Local-Probe Studies of Degradation of Composite LiNi[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2] Cathodes in High-Power Lithium-Ion Cells

Kostecki, Robert; McLarnon, Frank

doi:10.1149/1.1793771

Cited by 127 publications

(106 citation statements)

References 12 publications

(10 reference statements)

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“…The Raman spectra of individual cathode components recorded at different surface locations are shown in Figure 2C. The mapping and spectral analysis procedure was described in detail in [14]. Thousands of Raman spectra were deconvoluted, analyzed, and displayed as color-coded points on the composition image map.…”

Section: Resultsmentioning

confidence: 99%

“…In situ and ex situ application of non-invasive and non-destructive microscopies and spectroscopies, including Raman, fluorescence spectroscopy, SEM, and AFM to characterize physico-chemical properties of the electrode/electrolyte interface at nanometer resolution provide unique insight into the mechanism of specific chemical and electrochemical processes that may be responsible for the electrode and cell degradation. The extraordinary potential of Raman micro-spectroscopy was demonstrated by in situ acquisition of space-and time-resolved spectra of positive and carbon negative electrodes in Li-ion cells [4,9,11,12,13,14], single oxide or graphite particle in the composite electrode [10,15,16,17] or single graphite or LiMn 2 O 4 particle electrodes [16,19,20,21].…”

Section: Introductionmentioning

confidence: 99%

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Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

Kerlau

Marcinek

Srinivasan

et al. 2007

Electrochimica Acta

116

103

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Abstract13 C-carbon black substituted composite LiNi 0.8 Co 0.15 Al 0.05 O 2 cathodes were tested in model electrochemical cells to monitor qualitatively and quantitatively carbon additive(s) distribution changes within tested cells and establish possible links with other detrimental phenomena. Raman qualitative and semi-quantitative analysis of 13 C in the cell components was carried out to trace the possible carbon rearrangement/movement in the cell. Small amounts of cathode carbon additives were found trapped in the separator, at the surface of Li-foil anode, in the electrolyte. The structure of the carried away carbon particles was highly amorphous unlike the original 12 C graphite and 13 C carbon black additives. The role of the carbon additive, the mechanism of carbon retreat in composite cathodes and its correlation with the increase of the cathode interfacial charge-transfer impedance, which accounts for the observed cell power and capacity loss is investigated and discussed. [1,5]. Possible causes of the increase in cathode impedance and irreversible charge/discharge capacity loss include the formation of an electronic and/or ionic barrier at the cathode surface [6,7,8]. This is consistent with our earlier studies [9,10], in which we demonstrated that the non-uniform kinetic behavior of the individual oxide particles was attributed to the degradation of the electronically conducting matrix in the composite cathode upon testing. Carbon additive rearrangement in portions of the tested LiNi 0.8 Co 0.15 Al 0.05 O 2 cathodes and/or thin film formation on the surfaces of carbon and oxide particles is closely linked with the observed isolation of oxide active material.Because the composite cathodes typically consists of an active material, two types of carbon additive, and a binder, suitable instrumental techniques must be applied to obtain lateral resolution comparable to the size and morphology of electrode surface features. In situ and ex situ application of non-invasive and non-destructive microscopies and spectroscopies, including Raman, fluorescence spectroscopy, SEM, and AFM to characterize physico-chemical properties of the electrode/electrolyte interface at nanometer resolution provide unique insight into the mechanism of specific chemical

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

Kerlau

Marcinek

Srinivasan

et al. 2007

Electrochimica Acta

116

103

View full text Add to dashboard Cite

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“…The isolated particles will remain uncharged and therefore the connected active material will be charged (and discharged) at a higher effective rate. Raman spectroscopy and current sensing atomic force microscopy (AFM) diagnostic studies of LiNi 0.8 Co 0.15 Al 0.05 O 2 composite cathodes harvested from high-power Li-ion cells showed that the oxide particle SOC on the cathode surface varied strongly with location and that intergranular electronic contact within agglomerates deteriorates during cell cycling [16,17]. We compared the paramagnetic shift of fresh (0% PF) and cycled (9% and 23% PF) cathodes in function of the SOC of the electrodes, as illustrated in Fig.…”

Section: Resultsmentioning

confidence: 99%

Investigation of particle isolation in Li-ion battery electrodes using 7Li NMR spectroscopy

Kerlau

Reimer

Cairns

2005

Electrochemistry Communications

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“…The cells consisted of a positive cathode and a lithium metal anode separated by a porous polypropylene film. The electrolyte used was 1 M LiPF 6 The morphologies of the prepared powders were observed with Scanning Electron Microscopy (SEM, JSM-6340F, JEOL). To obtain local compositions of the FCG, cross sections of the particles were prepared by embedding the particles in an epoxy and grinding them flat.…”

Section: Methodsmentioning

confidence: 99%

Improved Performances of Li[Ni_0.65Co_0.08Mn_0.27]O₂Cathode Material with Full Concentration Gradient for Li-Ion Batteries

Yoon

Park

Lim

et al. 2014

J. Electrochem. Soc.

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Full concentration gradient (FCG) cathode material having nickel-rich core Li [Ni 0.89 Rechargeable lithium-ion batteries have received great attention as power sources for portable electronic device, plug-in hybrid vehicles (PHEVs), and electric vehicles (EVs) because of their high energy density, long cycle life, and excellent rate capability. However, commercialization of rechargeable lithium-ion battery system for the automobile industry requires further improvements in energy density and safety. In order to meet these requirements, numerous researches have been in progress for finding new electrode materials, especially cathode materials.1-4 So far, most of the studies have focused on the layered cathode materials, Li[Ni 1−y−z Co y Mn z ]O 2 , which combine the rate performance of LiCoO 2 , the high capacity of LiNiO 2 , and the structural stability imparted by the presence of Mn 4+ . 5 Particularly, the Ni-rich layered composite oxides Li[Ni 1−y−z Co y Mn z ]O 2 (1-y-z ≥ 0.8), are considered one of the most promising cathode materials because they offer higher capacity than currently commercialized cathode materials. 6,7 However, the Ni-rich materials have poor thermal stability due to the oxygen release at the charged state, which can lead to severe thermal runaway and possible explosion. [8][9][10] Moreover, the unstable Ni 4+ ions can be easily reduced to inactive NiO, resulting in increase of the interfacial impedance, and thus poor cycle life. 11,12To overcome these problems of the Ni-rich Li[Ni 1−y−z Co y Mn z ]O 2 layered cathode materials, we have developed a functional lithium nickel-cobalt-manganese oxide cathode material which have coreshell structure or core-shell with concentration gradient. These cathodes are composed of a Mn-rich outer surface providing the outstanding safety and a Ni-rich core delivering a high capacity. These cathodes show high capacity and good cycle life at high voltage cycling, and improved safety characteristics.3,13,14 Recently, we reported a highenergy cathode material with a full concentration gradient (FCG) of Ni, Co, and Mn ions consisting of rod-shaped primary particles grown in radial directions with a crystallographic texture, which improved the rate capability and safety characteristics. 15 Based on the proposed material design concept, we can design various cathode materials with different gradient compositions.In this study, we report newly designed FCG Li [Ni 0.65 ExperimentalThe FCG precursors were synthesized through the co-precipitation method.15 The Ni-poor aqueous solution (Ni:Co:Mn = 0.58:0.10:0.32 in molar ratio) from tank 2was slowly pumped into a Ni-rich aqueous solution (Ni:Mn=0.96:0.04 in molar ratio) in tank 1. The homogeneous mixture was then fed into a continuously stirred tank reactor (CSTR). At the same time, a 4.0 mol dm −3 solution of NaOH (aq.) and the desired amount of NH 4 OH solution (aq.) (chelating agent) under N 2 atmosphere were also separately pumped into the reactor. The molar ratio of ammonium hydroxide to transition metal...

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Local-Probe Studies of Degradation of Composite LiNi[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2] Cathodes in High-Power Lithium-Ion Cells

Cited by 127 publications

References 12 publications

Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

Investigation of particle isolation in Li-ion battery electrodes using 7Li NMR spectroscopy

Improved Performances of Li[Ni_0.65Co_0.08Mn_0.27]O₂Cathode Material with Full Concentration Gradient for Li-Ion Batteries

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Local-Probe Studies of Degradation of Composite LiNi[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2] Cathodes in High-Power Lithium-Ion Cells

Cited by 127 publications

References 12 publications

Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

Investigation of particle isolation in Li-ion battery electrodes using 7Li NMR spectroscopy

Improved Performances of Li[Ni0.65Co0.08Mn0.27]O2Cathode Material with Full Concentration Gradient for Li-Ion Batteries

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Product

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Improved Performances of Li[Ni_0.65Co_0.08Mn_0.27]O₂Cathode Material with Full Concentration Gradient for Li-Ion Batteries