Low-temperature performance of LiFePO4/C cathode in a quaternary carbonate-based electrolyte

Liao, Xiao‐Zhen; Ma, Zhenqiang; Gong, Qiang; He, Yu‐Shi; Li, Pei; Zeng, Ling-Jie

doi:10.1016/j.elecom.2008.02.017

Cited by 184 publications

(59 citation statements)

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“…LFP batteries therefore combine a good cycling stability with excellent thermal stability and long lifespan. [1][2][3][4][5] The volume decreases only 6.8% 6 when all Li ( x = 1) is extracted and these small volumetric changes do not influence the structure of LiFePO 4 and FePO 4 . Favorably, it almost fully counterbalances the volumetric changes of the graphite electrode during Li (de)insertion.…”

mentioning

confidence: 99%

Modeling the SEI-Formation on Graphite Electrodes in LiFePO₄Batteries

Danilov

Zhang

et al. 2015

J. Electrochem. Soc.

107

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An advanced model is proposed, describing the capacity losses of C 6 /LiFePO 4 batteries under storage and cycling conditions. These capacity losses are attributed to the growth of a Solid Electrolyte Interface (SEI) at the surface of graphite particles in the negative electrode. The model assumes the existence of an inner and outer SEI layer. The rate determining step is considered to be electron tunneling through the inner SEI layer. The inner SEI layer grows much slower than the outer SEI layer. Another contribution to the degradation process is the exfoliation of SEI near the edges of graphite particles during discharging and the formation of new SEI induced by the volumetric changes during the subsequent charging. The model has been validated by storage and cycling experiments. The simulation results show that the capacity losses are dependent on the State-of-Charge (SoC), the storage time, cycle number and graphite particle size. The model can be used to predict both the calendar and cycling life of the Li-ion batteries. Li-ion batteries, based on the C 6 /LiFePO 4 chemistry, attracts nowadays much attention for application in, for example, electric vehicles due to the excellent cycling stability of the LiFePO 4 electrode. The main electrochemical storage reactions of this battery type can be represented byDuring charging electrons and Li + ions are extracted from the LiFePO 4 (0 ≤ x ≤ 1) electrode and flow into the graphite electrode. The reverse reactions take place during discharging. The structure of LiFePO 4 (LFP) is highly robust due to the strong bonding between the P and O atoms. LFP batteries therefore combine a good cycling stability with excellent thermal stability and long lifespan.1-5 The volume decreases only 6.8% 6 when all Li ( x = 1) is extracted and these small volumetric changes do not influence the structure of LiFePO 4 and FePO 4 . Favorably, it almost fully counterbalances the volumetric changes of the graphite electrode during Li (de)insertion.Due to these favorable properties, the capacity losses caused by the LFP cathode are generally assumed to be negligible. Furthermore, Broussely et al. showed that the capacity of the graphite electrode can be fully recovered even after more than 1 year storage under 'floating' conditions at 60• C, demonstrating that the stability of the carbon electrode is also excellent.7 However, capacity losses are still found in LFP batteries. It is generally accepted, that the formation of a Solid Electrolyte Interface (SEI) is one of the main reasons for the capacity losses of graphite-based Li-ion batteries, especially under moderate conditions during the initial stages of aging.The SEI plays a dual-role in the performance of Li-ion batteries. On the one hand, it protects the negative electrode from solvent cointercalation, preventing exfoliation of the graphene layers. On the other hand, it consumes cyclable lithium inside the battery, which is therefore no longer available for the energy storage process and hence * Electrochemical Society Active Member...

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mentioning

confidence: 99%

Modeling the SEI-Formation on Graphite Electrodes in LiFePO₄Batteries

Danilov

Zhang

et al. 2015

J. Electrochem. Soc.

107

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“…其中(001)晶面的衍射峰对锂离子的脱嵌十分敏感, 在整个充放电过程中变化明显 [31] , 因此本实验选择(001)衍射峰来原位监测相变过程 [32,33] . [37,38] . 另外, 低温下的电压平台不如室温下明显.…”

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In SituObservation and Mechanism Investigation of Lattice Breathing in Vanadium Oxide Cathode

Zhang¹,

Xiong²,

Pan³

et al. 2016

Acta Chim. Sinica

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As cathode materials in lithium-ion batteries, layered vanadium oxides have been extensively studied and used in many aspects varying from industrial production to our daily life, due to their excellent physical property and gorgeous lithium storage performance. During lithiation/delithiation, layered vanadium oxides such as V 2 O 5 xerogel (with a bilayer structure), undergoes "lattice breathing" which leads to the deactivation of electrode materials and fast capacity fading, which limits its large-scale application. In this work, VO x is used as the cathode material of lithium-ion batteries to study the "lattice breathing" phenomenon. The phase evolution has been observed and studied via in situ method. The X-ray diffraction (XRD) patterns show typical (001) diffraction peaks characteristic of vanadium oxide xerogel structure and also confirm the good crystallinity. This compound with crystal parameters of a＝4.56 Å, b＝14.87 Å, c＝12.38 Å, α＝117.26°, β＝96.02°, γ＝ 81.86°, forms a triclinic structure. Results of scanning electron microscope (SEM) and transmission electron microscope (TEM) further verify the layered structure of VO x . The thermo gravimetric analysis (TGA) at air and nitrogen atmosphere shows that the carbon content of the sample is about 2.4 wt% and the water content is about 2.1%. As lithium-ion battery cathode the initial discharge capacity of the compound is about 136 mA•h/g at a current density of 100 mA/g, with a capacity retention of 92.6% after 50 cycles. To study the lithium storage mechanism of VO x , electrochemical discharge/charge processes are further investigated by in situ XRD. It is found that the lattice plane diffraction displays three different stages linked during the insertion and deinsertion of lithium ions, indicating three solid solution reactions. During discharge process, the three diffraction changes show continuous shifts to higher diffraction angles, demonstrating three different continuous contraction processes with the insertion of lithium ions. Nevertheless, the evolution of the (001) peak is swift during the beginning and the end of discharge, in contrast to the slow deviation of the intermediate process. In the whole process, the diffraction pattern displays periodic changes, confirming the reversibility of the reaction process. The corresponding calculations of d 001 during the discharge/charge process prove the notable discontinuity between these three stages. In addition, cycling experiments conducted at the higher and the lower temperature indicate that the electrochemical performance of this compound is highly sensitive to temperature.

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“…A spray dry (SP) method has been widely used to prepare spherical LiFePO 4 /C cathode materials to enhance the electrochemical performance [15][16][17][18][19]. The low-and high-temperature performance and capacity fading mechanism of LiFePO 4 /C materials have recently been intensively explored [20][21][22][23][24]. Surface coating is an effective method of solving the problems of high-temperature metal dissolution and cycling deterioration.…”

Section: Introductionmentioning

confidence: 99%

Study of electrochemical performances of lithium titanium oxide–coated LiFePO4/C cathode composite at low and high temperatures

2016

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Low-temperature performance of LiFePO4/C cathode in a quaternary carbonate-based electrolyte

Cited by 184 publications

References 20 publications

Modeling the SEI-Formation on Graphite Electrodes in LiFePO₄Batteries

Modeling the SEI-Formation on Graphite Electrodes in LiFePO₄Batteries

In SituObservation and Mechanism Investigation of Lattice Breathing in Vanadium Oxide Cathode

Study of electrochemical performances of lithium titanium oxide–coated LiFePO4/C cathode composite at low and high temperatures

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Low-temperature performance of LiFePO4/C cathode in a quaternary carbonate-based electrolyte

Cited by 184 publications

References 20 publications

Modeling the SEI-Formation on Graphite Electrodes in LiFePO4Batteries

Modeling the SEI-Formation on Graphite Electrodes in LiFePO4Batteries

In SituObservation and Mechanism Investigation of Lattice Breathing in Vanadium Oxide Cathode

Study of electrochemical performances of lithium titanium oxide–coated LiFePO4/C cathode composite at low and high temperatures

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Modeling the SEI-Formation on Graphite Electrodes in LiFePO₄Batteries

Modeling the SEI-Formation on Graphite Electrodes in LiFePO₄Batteries