Journal of Inorganic Materials ›› 2022, Vol. 37 ›› Issue (5): 481-492.DOI: 10.15541/jim20210502
Special Issue: 【虚拟专辑】锂金属电池,钠离子电池和水系电池(2020~2021)
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WANG Yutong1(), ZHANG Feifan1, XU Naicai2, WANG Chunxia1, CUI Lishan1, HUANG Guoyong1(
)
Received:
2021-08-13
Revised:
2021-10-22
Published:
2022-05-20
Online:
2021-11-01
Contact:
HUANG Guoyong, professor. E-mail:huanggy@cup.edu.cn
About author:
WANG Yutong (1992-), male, PhD candidate. E-mail: 1248736790@qq.com
Supported by:
CLC Number:
WANG Yutong, ZHANG Feifan, XU Naicai, WANG Chunxia, CUI Lishan, HUANG Guoyong. Research Progress of LiTi2(PO4)3 Anode for Aqueous Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2022, 37(5): 481-492.
Type | Operating voltage/V | Safety | Electrolyte | Solvent | Cost |
---|---|---|---|---|---|
Organic Li-ion battery | 3.6-4.2 | Low | LiPF6, LiAsF6, etc | EC, DMC, DEC, etc | High |
Aqeuous Li-ion battery | 1.5-2.0 | High | Li2SO4, LiNO3, etc | H2O | Moderate |
Table 1 Comparison of the characteristics of aqeuous and organic lithium-ion batteries[8]
Type | Operating voltage/V | Safety | Electrolyte | Solvent | Cost |
---|---|---|---|---|---|
Organic Li-ion battery | 3.6-4.2 | Low | LiPF6, LiAsF6, etc | EC, DMC, DEC, etc | High |
Aqeuous Li-ion battery | 1.5-2.0 | High | Li2SO4, LiNO3, etc | H2O | Moderate |
Anode material | Specific capacity/ (mAh·g-1) | Potential/ V(vs. Li+/Li) | Potential/ V(vs. NHE) | Features |
---|---|---|---|---|
LiTi2(PO4)3 | 138 | 2.5 | -0.5 | Moderate specific capacity, stable framework |
TiP2O7 | 121 | 2.6 | -0.4 | Low specific capacity, high Li-intercalation potential |
VO2 | 250 | 2.6 | -0.4 | High specific capacity, poor cycling performance |
LiV3O8 | 250 | 2.6 | -0.4 | Fragile during cycling |
Table 2 Parameters of some anode materials for aqeuous lithium-ion battery[14]
Anode material | Specific capacity/ (mAh·g-1) | Potential/ V(vs. Li+/Li) | Potential/ V(vs. NHE) | Features |
---|---|---|---|---|
LiTi2(PO4)3 | 138 | 2.5 | -0.5 | Moderate specific capacity, stable framework |
TiP2O7 | 121 | 2.6 | -0.4 | Low specific capacity, high Li-intercalation potential |
VO2 | 250 | 2.6 | -0.4 | High specific capacity, poor cycling performance |
LiV3O8 | 250 | 2.6 | -0.4 | Fragile during cycling |
Method | Starting materials | Product characteristic | Features | Ref. | ||
---|---|---|---|---|---|---|
Li source | Ti source | P source | Morphology | |||
Solid state | LiH2PO4 | TiO2 | NH4H2PO4 | Irregular particles | Long calcination time, high temperature | [ |
Sol-Gel | CH3COOLi | Ti(C4H9O)4 | H3PO4 | Particles | Short calcination time, low temperature | [ |
Hydrothermal synthesis | CH3COOLi | Ti(C4H9O)4 | NH4H2PO4 | Regular particles | Regular particle morphology, great crystallinity | [ |
Co-precipitation method | LiOH | Ti(C4H9O)4 | H3PO4 | Particles | Requiring precise control | [ |
Electrospinning | CH3COOLi | Ti(C4H9O)4 | NH4H2PO4 | Fiber | Ideal electrochemical performance, difficult industrialization | [ |
Table 3 Comparison of common synthetic methods of LiTi2(PO4)3
Method | Starting materials | Product characteristic | Features | Ref. | ||
---|---|---|---|---|---|---|
Li source | Ti source | P source | Morphology | |||
Solid state | LiH2PO4 | TiO2 | NH4H2PO4 | Irregular particles | Long calcination time, high temperature | [ |
Sol-Gel | CH3COOLi | Ti(C4H9O)4 | H3PO4 | Particles | Short calcination time, low temperature | [ |
Hydrothermal synthesis | CH3COOLi | Ti(C4H9O)4 | NH4H2PO4 | Regular particles | Regular particle morphology, great crystallinity | [ |
Co-precipitation method | LiOH | Ti(C4H9O)4 | H3PO4 | Particles | Requiring precise control | [ |
Electrospinning | CH3COOLi | Ti(C4H9O)4 | NH4H2PO4 | Fiber | Ideal electrochemical performance, difficult industrialization | [ |
Fig. 5 Comparison chart of rate performance of four coated carbon sources (a, b)[72](Blue and black in (a) indicating polydopamine and phenolic resin; blue and black in (b) indicating polyacrylonitrile and glucose), schematic illustration of the tentative Li+ insertion mechanism in mesoporous LiTi2(PO4)3 with carbon coating layer (c)[75], schematic diagram of the synthesis steps of rGO-LTP (d)[78], and cyclic performance of LC and LCG anodes at 5C for 1000 cycles (e)[80] Colorful figures are available on website
Calcination parameter | Coating method | Carbon source | Weight percentage of carbon/% | Current density/(mA·g-1) | Specific capacity (cycles)/(mAh·g-1) | Capacity retention/% | Ref. |
---|---|---|---|---|---|---|---|
800 ℃-12 h | In-situ | Citric acid | 6.2 | 138 | 106.1(1)-89(1300) | 84 | [36] |
900 ℃-12 h | Ex-situ | Toluene | 12 | 700 | 100(1)-83(200) | 83 | [31] |
800 ℃-12 h | Ex-situ | Acetylene Black | 18 | 140 | 106.3(1)-86.5(100) | 81 | [81] |
850 ℃-12 h | Ex-situ | Acetylene Black | - | 1400 | 91.3(1)-74.4(100) | 81 | [82] |
700 ℃-12 h | In-situ | Pitch | 17.5 | 1380 | 107(1)-75.5(1000) | 70 | [83] |
550 ℃-24 h | In-situ | Sucrose | 3.5 | 1400 | 110(1)-104(800) | 94 | [17] |
750 ℃-5 h | In-situ | Polyaniline | 5.9 | 276 | 115.2(1)-94.6(1000) | 82 | [84] |
750 ℃-5 h | In-situ | Polyacrylonitrile | 5.9 | 690 | 95(1)-82.1(1000) | 86 | [85] |
900 ℃-12 h | In-situ | Graphene oxide | 1.79 | ~1380 | 110(1)-100(100) | 91 | [78] |
800 ℃-10 h | In-situ | Graphene oxide | - | ~276 | 105(1)-97.86(100) | 93.2 | [77] |
700 ℃-5 h | In-situ | Graphene oxide, phenolic resin | 16.2 | ~690 | 101.1(1)-78(1000) | 77.2 | [80] |
800 ℃-8 h | Ex-situ | β-Cyclodextrin | 3.13 | ~690 | 120(1)-(200)111.3 | 88.7 | [86] |
Table 4 Comparison of electrochemical performance of different carbon sources and coating methods by Sol-Gel
Calcination parameter | Coating method | Carbon source | Weight percentage of carbon/% | Current density/(mA·g-1) | Specific capacity (cycles)/(mAh·g-1) | Capacity retention/% | Ref. |
---|---|---|---|---|---|---|---|
800 ℃-12 h | In-situ | Citric acid | 6.2 | 138 | 106.1(1)-89(1300) | 84 | [36] |
900 ℃-12 h | Ex-situ | Toluene | 12 | 700 | 100(1)-83(200) | 83 | [31] |
800 ℃-12 h | Ex-situ | Acetylene Black | 18 | 140 | 106.3(1)-86.5(100) | 81 | [81] |
850 ℃-12 h | Ex-situ | Acetylene Black | - | 1400 | 91.3(1)-74.4(100) | 81 | [82] |
700 ℃-12 h | In-situ | Pitch | 17.5 | 1380 | 107(1)-75.5(1000) | 70 | [83] |
550 ℃-24 h | In-situ | Sucrose | 3.5 | 1400 | 110(1)-104(800) | 94 | [17] |
750 ℃-5 h | In-situ | Polyaniline | 5.9 | 276 | 115.2(1)-94.6(1000) | 82 | [84] |
750 ℃-5 h | In-situ | Polyacrylonitrile | 5.9 | 690 | 95(1)-82.1(1000) | 86 | [85] |
900 ℃-12 h | In-situ | Graphene oxide | 1.79 | ~1380 | 110(1)-100(100) | 91 | [78] |
800 ℃-10 h | In-situ | Graphene oxide | - | ~276 | 105(1)-97.86(100) | 93.2 | [77] |
700 ℃-5 h | In-situ | Graphene oxide, phenolic resin | 16.2 | ~690 | 101.1(1)-78(1000) | 77.2 | [80] |
800 ℃-8 h | Ex-situ | β-Cyclodextrin | 3.13 | ~690 | 120(1)-(200)111.3 | 88.7 | [86] |
Fig. 6 Discharge capacity for successive cycling at different current densities (a), long-term cycling behavior at current densities of 4 and 6 A·g-1 (b) of LiTi2(PO4)3/C and LiTi1.8Sn0.2(PO4)3/C[24]
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