | t > 1 h | |
1.8 | Repeat steps 1.2 to 1.7 | – | Cycle number ≤ 6 | |
Step 2: OCV tests before aging | 2.1 | Soak to 25 °C | – | t > 4 h |
2.2 | Constant current charge | C/10 current | V > 4.2 V | |
2.3 | Constant voltage charge | 4.2 V | I < C/60 | |
2.4 | Rest | – | t > 4 h | |
2.5 | Partial constant current discharge | C/20 current | ΔQ > Qnom/120 | |
2.6 | Rest | – | t > 1 h | |
2.7 | Repeat steps 2.5 & 2.6 until V limit reached | – | V < 2.5 V | |
Step 3: Cell aging tests | 3.1 | Soak to 5 °C | – | t > 4 h |
3.2a: set A | Constant current charge | 1 C current | V > 4.2 V | |
3.2b: set A | Constant voltage charge | 4.2 V | I < C/4 | |
3.2a: set B | Constant current charge | 1 C current | V > 4.05 V | |
3.2b: set B | Constant voltage charge | 4.05 V | I < C/4 | |
3.2c: set B | Constant current charge | C/4 current | V > 4.2 V | |
3.3 | Rest | – | t > 4 h | |
3.4 | Constant current discharge | C/3 current | V < 2.5 V | |
3.5 | Rest | – | t > 1 h | |
3.6 | Repeat steps 3.2 to 3.5 until set A capacity drops to 80% | – | V < 2.5 V | |
Step 4: OCV tests after aging | Follows the same procedure as step 2 |
Test Case | SOH (%) | Cell Number | RMSE (mV) | Max Error (mV) |
---|---|---|---|---|
set A (aggressive charge profile) | 100 | 1 | 1.60 | 5.3 |
100 | 2 | 1.81 | 6.0 | |
100 | 3 | 1.81 | 6.0 | |
78.86 | 1 | 4.70 | 17.8 | |
84.39 | 2 | 3.80 | 12.2 | |
78.41 | 3 | 4.20 | 15.1 | |
set B (less aggressive charge profile) | 100 | 1 | 1.89 | 5.5 |
100 | 2 | 1.71 | 5.7 | |
100 | 3 | 1.51 | 5.6 | |
93.94 | 1 | 2.01 | 7.9 | |
94.71 | 2 | 1.81 | 8.4 | |
93.76 | 3 | 1.99 | 7.2 |
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Koleti, U.R.; Rajan, A.; Tan, C.; Moharana, S.; Dinh, T.Q.; Marco, J. A Study on the Influence of Lithium Plating on Battery Degradation. Energies 2020, 13, 3458. https://doi.org/10.3390/en13133458
Koleti UR, Rajan A, Tan C, Moharana S, Dinh TQ, Marco J. A Study on the Influence of Lithium Plating on Battery Degradation. Energies. 2020; 13(13):3458. https://doi.org/10.3390/en13133458
Chicago/Turabian StyleKoleti, Upender Rao, Ashwin Rajan, Chaou Tan, Sanghamitra Moharana, Truong Quang Dinh, and James Marco. 2020. "A Study on the Influence of Lithium Plating on Battery Degradation" Energies 13, no. 13: 3458. https://doi.org/10.3390/en13133458