Review on the recent development of Li3VO4 as anode materials for lithium-ion batteries

doi:10.1016/j.jmst.2021.02.020

Abstract

Abstract:

Among the various anodes, Li₃VO₄ is a potential intercalation kind anode used in lithium-ion batteries (LIBs) that exhibits safer discharge voltage and higher capacity than graphite, a lower voltage plateau than Li₄Ti₅O₁₂, and smaller volume difference in the Li⁺ intercalation/deintercalation process than metals and alloys. However, the comparatively low electronic conductivity, low initial coulombic efficiency (ICE) and serious capacity decay make the Li₃VO₄ anode unviable when it comes to practical implementation. Therefore, this paper reviews the research progress of Li₃VO₄ in recent years, mainly including the strategies of developing different synthesis methods to construct unique morphology, through coating, compositing or elemental doping to increase the ICE, electronic conductivity and the cycle constancy. Moreover, the application of Li₃VO₄ anode materials in other energy storage systems is summarized. Lastly, the development prospect and challenge of Li₃VO₄ anodes are discussed.

Key words: Lithium-ion batteries, Li₃VO₄, Anode material, Electrochemical performance

Limin Zhu, Zhen Li, Guochun Ding, Lingling Xie, Yongxia Miao, Xiaoyu Cao. Review on the recent development of Li₃VO₄ as anode materials for lithium-ion batteries[J]. J. Mater. Sci. Technol., 2021, 89: 68-87.

Figures/Tables 17

Fig. 1. (a, b) Crystal structure of Li3VO4 projected along the c-axis and a-axis, (c, d) Crystal structure of Li6VO4 projected along the c-axis and a-axis, (e) Basic groups and atoms of the structure and (f) Schematic description of graphite-like Li3VO4 upon full Li insertion. Reprinted with permission [16]. Copyright 2015, Elsevier.

Fig. 2. The comparison of Li3VO4 with two typical insertion anodes of Li4Ti5O12 and graphite in terms of intercalation potential, specific capacity and energy density. Reprinted with permission [18]. Copyright 2013, Wiley-VCH.

Table 1 The electrochemical properties of various Li3VO4 electrodes prepared by different methods.

Synthesis methods	Current density	Voltage range (V)	Initial charge capacity (mA h g^-1)	Initial coulombic efficiency (%)	Cycle number	Final charge capacity (mAh g^-1)	Refs.
solid-state process	1C	0.1-2.0	184.22	41.43	100	179.67	[36]
solution-based precipitation	1C	0.1-2.0	361.22	68.97	100	179.67	[36]
template-free solution method	-	0.2-3.0	323	-	-	-	[37]
hydrothermal method	0.1C (1C = 394 mA g^-1)	0.2-3.0	-	-	50	315	[38]
sol-gel method	0.1C (1C = 394 mA g^-1)	0.01-3.0	323	76.5	75	373	[39]
annealing in vacuum	200 mA g^-1	0.2-3.0	326	78	100	286	[40]
annealing in hydrogen	1 A g^-1	0.01-3.0	306 (discharge)	-	500	244 (discharge)	[41]
hydrothermal method	0.1C	0.2-2.0	315	61.4	-	-	[42]
microwave-assisted hydrothermal method	100 mA g^-1	0.2-3.0	163	-	100	104	[43]

Fig. 3. In-situ XRD patterns of the Li3VO4 material in the first cycle (a) and the second cycle (b); In-situ EIS profiles of Li3VO4 at (c) initial cycle and (d) second cycle. Reprinted with permission [39]. Copyright 2016, American Chemical Society.

Table 2 A comparison with previously reported Li3VO4 anode for LIBs synthesized by different modification methods.

Modification method	materials	Current density	Voltage range (V)	Initial charge capacity (mAh g^-1)	Initial coulombic efficiency (%)	Cycle number	Final charge capacity (mAh g^-1)	Refs.
carbon-coating	6.12 % carbon-coated Li₃VO₄	0.18C (1C = 500 mA g^-1)	0.1-2.5	485.1	71.7	-	-	[45]
carbon-coating	Li₃VO₄/C	90 mA g^-1	0.1-3.0	312 (discharge, -20 °C) 600 (discharge, 0 °C) 760 (discharge, 25 °C) 721 (discharge, 50 °C)	40.45 72.09 74.34 73.41	-	-	[46]
carbon-coating	Li₃VO₄/C	0.2C (1C = 400 mA g^-1)	0.1-3.0	547.1	78.0	100	394 (1C)	[16]
carbon-coating	Li₃VO₄-BMC	20 mA g^-1	0.05-3.0	315	79.5	50	245	[47]
carbon-encapsulated	Li₃VO₄/C	0.1C (1C = 400 mA g^-1)	0.2-3.0	392 (discharge)	-	50	401	[48]
carbon-coating	Li₃VO₄/C	0.1C (1C = 400 mA g^-1)	0.2-3.0	469 (discharge)	-	50	415 (0.5C)	[49]
carbon-coating	LVO/C@EG	100 mA g^-1	0.2-3.0	415	72.2	200	360	[50]
carbon-coating	LVO⊂C submicron sphere	0.2C (1C = 400 mA g^-1)	-	402	79.3	-	-	[51]
carbon-coating	C@LVO rods	0.2C (1C = 400 mA g^-1)	0.2-3.0	403.4	78.13	300	440 (discharge)	[52]
carbon-coating	LVO@C	0.5C	0.05-3.0	496.9	70	1000	399 (10C)	[53]
carbon-coating	LVO/C hollow spheres	0.2C (1C = 400 mA g^-1)	0.2-3.0	429.4	64.5	100	400	[54]
graphitized carbon-coating	HP-Li₃VO₄/C	200 mA g^-1	0.01-3.0	390	86.7	300	381	[55]
nitrogen-doped carbon coating	NC-LVO	197 mA g^-1	0.01-3.0	538.1 (discharge)	-	100	426.6(discharge)	[56]
LiVO₂-coating	LL@C-600	100 mA g^-1	0.01-3.0	678	65.4	100	689(discharge)	[57]
composite	Li₃VO₄/C-Ni	10C (1C = 180 mA g^-1)	0.02-3.0	265	84.1	2000	325	[58]
composite	Li₃VO₄/N-C	0.15 A g^-1	0.02-3.0	540	78.7	800	544	[59]
composite	Li₃VO₄/C	150 mA g^-1	0.02-3.0	594	70.8	300	549	[60]
composite	Li₃VO₄@C	40 mA g^-1	0.05-3.0	451	82.3	100	394	[61]
composite	LVO@C NW	0.2 A g^-1	0.2-3.0	417.7	64.6	200	404.9	[62]
composite	LVO/CS	0.1 A g^-1	0.01-3.0	599	59.2	100	716	[63]
composite	Li₃VO₄/N-doped C	150 mA g^-1	0.02-3.0	472	78.7	100	460	[64]
composite	LVO-m/c	0.1 A g^-1	0.2-3.0	413.4	73.2	1000	236.6 (4 A g^-1)	[65]
composite	Li₃VO₄/CNT	0.1 A g^-1	0.2-3.0	453 (discharge)	-	2000	250 (2 A g^-1)	[66]
composite	Li₃VO₄/C/CNT	0.5C	0.2-2.0	397	60.4	500	272 (10C)	[67]
composite	Li₃VO₄/graphene nanosheets	20 mA g^-1	0.2-3.0	-	-	50	394	[68]
composite	Li₃VO₄ nanoribbon/graphene	0.2C (1C = 400 mA g^-1)	0.2-3.0	335.5	59.1	200	452.5	[69]
composite	Li₃VO₄/3D graphene	200 mA g^-1	0.2-3.0	519	65	2500	259 (2 A g^-1)	[70]
composite	Li₃VO₄@GNS	0.5C	0.2-3.0	486	65.3	5000	163 (5C)	[71]
composite	Li₃VO₄/N-doped graphene	0.15 A g^-1	0.02-3.0	429	78	100	476	[72]
composite	LVO/CRGO	0.2C	0.2-3.0	487.5	78.9	100	476.0	[73]
composited	LVO/rGO	4 A g^-1	0.2-3.0	343.8	-	1500	257.9	[74]
composite	LVO/C/rGO	0.25C (1C = 400 mA g^-1)	0.2-3.0	399.5	94	5000	325 (10C)	[75]
composite	LVO/C/rGO	100 mA g^-1100 mA g ^-1	0.2-3.00.02-3.0	402.6 591	69.6 71.2	100 100	378 560	[76]
composite	HC-LVO/C/G	0.5C (1C = 400 mA g^-1)	0.2-3.0	436	61.2	200	387	[77]
composite	Li₃VO₄/MoS₂	100 mA g^-1	0.02-3.0	607	77	100	679	[78]
composite	Li₃VO₄/MoS₂	100 mA g^-1	0.02-3.0	735	77.3	100	781.2	[79]
composite	Li₃VO₄@LiVO₂	150 mA g^-1	0.02-3.0	448	78.7	100	468	[80]
composite	Li₃VO₄/NiO/Ni	70 mA g^-1	0.02-3.0	631	73.4	100	604	[81]
composite	Ag@Li₃VO₄	0.15A g^-1	0.02-3.0	492	73.6	150	492	[82]
composite	LVO/Ti₃C₂T_x MXene	2000 mA g^-1	0.01-3.0	187 (discharge)	-	1000	146 (discharge)	[83]
doping	Li_2.95Na_0.05VO₄	0.1C (1C = 394 mA g^-1)	0.05-3.0	523.4	73.7	150	398.3 (1C)	[84]
doping	Li_2.97Ca_0.03VO₄	0.1C (1C = 394 mA g^-1)	0.05-3.0	526.7	75	-	-	[85]
doping	Ni²⁺-doped LVO	200 mA g^-1	0.01-3.0	535 (discharge)	-	-	-	[86]
doping	Li₃V_0.99Mo_0.01O₄	5C (1C = 590 mA g^-1)	0.1-3.0	439 (discharge)	-	100	413 (discharge)	[87]
doping	Li_3.05Ti_0.05V_0.95O₄	1000 mA g^-1	0.2-3.0	-	-	500	∼328	[88]
doping	Li₃Nb_0.02V_0.98O₄	30 mA g^-1	0.1-3.0	549.4	76.4	100	410.7 (200 mA g^-1)	[89]
doping	Li₃V_0.99Fe_0.01O_4-δ	100 mA g^-1	0.01-3.0	482	76.8	100	484	[90]

Table 2 A comparison with previously reported Li3VO4 anode for LIBs synthesized by different modification methods.

Modification method	materials	Current density	Voltage range (V)	Initial charge capacity (mAh g^-1)	Initial coulombic efficiency (%)	Cycle number	Final charge capacity (mAh g^-1)	Refs.
carbon-coating	6.12 % carbon-coated Li₃VO₄	0.18C (1C = 500 mA g^-1)	0.1-2.5	485.1	71.7	-	-	[45]
carbon-coating	Li₃VO₄/C	90 mA g^-1	0.1-3.0	312 (discharge, -20 °C) 600 (discharge, 0 °C) 760 (discharge, 25 °C) 721 (discharge, 50 °C)	40.45 72.09 74.34 73.41	-	-	[46]
carbon-coating	Li₃VO₄/C	0.2C (1C = 400 mA g^-1)	0.1-3.0	547.1	78.0	100	394 (1C)	[16]
carbon-coating	Li₃VO₄-BMC	20 mA g^-1	0.05-3.0	315	79.5	50	245	[47]
carbon-encapsulated	Li₃VO₄/C	0.1C (1C = 400 mA g^-1)	0.2-3.0	392 (discharge)	-	50	401	[48]
carbon-coating	Li₃VO₄/C	0.1C (1C = 400 mA g^-1)	0.2-3.0	469 (discharge)	-	50	415 (0.5C)	[49]
carbon-coating	LVO/C@EG	100 mA g^-1	0.2-3.0	415	72.2	200	360	[50]
carbon-coating	LVO⊂C submicron sphere	0.2C (1C = 400 mA g^-1)	-	402	79.3	-	-	[51]
carbon-coating	C@LVO rods	0.2C (1C = 400 mA g^-1)	0.2-3.0	403.4	78.13	300	440 (discharge)	[52]
carbon-coating	LVO@C	0.5C	0.05-3.0	496.9	70	1000	399 (10C)	[53]
carbon-coating	LVO/C hollow spheres	0.2C (1C = 400 mA g^-1)	0.2-3.0	429.4	64.5	100	400	[54]
graphitized carbon-coating	HP-Li₃VO₄/C	200 mA g^-1	0.01-3.0	390	86.7	300	381	[55]
nitrogen-doped carbon coating	NC-LVO	197 mA g^-1	0.01-3.0	538.1 (discharge)	-	100	426.6(discharge)	[56]
LiVO₂-coating	LL@C-600	100 mA g^-1	0.01-3.0	678	65.4	100	689(discharge)	[57]
composite	Li₃VO₄/C-Ni	10C (1C = 180 mA g^-1)	0.02-3.0	265	84.1	2000	325	[58]
composite	Li₃VO₄/N-C	0.15 A g^-1	0.02-3.0	540	78.7	800	544	[59]
composite	Li₃VO₄/C	150 mA g^-1	0.02-3.0	594	70.8	300	549	[60]
composite	Li₃VO₄@C	40 mA g^-1	0.05-3.0	451	82.3	100	394	[61]
composite	LVO@C NW	0.2 A g^-1	0.2-3.0	417.7	64.6	200	404.9	[62]
composite	LVO/CS	0.1 A g^-1	0.01-3.0	599	59.2	100	716	[63]
composite	Li₃VO₄/N-doped C	150 mA g^-1	0.02-3.0	472	78.7	100	460	[64]
composite	LVO-m/c	0.1 A g^-1	0.2-3.0	413.4	73.2	1000	236.6 (4 A g^-1)	[65]
composite	Li₃VO₄/CNT	0.1 A g^-1	0.2-3.0	453 (discharge)	-	2000	250 (2 A g^-1)	[66]
composite	Li₃VO₄/C/CNT	0.5C	0.2-2.0	397	60.4	500	272 (10C)	[67]
composite	Li₃VO₄/graphene nanosheets	20 mA g^-1	0.2-3.0	-	-	50	394	[68]
composite	Li₃VO₄ nanoribbon/graphene	0.2C (1C = 400 mA g^-1)	0.2-3.0	335.5	59.1	200	452.5	[69]
composite	Li₃VO₄/3D graphene	200 mA g^-1	0.2-3.0	519	65	2500	259 (2 A g^-1)	[70]
composite	Li₃VO₄@GNS	0.5C	0.2-3.0	486	65.3	5000	163 (5C)	[71]
composite	Li₃VO₄/N-doped graphene	0.15 A g^-1	0.02-3.0	429	78	100	476	[72]
composite	LVO/CRGO	0.2C	0.2-3.0	487.5	78.9	100	476.0	[73]
composited	LVO/rGO	4 A g^-1	0.2-3.0	343.8	-	1500	257.9	[74]
composite	LVO/C/rGO	0.25C (1C = 400 mA g^-1)	0.2-3.0	399.5	94	5000	325 (10C)	[75]
composite	LVO/C/rGO	100 mA g^-1100 mA g ^-1	0.2-3.00.02-3.0	402.6 591	69.6 71.2	100 100	378 560	[76]
composite	HC-LVO/C/G	0.5C (1C = 400 mA g^-1)	0.2-3.0	436	61.2	200	387	[77]
composite	Li₃VO₄/MoS₂	100 mA g^-1	0.02-3.0	607	77	100	679	[78]
composite	Li₃VO₄/MoS₂	100 mA g^-1	0.02-3.0	735	77.3	100	781.2	[79]
composite	Li₃VO₄@LiVO₂	150 mA g^-1	0.02-3.0	448	78.7	100	468	[80]
composite	Li₃VO₄/NiO/Ni	70 mA g^-1	0.02-3.0	631	73.4	100	604	[81]
composite	Ag@Li₃VO₄	0.15A g^-1	0.02-3.0	492	73.6	150	492	[82]
composite	LVO/Ti₃C₂T_x MXene	2000 mA g^-1	0.01-3.0	187 (discharge)	-	1000	146 (discharge)	[83]
doping	Li_2.95Na_0.05VO₄	0.1C (1C = 394 mA g^-1)	0.05-3.0	523.4	73.7	150	398.3 (1C)	[84]
doping	Li_2.97Ca_0.03VO₄	0.1C (1C = 394 mA g^-1)	0.05-3.0	526.7	75	-	-	[85]
doping	Ni²⁺-doped LVO	200 mA g^-1	0.01-3.0	535 (discharge)	-	-	-	[86]
doping	Li₃V_0.99Mo_0.01O₄	5C (1C = 590 mA g^-1)	0.1-3.0	439 (discharge)	-	100	413 (discharge)	[87]
doping	Li_3.05Ti_0.05V_0.95O₄	1000 mA g^-1	0.2-3.0	-	-	500	∼328	[88]
doping	Li₃Nb_0.02V_0.98O₄	30 mA g^-1	0.1-3.0	549.4	76.4	100	410.7 (200 mA g^-1)	[89]
doping	Li₃V_0.99Fe_0.01O_4-δ	100 mA g^-1	0.01-3.0	482	76.8	100	484	[90]

Fig. 4. (a, b) HRTEM images of the carbon coated sample (Li3VO4-BMC); (c) The cases of lithium-ion diffusion and electron conduction in micro-sized Li3VO4, nano-sized Li3VO4 and fully carbon-coated nano-sized Li3VO4. (d) Cycle performances of Li3VO4-RAW, Li3VO4-BM and Li3VO4-BMC. Reprinted with permission [47]. Copyright 2015, The Royal Society of Chemistry. (e) Schematic diagram of the synthesis procedure of the hollow LVO/C microcuboid. (f) Capacity retention and Coulombic efficiency of LVO/C-600 at 0.5 C. (g) Capacity retention and Coulombic efficiency of the LVO and LVO/C-600 at 10 C (4 A g-1). Reprinted with permission [49]. Copyright 2015, American Chemical Society.

Fig. 5. (a) Schematic illustration of the formation process of LVO?C spheres; (b-d) SEM, TEM and HRTEM images of LVO?C spheres; (e) The first five discharge-charge voltage profiles of LVO?C at rate of 0.2C; (f) Cycle performance and CE for 1000 cycles at a current rate of 10C; (g) Rate performance at various rates from 0.2 to 30C. Reprinted with permission [51]. Copyright 2017, Wiley-VCH.

Fig. 6. (a) The formation mechanism of the mesoporous LVO/C hollow spheres, (b) SEM image of the LVO/C, (c) TEM images of the LVO/C, the inset is the corresponding SAED pattern indexed using the powder diffraction technique, (d) HRTEM image of the LVO/C, (e) Galvanostatic discharge-charge profiles of LVO/C in the voltage range of 0.2-3 V at a rate of 0.2C (1C = 400 mA g-1), (f) cycling performance of LVO/C and LVO at a current density of 0.2C, (g) discharge and charge capacities of LVO/C and LVO at various C-rates. Reprinted with permission. Copyright 2016 [54], The Royal Society of Chemistry.

Fig. 7. (a) Schematic illustration of the fabrication of HP-Li3VO4/C and its application in LIBs, (b) FE-SEM images of HP-Li3VO4/C, (c) cycling performance of HP-Li3VO4/C and Li3VO4 electrodes at a current density of 0.2 A g-1 and 1 A g-1 in the voltage range of 0.01-3.0 V (vs Li+/Li), (d) long life cycling performance of HP-Li3VO4/C and Li3VO4 electrodes at 4 A g-1 for 500 cycles. Reprinted with permission [55]. Copyright 2015, American Chemical Society.

Fig. 8. (a) A schematic illustration of the formation process of the hierarchically porous Li3VO4/C-Ni, (b) A schematic illustration of the hierarchical electron transmission and lithium ion diffusion in Li3VO4/C-Ni: (Ⅰ) The first level of the 3D porous architecture of the Ni foam, (Ⅱ) The second level of the porous architecture of the whole Li3VO4/C electrode, (Ⅲ) The third level of the porous architecture within the Li3VO4/C aggregation, (c) Discharge/charge capacity versus cycle number, (d) Discharge/charge capacity at 3 periods of various rates from 0.15C to 5.0C. Reprinted with permission [58]. Copyright 2016, The Royal Society of Chemistry.

Fig. 9. (a) SEM and (b, c) TEM images of the LVO@C NW, (d) Schematic illustration of the structural advantages and Li+ insertion mechanism of the LVO@C NW, (e) Cycling ability of the LVO@C NW and pristine LVO at 0.2 A g-1, (f) rate capability of the LVO@C NW from 0.2 A g-1 up to 32 A g-1. Reprinted with permission [62]. Copyright 2019, Wiley-VCH.

Fig. 10. (a) Schematic of the formation of the Li3VO4/CNT composite, (b) SEM image of the hollow Li3VO4/CNT composite, (c) Cycle performance of the hollow Li3VO4/CNT composite at 2 A g-1, (d) Discharge/charge curves for the hollow Li3VO4/CNT composite anode at different current densities. Reprinted with permission [66]. Copyright 2014, The Royal Society of Chemistry.

Fig. 11. (a) Schematic illustration of the fabrication of LVO/G, (b) FESEM and (c) TEM micrograph of LVO/G, (d) Cycling performance at the current density of 20 mA g-1 between 0.2 and 3 V (the inset is their cycling performance at 4 A g-1), (e) Rate performance between 0.2 and 3 V. Reprinted with permission [68]. Copyright 2013, American Chemical Society.

Fig. 12. (a) The proposed formation mechanism of the mesoporous LVO/C, (b) Schematic illustration for the synthesis procedure of the LVO/C/rGO, (c) SEM, (d) TEM images of LVO/C/rGO, (e) The first and second discharge/charge curves for the LVO/C and LVO/C/rGO at 0.1 A g-1, (f) Cycling performance of LVO/C/rGO at 4 and 20 A g-1. Reprinted with permission [75]. Copyright 2016, WILEY-VCH; (g) Schematic illustration of the synthesis process of the deflated balloon-like LVO/C/rGO microspheres, (h) SEM images of LVO/C/rGO, (i) Galvanostatic discharge/charge profiles of LVO/C/rGO at 100 mA g-1 and (j) Long-term cycling performance of LVO/C/rGO at 2000 mA g-1 in the potential window of 0.02-3.0 V. Reprinted with permission [76]. Copyright 2018, American Chemical Society.

Fig. 13. (a) The preparation procedure of the HC-LVO/C/G composite, (b) SEM and (c) TEM images of the HC-LVO/C/G composite, (d) View of the optimized crystal structure of Li3VO4, Li5VO4 and Li6VO4, (e) Typical galvanostatic charge-discharge curves and (f) Capacity retention and Coulombic efficiency of HC-LVO/C/G at 0.5C (1C = 0.4 A g-1). Reprinted with permission [77]. Copyright 2017, Elsevier.

Fig. 14. (a) Schematic illustration for the formation of Li3VO4@LiVO2, (b) Schematic advantages for the Li3VO4@LiVO2 in terms of electron transmission and lithium ion diffusion, (c) EIS spectra for pristine Li3VO4 and Li3VO4@LiVO2, (d) Typical galvanostatic charge-discharge curves at 0.15 A g-1 within a cut-off voltage window of 0.02-3.0 V. Reprinted with permission. Copyright 2018 [80], Elsevier.

Fig. 15. The crystal structure of LVO (a) and LTVO (b), (c) Schematic advantages for the LTVO, (d) cycle stability at 1000 mA g-1 and (e) rate capability of LVO and LTVO. Reprinted with permission [88]. Copyright 2017, American Chemical Society.

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Review on the recent development of Li₃VO₄ as anode materials for lithium-ion batteries

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