CIESC Journal ›› 2024, Vol. 75 ›› Issue (9): 3028-3040.DOI: 10.11949/0438-1157.20240283
• Reviews and monographs • Previous Articles Next Articles
Dan PENG(), Junjie LU, Wenjing NI, Yuan YANG, Jinglun WANG(
)
Received:
2024-03-08
Revised:
2024-04-19
Online:
2024-10-10
Published:
2024-09-25
Contact:
Jinglun WANG
通讯作者:
汪靖伦
作者简介:
彭丹(1997—),女,硕士研究生,1197613686@qq.com
基金资助:
CLC Number:
Dan PENG, Junjie LU, Wenjing NI, Yuan YANG, Jinglun WANG. Research progress of functional electrolyte for high-voltage LiCoO2 battery[J]. CIESC Journal, 2024, 75(9): 3028-3040.
彭丹, 卢俊杰, 倪文静, 杨媛, 汪靖伦. 高电压钴酸锂电池电解液研究进展[J]. 化工学报, 2024, 75(9): 3028-3040.
电池体系 | 电解液 | 电压/V | 容量保持率/% | 文献 |
---|---|---|---|---|
Li/LiCoO2 | 1.2 mol/L LiPF6+0.15 mol/L LiDFOB-FEC∶DMC∶HFE (1∶1∶1,体积比) | 2.75~4.50 | 83.4(200 mA/g,300 cycles) | [ |
Li/Li-Al-F@LiCoO2 | 1.0 mol/L LiPF6-FEC∶DFEC∶DMC (1∶1∶8,体积比) | 3.0~4.60 | >78.0(0.5 C,500 cycles) | [ |
MCMB/LiCoO2 | 1.0 mol/L LiPF6-FEC∶FEMC∶TTE (3∶6∶1,质量比) | 3.0~4.45 | 76.0(0.5 C,100 cycles) | [ |
Li/LiCoO2 | 1 mol/L LiPF6-MTFP | 2.8~4.50 | 97.0(25 mA/g,50 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-FEC∶F5EON (1∶3,体积比) | 2.8~4.50 | 77.4(0.3 C,200 cycles) | [ |
Li/LiCoO2 | 3.0 mol/L LiFSI-FMS | 3.0~4.60 | 92.5(0.2 C,100 cycles) | [ |
2.2 mol/L LiFSI-FMS | 3.0~4.50 | 95.0(0.2/0.5 C,400 cycles) | [ | |
1.5 mol/L LiFSI-TFTMS | 2.8~4.60 | 90.0(0.2/0.5 C,320 cycles) | [ |
Table 1 Electrochemical performances of fluorinated solvent for high-voltage LiCoO2 cells
电池体系 | 电解液 | 电压/V | 容量保持率/% | 文献 |
---|---|---|---|---|
Li/LiCoO2 | 1.2 mol/L LiPF6+0.15 mol/L LiDFOB-FEC∶DMC∶HFE (1∶1∶1,体积比) | 2.75~4.50 | 83.4(200 mA/g,300 cycles) | [ |
Li/Li-Al-F@LiCoO2 | 1.0 mol/L LiPF6-FEC∶DFEC∶DMC (1∶1∶8,体积比) | 3.0~4.60 | >78.0(0.5 C,500 cycles) | [ |
MCMB/LiCoO2 | 1.0 mol/L LiPF6-FEC∶FEMC∶TTE (3∶6∶1,质量比) | 3.0~4.45 | 76.0(0.5 C,100 cycles) | [ |
Li/LiCoO2 | 1 mol/L LiPF6-MTFP | 2.8~4.50 | 97.0(25 mA/g,50 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-FEC∶F5EON (1∶3,体积比) | 2.8~4.50 | 77.4(0.3 C,200 cycles) | [ |
Li/LiCoO2 | 3.0 mol/L LiFSI-FMS | 3.0~4.60 | 92.5(0.2 C,100 cycles) | [ |
2.2 mol/L LiFSI-FMS | 3.0~4.50 | 95.0(0.2/0.5 C,400 cycles) | [ | |
1.5 mol/L LiFSI-TFTMS | 2.8~4.60 | 90.0(0.2/0.5 C,320 cycles) | [ |
Fig.2 Cycling performance of high-voltage Li/LiCoO2 cells in 1.2 mol/L LiPF6+0.15 mol/L LiDFOB-FEC∶DMC∶HFE (1∶1∶1, volume ratio) electrolytes (a) and LSV chart (b)[24]
Fig.3 The binding energies between Li+ and various solvents (a); Raman spectra of different concentrations of FMS electrolytes (b); schematic diagram illustrating SEI/CEI formation mechanism of FMS-based electrolytes (c)[29]
电池体系 | 电解液 | 电压/V | 容量保持率/% | 文献 |
---|---|---|---|---|
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶PC∶DEC∶PP (1∶1∶1,质量比)+5.0%(质量分数) FEC+ 2.0%(质量分数) HTCN | 3.0~4.50 | 90.0(1.0 C,800 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)10%FEC+ 1.0%(质量分数) SUN/HTCN | 3.0~4.60 | 72.0 (1.0 C,300 cycles) 75.0(1.0 C,300 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶DEC (1∶1,体积比)+0.1%(质量分数) TTEP | 3.0~4.40 | 90.72(1.0 C,130 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.2%(质量分数) TPPSe | 3.0~4.65 | 74.1(1.0 C,500 cycles) | [ |
graphite/LiCoO2 | 1.15 mol/L LiPF6-EC∶PC∶DEC∶PP (1∶1∶1,质量比)+5.0%(质量分数) FEC+3.0%(质量分数) ADN+0.5%(质量分数) DMTMSP | 3.0~4.45 | 90.5(1.0 C,400 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-PC∶EC∶EMC (5∶25∶70,体积比)+2.0%(质量分数) TTFPB | 3.0~4.70 | 74.0(0.5 C,150 cycles) | [ |
1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.5%(质量分数) TPCB | 3.0~4.60 | 82.2(1.0 C,200 cycles) | [ | |
1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.1%(质量分数) TFPB | 3.0~4.60 | 84.6(1.0 C,200 cycles) | [ | |
1.0 mol/L LiPF6-EC∶EMC∶DEC (1∶1∶1,体积比)+2.0%(质量分数) TCEB | 2.75~4.50 | 78.2(1.0 C,200 cycles) | [ | |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC∶DEC (3∶5∶2,质量比)+1.0%(质量分数) LiDFOB | 3.0~4.50 | 80.2(1.0 C,300 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶DMC∶DEC (1∶1∶1,体积比)+1.0%(质量分数) BBSI | 3.0~4.60 | 81.3(0.5 C,300 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) HBAG | 3.0~4.40 | 94.88(1.0 C,160 cycles) | [ |
1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) MDFA | 3.0~4.45 | 93.1(1.0 C,100 cycles) | [ | |
1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) PTSI | 3.0~4.40 | 95.3(0.5 C,200 cycles) | [ | |
1.0 mol/L LiPF6-EC∶DMC∶EMC (1∶1∶1,质量比)+0.5%(质量分数) DMSE | 3.0~4.50 | 66.5(0.2 C,100 cycles) | [ | |
1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) TFBS | 3.0~4.50 | 96.8(0.5 C,100 cycles) | [ | |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.03%(质量分数) MMD | 3.0~4.60 | 83.5(1.0 C,200 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,体积比)+2.0%(质量分数) NPA | 3.0~4.60 | 77.1(0.3 C,200 cycles) | [ |
graphite/LiCoO2 | 1.3 mol/L LiPF6-EC/PC/EB (10∶15∶75,体积比)+7% FEC+ 1% LiFMDFB+3% HTCN+0.2% TMSP | 3.0~4.55 | 51.8(1.5 C charge/ 0.5 C discharge,500 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) DMMA | 3.0~4.65 | 70.7(1.0 C,500 cycles) | [ |
Table 2 Electrochemical performances of functional additives for high-voltage LiCoO2 cells
电池体系 | 电解液 | 电压/V | 容量保持率/% | 文献 |
---|---|---|---|---|
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶PC∶DEC∶PP (1∶1∶1,质量比)+5.0%(质量分数) FEC+ 2.0%(质量分数) HTCN | 3.0~4.50 | 90.0(1.0 C,800 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)10%FEC+ 1.0%(质量分数) SUN/HTCN | 3.0~4.60 | 72.0 (1.0 C,300 cycles) 75.0(1.0 C,300 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶DEC (1∶1,体积比)+0.1%(质量分数) TTEP | 3.0~4.40 | 90.72(1.0 C,130 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.2%(质量分数) TPPSe | 3.0~4.65 | 74.1(1.0 C,500 cycles) | [ |
graphite/LiCoO2 | 1.15 mol/L LiPF6-EC∶PC∶DEC∶PP (1∶1∶1,质量比)+5.0%(质量分数) FEC+3.0%(质量分数) ADN+0.5%(质量分数) DMTMSP | 3.0~4.45 | 90.5(1.0 C,400 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-PC∶EC∶EMC (5∶25∶70,体积比)+2.0%(质量分数) TTFPB | 3.0~4.70 | 74.0(0.5 C,150 cycles) | [ |
1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.5%(质量分数) TPCB | 3.0~4.60 | 82.2(1.0 C,200 cycles) | [ | |
1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.1%(质量分数) TFPB | 3.0~4.60 | 84.6(1.0 C,200 cycles) | [ | |
1.0 mol/L LiPF6-EC∶EMC∶DEC (1∶1∶1,体积比)+2.0%(质量分数) TCEB | 2.75~4.50 | 78.2(1.0 C,200 cycles) | [ | |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC∶DEC (3∶5∶2,质量比)+1.0%(质量分数) LiDFOB | 3.0~4.50 | 80.2(1.0 C,300 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶DMC∶DEC (1∶1∶1,体积比)+1.0%(质量分数) BBSI | 3.0~4.60 | 81.3(0.5 C,300 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) HBAG | 3.0~4.40 | 94.88(1.0 C,160 cycles) | [ |
1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) MDFA | 3.0~4.45 | 93.1(1.0 C,100 cycles) | [ | |
1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) PTSI | 3.0~4.40 | 95.3(0.5 C,200 cycles) | [ | |
1.0 mol/L LiPF6-EC∶DMC∶EMC (1∶1∶1,质量比)+0.5%(质量分数) DMSE | 3.0~4.50 | 66.5(0.2 C,100 cycles) | [ | |
1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) TFBS | 3.0~4.50 | 96.8(0.5 C,100 cycles) | [ | |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶DEC (3∶7,质量比)+0.03%(质量分数) MMD | 3.0~4.60 | 83.5(1.0 C,200 cycles) | [ |
graphite/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,体积比)+2.0%(质量分数) NPA | 3.0~4.60 | 77.1(0.3 C,200 cycles) | [ |
graphite/LiCoO2 | 1.3 mol/L LiPF6-EC/PC/EB (10∶15∶75,体积比)+7% FEC+ 1% LiFMDFB+3% HTCN+0.2% TMSP | 3.0~4.55 | 51.8(1.5 C charge/ 0.5 C discharge,500 cycles) | [ |
Li/LiCoO2 | 1.0 mol/L LiPF6-EC∶EMC (3∶7,质量比)+1.0%(质量分数) DMMA | 3.0~4.65 | 70.7(1.0 C,500 cycles) | [ |
Fig.10 Gibbs free energies (ΔG) of MMD reacting with H2O, HF and PF5 (a); 19F NMR spectra of baseline (b) and 0.03% MMD-containing electrolytes (c) added with 0.06% water after being stored for 7 d[54] (1 cal=4.184 J)
电池体系 | 电解液 | 容量保持率/% | 文献 |
---|---|---|---|
3.0~4.50 V Li/LiCoO2 | [5 mol/L LiTFSI-MP-FEC (9∶1,体积比)]∶TTE(2∶1,质量比) | 87.7(1.0 C,300 cycles) | [ |
1.4 mol/L LiFSI-DME-TTME (1∶4,体积比) | 90.0(0.2 C charge/0.5 C discharge,170 cycles) | [ | |
1.9 mol/L LiFSI-DME-HM (2∶1,体积比) | 80.0(0.2 C charge/0.5 C discharge,505 cycles) | [ | |
LiFSI∶DME∶FB∶3FB (1∶1.2∶2.8∶0.2,摩尔比) | 80.0(2.0 C,600 cycles) | [ | |
2.0 mol/L LiDFOB-DME∶DFEC (1∶1,体积比) | 82.32(0.3 C,1000 cycles) | [ | |
1.4 mol/L LiFSI-DME∶HFC (1∶3,摩尔比) | 88.0(0.2 C charge/0.5 C discharge,200 cycles) | [ |
Table 3 Electrochemical performances of high-voltage LiCoO2 cells based on localized high concentration electrolyte
电池体系 | 电解液 | 容量保持率/% | 文献 |
---|---|---|---|
3.0~4.50 V Li/LiCoO2 | [5 mol/L LiTFSI-MP-FEC (9∶1,体积比)]∶TTE(2∶1,质量比) | 87.7(1.0 C,300 cycles) | [ |
1.4 mol/L LiFSI-DME-TTME (1∶4,体积比) | 90.0(0.2 C charge/0.5 C discharge,170 cycles) | [ | |
1.9 mol/L LiFSI-DME-HM (2∶1,体积比) | 80.0(0.2 C charge/0.5 C discharge,505 cycles) | [ | |
LiFSI∶DME∶FB∶3FB (1∶1.2∶2.8∶0.2,摩尔比) | 80.0(2.0 C,600 cycles) | [ | |
2.0 mol/L LiDFOB-DME∶DFEC (1∶1,体积比) | 82.32(0.3 C,1000 cycles) | [ | |
1.4 mol/L LiFSI-DME∶HFC (1∶3,摩尔比) | 88.0(0.2 C charge/0.5 C discharge,200 cycles) | [ |
Fig.11 Schematic illustration model of TTME based electrolyte solvation structure (a); radial distribution functions between Li+ and O atom in FSI-/DME/TTME (inset: radial distribution functions between Li+ and O atom in TTME) (b)[68]; schematic illustration of the electrolyte structure and the correspondingly formed SEI/CEI in DFEC based electrolyte (c) and cycling performance of Li/LiCoO2 cells (d)[71] (1 Å=0.1 nm)
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