Acta Phys. -Chim. Sin. ›› 2023, Vol. 39 ›› Issue (5): 2211005.doi: 10.3866/PKU.WHXB202211005
• REVIEW • Previous Articles Next Articles
Chenyang Chen1, Yongzhi Zhao1, Yuanyuan Li2,*(
), Jinping Liu1,*(
)
Received:2022-11-03
Accepted:2022-12-12
Published:2022-12-19
Contact:
Yuanyuan Li, Jinping Liu
E-mail:liyynano@hust.edu.cn;liujp@whut.edu.cn
Supported by:Chenyang Chen, Yongzhi Zhao, Yuanyuan Li, Jinping Liu. Research Progress of High-Voltage/Wide-Temperature-Range Aqueous Alkali Metal-Ion Batteries[J]. Acta Phys. -Chim. Sin. 2023, 39(5), 2211005. doi: 10.3866/PKU.WHXB202211005
Fig 2
(a) Illustration of the evolution of the Li+ primary solvation sheath in diluted and water-in-salt solutions 18; (b) predicted reduction potentials of LiTFSI complexes from theoretical calculations 18; (c) illustration of expanded ESW for WIS electrolytes and the redox couples change of electrode caused by high salt concentration 18; (d) the ESW of WIBS and WIS electrolyte 28; (e) the ESW of the hydrate melt electrolyte and redox reaction potentials of LTO, LCO and LNMO 29; (f) the ESW of monohydrate melt as compared to dilute 1.0 mol∙L−1 LiPTFSI/H2O 30. (a–c) Adapted with permission from Ref. 18, Copyright 2015, American Association for the Advancement of Science; (d) Adapted with permission from Ref. 28, Copyright 2016, Wiley-VCH; (e) Adapted with permission from Ref. 29, Copyright 2016, The Springer Nature; (f) Adapted with permission from Ref. 30, Copyright 2019, Elsevier."
Fig 3
In 21 m LiTFSI-0.1% (w) TMSB electrolytes, (a) TEM image for the HVLCO electrodes after the first cycle 38; (b) HOMO levels of TMSB, H2O, LiTFSI and TFSI− 38; (c) schematic of possible mechanisms for electrochemical oxidative decomposition of TMSB 38; snapshots of inner-Helmholtz interfacial regions of the anode surface at (d) 2.5 V and (e) 0.5 V vs. Li, respectively 40; (f) CV profiles of a graphite anode pre-coated with LiTFSI-HFE gel and a LiVPO4F cathode 40; (g) illustration of the evolution of SEI at 1.9 and 0.5 V (vs. Li+/Li) in WISE, 1.9 and 0.5 V (vs. Li+/Li) in WISE-PAM, respectively 41; (h) LSV curves of WISE and WISE-PAM based on stainless steel electrodes 41; (i) the viscosity and conductivity of WISE-AM electrolytes at 30 ℃ 42; (j) comparison of the rate performance in WISE, WISE-PAM and WISE-AM electrolytes 42. (a–c) Adapted with permission from Ref. 38, Copyright 2016, The Royal Society of Chemistry; (d–f) Adapted with permission from Ref. 40, Copyright 2017, Elsevier; (g–h) Adapted with permission from Ref. 41, Copyright 2021, Wiley-VCH; (i–j) Adapted with permission from Ref. 42, Copyright 2022, Wiley-VCH."
Fig 4
(a) Illustration of the Li+ primary solvation sheath in 1 m LiClO4 and 1LiClO4-3H2O-2urea electrolyte 27; TEM image of (b) LMO and (c) Mo6S8 after ten cycles 27; (d) stoichiometric amounts of urea, LiTFSI and H2O used to prepare 4.5 m electrolyte 44; (e) CV profiles of LTO, LMO and LiVPO4F in 4.5 m electrolytes 44; (f) schematic illustration of the formation of the inorganic/organic mixed SEI 44; (g) Ar ion sputtering XPS and TEM images of cycled Mo6S8 electrode in WIS-Ar electrolyte 46; (h) illustration of the evolution of SEI formation in CO2-SIW electrolytes 46; (i) the cycling performance of the LMO//Mo6S8 aqueous full-cell in CO2-SIW electrolytes at low temperature (−40 ℃) 46. (a–c) Adapted with permission from Ref. 27, Copyright 2020, WILEY-VCH; (d–f) Adapted with permission from Ref. 44, Copyright 2022, The Springer Nature; (g–i) Adapted with permission from Ref. 46, Copyright 2021, The Springer Nature."
Fig 5
(a) Representative liquid structure for the H1D1HANE 47; (b) reduction potentials of DMC-2Li+ complexes from theoretical calculations 47; (c) schematic illustration of the anode SEI formation in HANE 47; (d) snapshots of the interfacial regions at the cathode surface from MD simulations of the graphite|H1D1HANE interfaces 47; (e) ESW of the H1D1HANE and CVs of LTO and LNMO in H1D1HANE 47; (f) ESW of electrolytes and CVs of LTO and LMO obtained in WISE, BSiS-AN0.5 and BSiS-DOL0.5 electrolytes 48; (g) snapshots of the equilibrated electrolyte systems and the structure of the ion aggregations LiTFSI/(H2O)2.6/(AN)3.5 50. (a–e) Adapted with permission from Ref. 47, Copyright 2018, Elsevier; (f) Adapted with permission from Ref. 48, Copyright 2019, WILEY-VCH; (g) Adapted with permission from Ref. 50, Copyright 2019, WILEY-VCH."
Fig 6
(a, b) Normalized FTIR of a series of 2 m LiTFSI-xPEG-(1 − x)H2O electrolytes 51; (c) CVs collected in 2 m LiTFSI-94% PEG-6% H2O for LMO and L-LTO, the grey dashed line shows the ESW 51; (d) conductivity of 2 m LiTFSI-94% PEGDME-6% H2O and 2 m LiTFSI-94% PEG400-6% H2O 52; (e) schematic illustration of intermolecular interactions of H2O-crowding agent, crowding agent-crowding agent and H2O-H2O 52; (f) ESWs for various low-concentration and super-concentrated sugar solutions 53; (g) the hypothetical diagrams of solvation structures, (h) ionic conductivities and (i) ESW of the 12.5 m LiNO3 in H2O: PD and LWIS gel electrolytes 54. (a–c) Adapted with permission from Ref. 51, Copyright 2020, The Springer Nature; (d–e) Adapted with permission from Ref. 52, Copyright 2022, American Chemical Society; (f) Adapted with permission from Ref. 53, Copyright 2020, WILEY-VCH; (g–i) Adapted with permission from Ref. 54, Copyright 2021, Wiley-VCH."
Fig 7
(a) Preparation of a MSM-based room-temperature DES 56; (b) liquid structure of MSM : LiClO4 : H2O = 2 : 1 : 1 DES electrolyte calculated from DFT 56; (c) the normalized FTIR spectra of 3.6 m LiTFSI/sulfolane-H2O(x: 8) electrolytes 57; (d) schematic illustration of the interaction between water and sulfolane 57; (e) FTIR spectra of Li-H2O-MUx (x = 0.00–0.65) solutions 59; (f) solution structures of Li-H2O-MU0.27 over a larger length scale 59. (a, b) Adapted with permission from Ref. 56, Copyright 2019, American Chemical Society; (c, d) Adapted with permission from Ref. 57, Copyright 2021, Elsevier.; (e, f) Adapted with permission from Ref. 59, Copyright 2022, Elsevier."
Table 1
High-voltage AABs achieved by electrolyte modification."
| Strategy | Electrolyte | ESW (V vs. Li/Na/K) | Ionic conductivity (mS∙cm−1)@.(℃) | Cathode//Anode | Output voltage (V) | Energy density* (Wh∙kg−1) | Ref. | |
| Highly Concentrated Salt | Li+ | 21 m LiTFSI | 3.0 (1.9–4.9) | 8.21@25 | LiMn2O4//Mo6S8 | 2.0 | 84 | |
| 21 m LiTFSI + 7 m LiOTf | 3.1 (1.8–4.9) | 6.5@25 | LiMn2O4//TiO2 | 2.1 | 100 | |||
| 19.4 m LiTFSI + 8.3 m LiBETI | 3.8 (1.2–5.0) | 3.0@30 | LiCoO2//Li4Ti5O12 | 2.35 | – | |||
| 22.2 m LiTFSI + 33.3 m LiPTFSI | 2.7 (2.3–5.0) | 0.1@25 | LiCoO2//Li4Ti5O12 | 2.4 | – | |||
| 40.4 m KOAc + 9.8 m LiOAc | 2.85 (1.55–4.4) | 25.2@25 | LiMn2O4//AC | 2.0 | 77.9 | |||
| 42 m LiTFSI + 21 m Me3EtN·TFSI | 3.25 (1.75–5.0) | 0.91@25 | LiMn2O4//Li4Ti5O12 | 2.55 | 145 | |||
| 50 m LiTFSI + 25 m TMBTFSI | 3.25 | – | LiMn2O4//TiO2(B) | 2.35 | 150 | |||
| Na+ | 17 m NaClO4 | 2.8 (1.7–4.4) | 108@25 | Na4Fe3(PO4)2(P2O7)// NaTi2(PO4)3 | – | 36 | ||
| 17 m NaClO4 + 2 m NaOTF | 2.8 (1.6–4.4) | 95.25@25 | Na3V2(PO4)3// Na3V2(PO4)3 | 1.75 | 70 | |||
| 32 m KOAc + 8 m NaOAc | 2.4 (0.7–3.1) | 12@25 | Na2VTi(PO4)3// Na2VTi(PO4)3 | 1.13 | – | |||
| 9 m NaOTF + 22 m TEAOTF | 3.3 (0.8–4.1) | 11.2@25 | Na1.88Mn[Fe(CN)6]0.97∙1.35H2O//NaTiOPO4 | – | – | |||
| Na(PTFSI)0.65(TFSI)0.14 (OTf)0.21∙3H2O | 2.7 (1.9–4.6) | 14@25 | Na3V2(PO4)2F3// NaTi2(PO4)3 | 1.75 | 77.9 | |||
| 35 m NaFSI | 2.6 (1.8–4.4) | 8@25 | Na3(VOPO4)2F// NaTi2(PO4)3 | – | – | |||
| K+ | 30 m KFSI | 3.97 (1.14–5.11) | – | K1.85Fe0.33Mn0.67 [Fe(CN)6]0.98∙ 0.77H2O//β-PTCDA | ||||
| K(PTFSI)0.12(TFSI)0.08 (OTf)0.8∙2H2O | 2.5 (2.1–4.6) | 34.6@25 | – | – | – | |||
| 61.7 m K(FSI)0.55(OTf)0.45∙ 0.9H2O | 2.7 (2.1–4.8) | 12@25 | KVPO4F// NaTi2(PO4)3 | 3.0 | – | |||
| 37 m KFSI | 2.8 (1.6–4.4) | 23.12@25 | AC//AC | 2.3 | 20.5 | |||
| Additive | Li+ | Urea-LiClO4 | 3.6 (1.2–4.8) | – | LiMn2O4//Li4Ti5O12 | 2.3 | 140 | |
| 0.1wt% TMSB- 21 m LiTFSI | 3.0 | – | LiCoO2/Mo6S8 | 2.5 | 120 | |||
| HFE gel-21 m LiTFSI + 7 m LiOTf | 4.9 (0–4.9) | – | LiVPO4F//Graphite | 4.0 | ~400 | |||
| 5% PAM-21 m LiTFSI | 3.1 (1.8–4.9) | 6.5@30 | LiMn2O4//L-TiO2 | – | – | |||
| 5% AM-21 m LiTFSI | 3.1 (1.8–4.9) | 9.6@25 | LiMn2O4//L-TiO2 | – | – | |||
| Urea-LiTFSI | 3.3 (1.5–4.8) | 1@25 | LiMn2O4//Li4Ti5O12 | 2.5 | - | |||
| CO2-5 m LiTFSI | 3.08 (1.67–4.75) | 54.6@25 | LiMn2O4/Mo6S8 | – | – | |||
| Urea-LiClO4 | 3.2 | 26@25 | LiMn2O4//Li4Ti5O12 | 2.2 | 135 | |||
| Co-solvent | Li+ | DMC-LiTFSI | 4.1 (1.0–5.1) | 5.0@25 | LiNi0.5Mn1.5O4// Li4Ti5O12 | 3.2 | 165 | |
| AN-LiTFSI | 4.5 (0.7–5.2) | 3.27@30 | LiMn2O4//Li4Ti5O12 | 2.55 | 109 | |||
| TEGDME-LiTFSI | 4.2 (0.6–4.8) | 0.625@25 | LiMn2O4//Li4Ti5O12 | 2.5 | 120 | |||
| PEG(400)-LiTFSI | 3.2 (1.3–4.5) | 0.8@25 | LiMn2O4//Li4Ti5O12 | 2.5 | 75–100 | |||
| PEGDME(450)-LiTFSI | 3.2 (1.3–4.5) | 2.4@25 | LiMn2O4//Li4Ti5O12 | 2.5 | – | |||
| PD-LiNO3 | 2.9 (2.2–5.2) | 22.8@25 | LiMn2O4//Mo6S8 | – | – | |||
| MSM-LiClO4 | 3.5 (1.6–5.1) | 3.71@25 | LiMn2O4//Li4Ti5O12 | 2.6 | – | |||
| Sulfolane-LiTFSI | 3.4 (1.3–4.7) | 2.5@25 | LiMn2O4//Li4Ti5O12 | 2.5 | 141 | |||
| TMS-LiTFSI | 5.4 (0.3–5.7) | 0.41@25 | LiNi0.5Mn1.5O4// Li4Ti5O12 | 3.15 | 136 | |||
| MU-LiTFSI | 4.5 (0.5 – 5.0) | 3.2@25 | LiMn2O4//Li4Ti5O12 | – | – | |||
| DOL-LiTFSI | 4.7 (0.3 – 5.0) | 7.09@60 | LiMn2O4//Li4Ti5O12 | – | – | |||
| SL-LiClO4 | 3.8 (1.1–4.9) | 3.74@25 | LiMn2O4//Li4Ti5O12 | 2.45 | 71 | |||
| Na+ | Urea-DMF-NaClO4 | 2.8 (1.1–3.9) | 8.1@20 | NiHCF//NaTi2(PO4)3 | – | – | ||
| Sugar-NaNO3 | 2.812 | 8.536@25 | – | – | – | |||
| TMP-NaClO4 | 3.0 (1.2–4.2) | 23@25 | – | – | – | |||
| DMSO-NaClO4 | 3.1 (1.0–4.1) | – | Na3V2(PO4)3// Na3V2(PO4)3 | 1.7 | – |
Fig 8
(a) Discharge capacities of LCO in sat. LiCl, sat. LiNO3, sat. Li2SO4 at different temperatures 77; (b) photograph of the AEE and control electrolytes at −40 ℃ 80; (c) phase diagram of the LiTFSI-H2O binary mixtures 80; (d) the ionic conductivity of 3.86 m CaCl2 + 1 m NaClO4 electrolyte at different temperatures 82. (a) Adapted with permission from Ref. 77, Copyright 2018, WILEY-VCH; (b, c) Adapted with permission from Ref. 80, Copyright 2020, Elsevier; (d) Adapted with permission from Ref. 82, Copyright 2022, Wiley-VCH."
Fig 9
(a) DSC analysis of electrolyte with different amounts of anti-freezing additives (EG) 86; (b) the ionic conductivity of a 1 mol∙L−1 Li2SO4 aqueous electrolyte with different amounts of anti-freezing additives (EG) at −20 ℃ 86; (c) DSC curve of 12SL-4H2O-3LiClO4 electrolyte 68; (d) GCD curves at different temperatures for LMO//LTO full battery in the 12SL-4H2O-3LiClO4 electrolyte 68; (e) photographs of WISE, BSiS-D0.28, and BSiS-A0.5 electrolytes at 0 and −20 ℃ 48; (f) ionic conductivity of BSiS-D0.28 and BSiS-A0.5 hybrid electrolytes in temperature range of −20 to 60 ℃ 48. (a, b) Adapted with permission from Ref. 86, Copyright 2019, American Chemical Society; (c, d) Adapted with permission from Ref. 68, Copyright 2021, Wiley-VCH; (e, f) Adapted with permission from Ref. 48, Copyright 2019, WILEY-VCH"
Fig 10
(a) Ionic conductivity of electrolytes over a wide temperature range 67; (b) DSC curves of BSiS-AN0.5 and BSiS-DOL0.5 hybrid electrolytes from −140 to 60 ℃ 67; (c) optimized structures and solvation energy of Li+-H2O and Li+-DOL from DFT calculations 67; (d) Arrhenius behavior of the temperature-dependent of RCT in LMO/LTO cells in BSiS-AN0.5 and BSiS-DOL0.5 hybrid electrolytes and the calculated Ea 67; (e) local structure of 2 m NaClO4-DMSOx=0.3 electrolyte from MD simulations 69; (f) temperature-dependent ionic conductivity in 2 m NaClO4-DMSOx=0.3 69. (a–d) Adapted with permission from Ref. 67, Copyright 2021, Elsevier; (e, f) Adapted with permission from Ref. 69, Copyright 2019, WILEY-VCH."
Fig 11
(a) Molecular structures of betaine and proline 91; (b) proposed Li+ migration mechanism in polySH electrolyte, where hydrated Li+ hopping through SO3− sites 93; (c) ionic conductivity of polySH, polyHEA, and PVA electrolyte 93; (d) DSC results of polySH electrolytes with different LiCl concentrations 93; (e) ionic conductivities of polySH electrolytes at different temperatures 93; (f) schematic illustration of the preparation of OHEC 94. (a) Adapted with permission from Ref. 91, Copyright 2019, WILEY-VCH; (b–e) Adapted with permission from Ref. 93, Copyright 2021, Wiley-VCH; (f) Adapted with permission from Ref. 94, Copyright 2020, Wiley-VCH."
Table 2
Wide-temperature-range AABs achieved by electrolyte modification."
| Strategy | Electrolyte | Freezing point (℃) | Ionic conductivity (mS∙cm−1)@.(℃) | Cathode//Anode | Capacity retention (%)@.(℃) | Ref. | |
| Highly Concentrated Salt | Li+ | 40.4 m KOAc + 9.8 m LiOAc | ~ −30 | 1.2@−30 | LiMn2O4//AC | 60@−20 | |
| 5.2 m LiTFSI | < −40 | 1.8@−40 | LiCoO2//Li4Ti5O12 | 66.49@−40 | |||
| Saturated LiCl | ~ −50 | - | LiCoO₂ (Three-electrode system) | 72@−40 | |||
| 21 m LiTFSI | - | LiMn2O4//TiO2 | 79@0 | ||||
| LiCl-P(SBMA-co-HEA) Gel | - | 12.6@−40 | AC//AC | 78@−30 | |||
| Li2SO4-EMIMBF4- PVA/Agar Gel | - | - | AC//AC | 90@−30 | |||
| LiCl/KCl-CG/PAM Gel | - | 19@−40 | AC//AC | 78.9@−40 | |||
| LiTFSI-ARS-PAM Gel | - | 4@−15 | MnO2//MnO2 | 72.5@−15 | |||
| NaCl-Li2SO4- CS-P(AM-co-AA) Gel | < −41 | 36@−20 | Ti3C2Tx MXene//CNTs | 50.5@−20 | |||
| Na+ | 2 m NaClO4 | < −20 | 3.49 | Ni(OH)2//NaTi2(PO4)3 | 85@−20 | ||
| CaCl2-NaClO4 | < −100 | 7.13@−50 | Na2CoFe(CN)6//AC | 64.8@−30 | |||
| K+ | 22 mol∙L−1 KCF3SO3 | - | 10@−20 | K1.85Fe0.33Mn0.67[Fe(CN)6]0.98 ·0.77H2O//PTCDI | 76.3@−20 | ||
| Co-solvent | Li+ | AN-LiTFSI | < −60 | 0.63@−60 | LiMn₂O₄//Li4Ti5O12 | 95@0 | |
| TMS-LiTFSI | < −85 | 1.03 × 10−4 @−80 | LiNi0.5Mn1.5O4//Li4Ti5O12 | 86.1@−20 | |||
| DOL-LiTFSI | < −95 | – | LiMn2O4//Li4Ti5O12 | 52@−50 | |||
| SL-LiClO4 | ~ −110 | 0.05@−50 | LiMn2O4//Li4Ti5O12 | 98@−20 | |||
| EG-LiCl- P(AMPS-co-AM) Gel | - | 1.9@−20 | AC//AC | 71@−20 | |||
| EG-Li2SO4 | ~ −24.6 | 4.25@−20 | LiFePO4 (Three-electrode system) | 82@−20 | |||
| Gly-LiClO4-HPC/PVA Gel | - | 5.7@−40 | AC//AC | 73.75@−40 | |||
| EG-LiCl-PVA Gel | < −62.8 | 0.83@−40 | AC//AC | 68.3@−30 | |||
| EG-LiTFSI-PAM Gel | < −100 | 1.5@−40 | PANI//PANI | 70.4@−40 | |||
| Na+ | TMP-NaClO4 | – | - | aMEGO//aMEGO | 67.9@−20 | ||
| DMSO-NaClO4 | < −130 | 0.11@−50 | AC//NaTi2(PO4)3 | 60@−50 | |||
| AN-NaClO4 | - | 4.95@−50 | AC//AC | 86.5@−50 | |||
| MeOH-Na2SO4-SiO2 Gel | - | 0.07@−30 | AC//NaTi2(PO4)3 | 65.05@−30 |
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