In the process of Li-ion cell formation, a part of the active lithium from the cathode is consumed to form a solid-electrolyte interphase layer on the anode surface, resulting in an irreversible capacity loss. Especially in the case of adding high-capacity silicon-based anode materials to graphite, this kind of active lithium loss leads to an extremely low-first cycle coulomb efficiency and battery capacity. The problem can be effectively solved via the compensation of active lithium. The various ways used to supply active lithium are mainly divided into two categories: anode and cathode prelithiations. Anode prelithiation methods include physical mixing and chemical, self-discharge, and electrochemical pre-lithiations. The physical mixing lithiation method involves the addition of lithium metal powder to the anode or plate lithium metal foil to the anode surface, whereas the solution containing sacrificial lithium-rich compounds, such as butyl lithium, is used to prelithiate the anode in the case of chemical lithiation. Self-discharge lithiation is accomplished by the contact between the anode and lithium metal in the electrolyte. For electrochemical prelithiation, lithium metal is introduced into the battery as the third electrode, and the prelithiation is completed by discharging the anode. In the case of cathode prelithiation, sacrificial lithium-rich compounds with a high irreversible capacity are added to the cathode. Sacrificial lithium-rich compounds can be divided into binary lithium-containing compounds, such as Li2O, Li2O2, and Li2S; ternary lithium-containing compounds, including Li6CoO4 and Li5FeO4; organic lithium-containing compounds represented by Li2DHBN and Li2C2O4. The prelithiation technology can not only increase the capacity of lithium-ion cells but also benefit its cycling performances, especially for cells with silicon-containing anode. In this paper, the recent developments of lithium prelithiation technology are summarized, and several of our own works are introduced. The application prospect of lithium prelithiation technology is also forecasted.
Fig. 1
Roll-to-roll prelithiation method for preparation of LixSn, LixAl and LixSi/C anode electrodes:(a) illustration of roll-to-roll prelithiation method; (b) specific operation of roll-to-roll mechanical prelithiation method; (c) visual image of as-prepared LixSn foil (8 cm×16 cm), where dark layer is Li-Sn alloy and underlay with metallic luster is Sn; (d) cross-sectional SEM image of LixSn alloy foil, where top layer is LixSn and sublayer is pure Sn; (e and f) visual images of as-prepared LixAl foil and LixSi/C, respectively; (g) XRD result of LixSn alloy foil; (h) capacity and cycle stability of LixSn foil and Sn foil in full-cell cycling, The blue symbols represent LixSn and the red ones represent Sn foil[5]
稳定金属锂粉SLMP(stabilized lithium metal powder)是由FMC公司生产的一款商业产品,其具有核壳结构,由97%的锂和3%碳酸锂包覆层组成[10]。该碳酸锂保护层均匀包覆在锂粉的表面,可阻止锂粉的不良副反应,使SLMP在干燥的环境中就可以使用,而不必在惰性气氛下[11]。SLMP具有高达3600 mA·h/g的比容量,将其用于负极补锂不仅可以提高锂离子电池的容量,且可以提高其首周库容效率和循环寿命[12],如图3所示。
Fig. 6
(a) schematic structure of three-electrode lithium-ion hybrid capacitor[37]; (b) schematic of a cell in pre-lithiation reaction with porous graphite[38]
Fig. 7
(a) structural formula and specific capacity of compounds corresponding to 4 “sacrificial salt” families; (b) initial voltage profile of LiN3 (1), Li2C4O4 (2), Li2C3O5 (3), Li2C4O6 (4), [COCON(Li)N(Li)]n(5) and Li2C2O4 (6)[40]
Fig. 10
(a) HRTEM images of Li2S/KB; (b) enlarged region corresponding to black square in (a);(c) initial voltage profile of core-shell Li2S/KB half cell[49]
Fig. 11
(a) initial voltage profiles of Li2C2O4 and Li2C2O4(LNMO) half cells; (b) initial voltage profiles of LiNi0.5Mn1.5O4 and LiNi0.5Mn1.5O4(Li2C2O4) half cells; (c) corresponding cycling performance[44]
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... [5]Roll-to-roll prelithiation method for preparation of LixSn, LixAl and LixSi/C anode electrodes:(a) illustration of roll-to-roll prelithiation method; (b) specific operation of roll-to-roll mechanical prelithiation method; (c) visual image of as-prepared LixSn foil (8 cm×16 cm), where dark layer is Li-Sn alloy and underlay with metallic luster is Sn; (d) cross-sectional SEM image of LixSn alloy foil, where top layer is LixSn and sublayer is pure Sn; (e and f) visual images of as-prepared LixAl foil and LixSi/C, respectively; (g) XRD result of LixSn alloy foil; (h) capacity and cycle stability of LixSn foil and Sn foil in full-cell cycling, The blue symbols represent LixSn and the red ones represent Sn foil[5]Fig. 1
... [37];(b) 多层多孔电极原位补锂电池[38](a) schematic structure of three-electrode lithium-ion hybrid capacitor[37]; (b) schematic of a cell in pre-lithiation reaction with porous graphite[38]Fig. 62.2 正极补锂技术
... [38](a) schematic structure of three-electrode lithium-ion hybrid capacitor[37]; (b) schematic of a cell in pre-lithiation reaction with porous graphite[38]Fig. 62.2 正极补锂技术
... [40](a) structural formula and specific capacity of compounds corresponding to 4 “sacrificial salt” families; (b) initial voltage profile of LiN3 (1), Li2C4O4 (2), Li2C3O5 (3), Li2C4O6 (4), [COCON(Li)N(Li)]n(5) and Li2C2O4 (6)[40]Fig. 7
... [44](a) initial voltage profiles of Li2C2O4 and Li2C2O4(LNMO) half cells; (b) initial voltage profiles of LiNi0.5Mn1.5O4 and LiNi0.5Mn1.5O4(Li2C2O4) half cells; (c) corresponding cycling performance[44]Fig. 112.3 小结
... [49](a) HRTEM images of Li2S/KB; (b) enlarged region corresponding to black square in (a);(c) initial voltage profile of core-shell Li2S/KB half cell[49]Fig. 102.2.2 三元含锂化合物