Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials and Characterization Methods
2.2. Preparation of Gelled Electrolyte
2.3. Preparation of the Cathode (LiFePO4) and Assembly of the Cell
3. Results & Discussion
3.1. Transport Properties in Phosphonium Electrolyte
3.1.1. Ionic Conductivity
3.1.2. Diffusion Coefficient
3.1.3. Lithium Solubility
3.2. IL Confinement within the Epoxy Network
3.2.1. Effect of IL Content on the Exudation
3.2.2. Effect of IL on Reaction Progress
3.3. Influence of the Electrolyte on the Final Properties of Epoxy Based-Networks
3.3.1. On the Thermal Stability of Networks
3.3.2. On the Viscoelastic Properties
3.4. Effect of Electrolyte on the Transport and Electrochemical Properties
3.4.1. Transport Properties
3.4.2. Electrochemical Stability
3.4.3. Cycling Performance of Li|LiFePO4 Cell
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Name | Structure | Characteristics |
---|---|---|
PPO | | Sigma Aldrich; 320 g/eq |
Jeffamine®D2000 | | Supplied by Huntsmann; 514 g/eq |
[P66614][TMP] | | Supplied by Cytec; Molar mass = 773.27 g·mol−1 m.p. =−72 °C Td max = 350 °C |
[P66614][TFSI] | | Supplied by Cytec; Molar mass = 764.0 g·mol−1 m.p. = −72.4 °C Td = 450 °C |
LiTFSI | | Supplied by Sigma Aldrich; Molar mass = 287.0 g·mol−1 |
LiTMP | | Supplied by Solvionic Molar mass = 780.27 g·mol−1 |
Sample | Ea (J·mol−1) | R2 |
---|---|---|
[P66614][TFSI] + LiTFSI | 470 | 0.999 |
[P66614][TMP] + LiTMP | 530 | 0.998 |
T (°C) | [P66614][TFSI] + LiTFSI | T (°C) | [P66614][TMP] + LiTMP | |
---|---|---|---|---|
D [H] | 28.5 | 9.25 × 10−8 | 54 | 2.3 × 10−8 |
86 | 1.1 × 10−7 | |||
D [Li] | 21 | 9.35 × 10−9 | 54 | No signal |
86 | No signal |
Sample | Composition (wt %) | Exudation | ||
---|---|---|---|---|
Polymer | IL | LiTFSI | ||
PPO [TFSI]-50 | 50 | 41.0 | 9.0 | No |
PPO [TFSI]-60 | 40 | 49.2 | 10.8 | No |
PPO [TFSI]-65 | 35 | 53.3 | 11.7 | No |
PPO [TFSI]-70 | 30 | 57.4 | 12.6 | No |
Wavenumber (cm−1) | Peak Assignment |
---|---|
7099 | O–H overtone |
6600–6480 | Primary and Secondary amine combination band Overtones of N–H stretching |
6072 | Terminal epoxy first overtone of C–H stretching |
5880–5500 | C–H overtone (CH2, CH3) |
5249 | −OH due to moisture (O–H asymmetric stretching and bending) |
4935 | Primary amine combination band N–H stretching and bending |
4530 | Epoxy combination band (C–H stretching and epoxy ring breathing) |
System | PPO-Jeffamine | PPO-Jeffamine + ([P66614][TFSI] + LiTFSI) | ||
---|---|---|---|---|
Step of Curing | First Step | Second Step | First Step | Second Step |
kE (h−1/2) | 0.272 | 0.988 | 0.268 | 7.989 |
(R2) | (0.994) | (0.996) | (0.989) | (0.993) |
kPA (h−1/2) | 0.534 | 0.534 | 0.532 | 30.266 |
(R2) | (0.999) | (0.999) | (0.999) | (0.999) |
kSA (h−1/2) | 0.190 | 0.243 | 0.186 | 3.039 |
(R2) | (0.988) | (0.996) | (0.990) | (0.990) |
Electrolyte Content | Tα (°C) | Rubbery State E′ (MPa) |
---|---|---|
(wt %) | ||
0 | −49.2 | 0.33 |
50 | −48.8 | 0.25 |
60 | −46.9 | 0.20 |
70 | −43.0 | 0.06 |
Sample | Ea (J·mol−1) | R2 |
---|---|---|
[P66614][TFSI] + LiTFSI | 440 | 0.999 |
PPO [TFSI]-50 | 500 | 0.999 |
PPO [TFSI]-60 | 470 | 0.997 |
PPO [TFSI]-65 | 475 | 0.999 |
PPO [TFSI]-70 | 490 | 0.999 |
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Leclère, M.; Bernard, L.; Livi, S.; Bardet, M.; Guillermo, A.; Picard, L.; Duchet-Rumeau, J. Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries. Nanomaterials 2018, 8, 435. https://doi.org/10.3390/nano8060435
Leclère M, Bernard L, Livi S, Bardet M, Guillermo A, Picard L, Duchet-Rumeau J. Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries. Nanomaterials. 2018; 8(6):435. https://doi.org/10.3390/nano8060435
Chicago/Turabian StyleLeclère, Mélody, Laurent Bernard, Sébastien Livi, Michel Bardet, Armel Guillermo, Lionel Picard, and Jannick Duchet-Rumeau. 2018. "Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries" Nanomaterials 8, no. 6: 435. https://doi.org/10.3390/nano8060435