Deciphering Electrolyte Degradation in Sodium-Based Batteries: The Role of Conductive Salt Source, Additives, and Storage Condition
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemicals and Sample Preparation
2.2. Instrumentation
3. Results and Discussion
3.1. NaPF6 with 99.5% Purity
3.1.1. Degradation Product Formation
3.1.2. Degradation Product Formation in the Presence of NaDFOB and FEC
3.1.3. Analysis of Diol Formation
3.2. NaPF6 with 99.9% Purity
3.3. NaTFSI with 99.9% Purity
3.4. FEC Reactivity and Color Changes
- In PE vials at 40 °C, FEC disappears after 3 weeks when sodium metal is present (c1) but remains stable over 18 weeks when sodium metal is absent (c2).
- In aluminum vials at 40 °C, regardless of the presence (c7) or absence (c3) of sodium metal, FEC remains stable over the 18 weeks duration.
- At 65 °C in PE vials, FEC disappears after 3 weeks when sodium metal is present (c4), and after 6 weeks when sodium metal is absent (c5).
- In aluminum vials at 65 °C, FEC remains stable over 18 weeks when sodium metal is absent (c6), but it disappears after 12 weeks when sodium metal is present (c8).
- In PE vials at 40 °C, FEC disappears after 9 weeks when sodium metal is present (f1) but remains stable over 18 weeks when sodium metal is absent (f5).
- In aluminum vials at 40 °C, regardless of the presence (f2) or absence (f6) of sodium metal, FEC remains stable over the 18 weeks duration.
- At 65 °C in PE vials, FEC disappears after 3 weeks when sodium metal is present (f3), and after 12 weeks when sodium metal is absent (f4).
- In aluminum vials at 65 °C, FEC remains stable over 18 weeks, irrespective of the presence (f8) or absence (f7) of sodium metal.
4. Conclusions
- Temperature effects: In both sets of samples, FEC appears to degrade faster at higher temperatures. This behavior aligns with the general principle of chemical kinetics that reaction rates typically increase with temperature. This is usually explained by the Arrhenius equation, which states that a higher temperature increases the fraction of molecules possessing energy greater than the activation energy, leading to an increased rate of reaction. In the context of our study, higher temperatures could facilitate degradation reactions involving FEC, thereby causing its faster consumption.
- Effects of sodium metal presence: The presence of sodium metal seems to accelerate the disappearance of FEC. This suggests that FEC reacts with sodium, possibly through a reductive decomposition mechanism. The resulting products could contribute to the formation of a stable SEI layer, which could help improve the overall stability of the electrolyte system.
- Effects of vial material: FEC tends to last longer in aluminum vials than in PE vials, indicating that the material of the storage vial can impact the stability of the additive. The reason behind this observation could be the better thermal conductivity of aluminum compared to PE, which could help dissipate heat more efficiently, thereby reducing the rate of degradation reactions.
- Effects of conductive salt: Although both types of salts studied (NaPF6 and NaTFSI) are sodium salts, differences in the reactivity of FEC were observed between them. This suggests that the anion part of the salt might play a role in the reactions involving FEC. Some reports in the literature suggest that is less reactive and more thermally stable than , which could explain the observed behavior [76,77].
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Solvent | Mw [g·mol−1] | ρ at 25 °C [g·cm−3] | Tb [°C] | ε at 40 °C | η at 40 °C [mPa·s] | Refs. |
---|---|---|---|---|---|---|
EC | 88.06 | 1.321 a | 248 | 89.78 | 1.93 | [70] |
PC | 102.09 | 1.205 b | 242 | 66.14 b | 2.53 c | [70] |
FEC | 106.05 | 1.454 | 212 | 78.4 | 4.10 | [71,72] |
Salt | Structure of Anion | Mw [g·mol−1] | Tm [°C] | σ in 1 M PC Solution [mS·cm−1] | Anodic Stability/V vs. Na+/Na0 | Refs. |
---|---|---|---|---|---|---|
NaPF6 | 167.95 | dec. 300 | 7.98 | 5 a | [41,73] | |
NaTFSI | 303.13 | 257 | 6.20 | 3.4/5 a,b | [41,73] | |
NaDFOB | 159.82 | - | 4.27 | 5.51 c | [30,41] |
Solvent | EC/PC | |||||||||||||||||
Salt | NaPF6; 99.5% | |||||||||||||||||
Additive | - | NaDFOB | FEC | |||||||||||||||
T [°C] | 40 | 65 | 40 | 65 | 40 | 65 | ||||||||||||
Vial | PE | PE | Al | PE | PE | Al | PE | PE | Al | PE | PE | Al | PE | PE | Al | PE | PE | Al |
Na | + | - | - | + | - | - | + | - | - | + | - | - | + | - | - | + | - | - |
name/code | a1 | a2 | a3 | a4 | a5 | a6 | b1 | b2 | b3 | b4 | b5 | b6 | c1 | c2 | c3 | c4 | c5 | c6 |
Solvent | EC/PC | |||||||||||
Salt | NaPF6; 99.9% | |||||||||||
Additive | - | NaDFOB | FEC | |||||||||
T [°C] | 25 | 40 | 50 | 58 | 65 | 40 | 65 | 40 | 65 | |||
Vial | PE | Al | Al | PE | Al | PE | Al | Al | Al | Al | Al | Al |
Na | + | + | + | + | + | + | + | + | + | + | + | + |
name/code | a7 | a8 | a9 | a10 | a11 | a12 | a13 | a14 | b7 | b8 | c7 | c8 |
Solvent | EC/PC | |||||||||||
Salt | NaTFSI | |||||||||||
Additive | - | NaDFOB | FEC | |||||||||
T [°C] | 65 | 65 | 40 | 65 | ||||||||
Vial | PE | Al | PE | Al | PE | Al | PE | Al | PE | Al | PE | Al |
Na | + | + | + | + | + | + | - | - | + | + | - | - |
name/code | d1 | d2 | e1 | e2 | f1 | f2 | f5 | f6 | f3 | f4 | f7 | f8 |
№ | Compound | CAS | Ret. Time a [min] | RI b | RI c NIST | Mass Frag. m/z | Confirmed d |
---|---|---|---|---|---|---|---|
1 | 1,2-ethanediol | 107-21-1 | 4.90 | 692 | 702 ± 10 | 43, 33, 42, 62, 61 | yes |
2 | 1,2-propanediol | 57-55-6 | 5.35 | 739 | 740 ± 18 | 45, 43, 61, 75, 76 | yes |
3 | 2-ethyl-1,3-dioxolane | 2568-96-9 | 5.54 | 753 | 780 ± 7 | 73, 45, 57, 72, 101 | yes |
4 | 2-ethyl-4-methyl-1,3-dioxolane | 4359-46-0 | 5.86, 5.95 | 790, 799 | NA | 87, 59, 41, 57, 72, 115 | yes |
5 | EC | 96-49-1 | 7.70 | 978 | NA | 43, 88, 44, 58, 42 | yes |
6 | PC | 108-32-7 | 7.91 | 1000 | NA | 57, 43, 87, 58, 42 | yes |
7 | amylene hydrate | 75-85-4 | 4.37 | 637 | 615 ± 16 | 59, 73, 55, 43, 41 | yes |
8 | 1,4-dioxane | 123-91-9 | 5.08 | 710 | 675 ± 19 | 88, 58, 57, 87, 89 | yes |
9 | ethanediol monoformate | 628-35-3 | 5.63 | 764 | NA | 60, 44, 43, 45, 61 | yes |
10 | FEC | 1144335-02-8 | 6.55 | 859 | NA | 62, 44, 58, 106, 73 | yes |
11 | diethylene glycol | 111-46-6 | 7.65 | 978 | 980 | 45, 75, 76, 43, 44 | yes |
12 | triethylene glycol | 112-27-6 | 9.77 | 1256 | 1255 | 45, 89, 58, 75, 43 | yes |
13 | 1,3-dioxolane-2-methanol | 5694-68-8 | 6.72 | 883 | 881 | 73, 45, 43, 44, 74 | yes |
Sample | Weeks | |||
---|---|---|---|---|
3 | 6 | 9 | 18 | |
a1 | --- | (1), (2) | 1, 2 | 1, 2, (8) |
a2 | --- | --- | 7 | 3, 4/4′, 7 |
a3 | --- | --- | (7) | 7 |
a4 | 1, 2 | 1, 2, (3), (4/4′) | 1, 2, (3), (4/4′) | 1, 2, 3, 4/4′, (8) |
a5 | 3, 4/4′ | 1, 2, 3, 4/4′ | 1, 2, 3, 4/4′ | 1, 2, 3, 4/4′, (8) |
a6 | --- | (4/4′), (7) | (3), (4/4′), 7 | 3, 4/4′, 7 |
Sample | Weeks | |||
---|---|---|---|---|
3 | 6 | 9 | 18 | |
b1 | --- | --- | (1), (2) | 1, 2 |
b2 | (7) | (7) | 7, (9) | 1, 2, 3, 4/4′, 7, 9 |
b3 | --- | (7) | (7) | 7 |
b4 | --- | (1), 2, (3), (4/4′), 9 | 1, 2, 3, 4/4′, 9 | 1, 2, 3, 4/4′, 9 |
b5 | (3) | 1, 2, 3, 4/4′, 9 | 1, 2, 3, 4/4′, 9 | 1, 2, 3, 4/4′, 9 |
b6 | --- | --- | 7 | 7 |
c1 | --- | (1), (2) | 1, 2 | 1, 2 |
c2 | 10 | 10 | 7, 10 | 3, 4/4′, 7, 10 |
c3 | 10 | 10 | (7), 10 | 7, 10 |
c4 | 1, 2 | 1, 2 | 1, 2, 3, 4/4′ | 1, 2, 3, 4/4′ |
c5 | 10 | 1, 2, 3, 4/4′, (10) | 1, 2, 3, 4/4′ | 1, 2, 3, 4/4′ |
c6 | 10 | 10 | 7, 10 | 3, (4/4′), 7, 10 |
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Hashimov, M.; Hofmann, A. Deciphering Electrolyte Degradation in Sodium-Based Batteries: The Role of Conductive Salt Source, Additives, and Storage Condition. Batteries 2023, 9, 530. https://doi.org/10.3390/batteries9110530
Hashimov M, Hofmann A. Deciphering Electrolyte Degradation in Sodium-Based Batteries: The Role of Conductive Salt Source, Additives, and Storage Condition. Batteries. 2023; 9(11):530. https://doi.org/10.3390/batteries9110530
Chicago/Turabian StyleHashimov, Mahir, and Andreas Hofmann. 2023. "Deciphering Electrolyte Degradation in Sodium-Based Batteries: The Role of Conductive Salt Source, Additives, and Storage Condition" Batteries 9, no. 11: 530. https://doi.org/10.3390/batteries9110530