A Cell for In Situ X‐Ray Diffraction Based on Coin Cell Hardware and Bellcore Plastic Electrode Technology

Richard, Monique; Koetschau, I.; Dahn, J. R.

doi:10.1149/1.1837447

Cited by 87 publications

(68 citation statements)

References 4 publications

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“…However, there are experimental data published by other research groups that show two-phase coexistence in lithiumrich spinels. For example, Richard et al 7 have reported their in situ XRD studies with the observation of two-phase coexistence in the 0.60 > x > 0.27 range for Li x Mn 2 O 4 material, where the x value before charge was similar to that in the studies of Ref. 5 (x = 1.02 vs. x = 1.04).…”

mentioning

confidence: 54%

In Situ Synchrotron X-Ray Diffraction Studies of the Phase Transitions in Li[sub x]Mn[sub 2]O[sub 4] Cathode Materials

Yang

Sun

Lee

et al. 1999

Electrochem. Solid-State Lett.

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In situ X-ray diffraction studies of Li x Mn 2 O 4 spinel cathode materials during charge-discharge cycling were carried out using a synchrotron as the X-ray source. Lithium-rich (x = 1.03-1.06) spinel materials, obtained from two different sources, were studied. Three cubic phases with different lattice constants were observed during charge-discharge cycles in all of the samples when a sufficiently low charge-discharge rate (≤C/10) was used. There were two regions of two-phase coexistence, which indicates that both phase transitions are first order. The separation of the Bragg peaks representing these three phases varied from sample to sample and also depended on the charge-discharge rate. These results show that the deintercalation of lithium in lithium-rich spinel cathode materials proceeds through a series of phase transitions from a lithium-rich phase to a lithium-poor phase and finally to a λ-MnO 2 -like cubic phase, rather than through a continuous lattice constant contraction in a single phase.The Li x Mn 2 O 4 spinel is one of the most promising cathode materials for lithium rechargeable batteries because of its low cost and low toxicity. Recent studies have focused on the problem of capacity fading of this material during cycling, especially at elevated temperature. This fading has been attributed to two sources, the dissolution of Mn 2+ into the nonaqueous electrolytes 1 and the inhomogeneity of the spinel local structure. 2,3 Early ex situ X-ray diffraction studies of Li x Mn 2 O 4 were performed by Ohzuku et al. 4 They found that two cubic phases coexist for 0.60 > x > 0.27, and a single cubic phase is present for 1.0 > x >0.6. Xia and Yoshio 5 reported in their studies that the two-phase coexistence was suppressed in cathode materials which were prepared lithium rich (x = 1.04) or oxygen rich. They also claimed that the two-phase coexistence is one of the key factors for the capacity fading during cycling. By suppressing this phase transition, the capacity fading of the lithium-rich cathode materials was significantly improved at the expense of lower initial capacity. In their later X-ray diffraction (XRD) studies, 6 an in situ technique was used, and the same conclusion that there was a onephase structure for lithium-rich spinel was presented. This interesting work raised an important issue: the relationship between the structural change and the capacity fading of these spinel materials during cycling. However, there are experimental data published by other research groups that show two-phase coexistence in lithiumrich spinels. For example, Richard et al. 7 have reported their in situ XRD studies with the observation of two-phase coexistence in the 0.60 > x > 0.27 range for Li x Mn 2 O 4 material, where the x value before charge was similar to that in the studies of Ref. 5 (x = 1.02 vs. x = 1.04). The main difference between these two studies is the charge rate (C/40 in Ref. 7 vs. C/3 in Ref. 5). The first issue to address in this article is whether the two-phase coexistence region is being suppre...

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mentioning

confidence: 54%

In Situ Synchrotron X-Ray Diffraction Studies of the Phase Transitions in Li[sub x]Mn[sub 2]O[sub 4] Cathode Materials

Yang

Sun

Lee

et al. 1999

Electrochem. Solid-State Lett.

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“…In situ X-ray experiments were conducted using an in situ cell as reported in Ref. 9. For all in situ measurements the counting time was set to be 15 s for a step of 0.05Њ.…”

Section: Methodsmentioning

confidence: 99%

In Situ X-Ray Study of the Electrochemical Reaction of Li with ηʹ-Cu[sub 6]Sn[sub 5]

Larcher¹,

Beaulieu²,

MacNeil

et al. 2000

J. Electrochem. Soc.

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192

154

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Lithium-ion cells normally use graphite negative electrodes and lithium transition metal oxide positive electrodes. In order to increase the energy density and specific energy of such cells, new electrode materials must be found. Lithium alloys offer larger specific and volumetric capacities than graphite, and these have been the subject of recent research. In particular, Mao et al. have shown that intermetallic compounds like FeSn 2 1 and active/inactive nanocomposites like FeSn 2 /SnFe 3 C 2 function well as anodes although their cycle life is limited. The limited cycle life of such alloys is probably caused by relatively large volume changes associated with the reversible reaction of Li.In recent papers Kepler et al. and Thackeray et al. 3,4 have reported electrochemical data on Li/Cu 6 Sn 5 cells. It was found that Cu 6 Sn 5 reacts reversibly with lithium to deliver an initial discharge capacity of approximately 350 mAh/g. Based on structural similarity, it was proposed that this reaction could be described as an insertion of lithium in the Cu 6 Sn 5 structure to reversibly form Li 2.17 CuSn 0.83 (or Li 13 Cu 6 Sn 5 ) that has the same structure as Li 2 CuSn. In this paper we do not distinguish between Li 2.17 CuSn 0.83 and Li 2 CuSn. In Ref. 3 and 4, it is suspected that further reaction of Li with Li 2 CuSn could result in the formation of Li-Sn alloys and the simultaneous expulsion of Cu. Surprisingly, even when discharged to 0 V, this reaction does not occur under the conditions used in Ref. 3 and 4. It is also shown that better cycling life is achieved when the discharge cut-off voltage is raised to 200 mV from 0 V.In other work, Thackeray's group studied the material discharged to zero volts and the reaction below 400 mV was attributed to the extrusion of Cu and the formation of Li-Sn alloy. 5 The extraction of lithium from Li 2 CuSn was studied in Ref. 6. However the results in Ref. 3-6 are not self-consistent, nor are they of the highest possible quality. Thus, we decided to undertake a careful study of the reaction of lithium with Cu 6 Sn 5 .Here, we show that the reaction of Li with Cu 6 Sn 5 results first in the formation of Li 2 CuSn as an intermediate phase through a twophase reaction, and finally leads to a disordered Li 4.4 Sn alloy and nanoscopic grains of Cu. These reactions are found to be basically reversible although some aspects of the mechanism are different during discharge and charge. The changes we observe in the charge-discharge cycle life depending on the selected voltage window are easily explained by the structural changes involved in these two reactions. ExperimentalSamples of Ј-Cu 6 Sn 5 powder were prepared by heating stoichiometric mixtures of elemental Cu and Sn powders (purity >99.9%) under argon flow at 400ЊC for a 10 h period. 3 The heating rate was 1ЊC/min. To ensure good homogeneity and contact of the reactants, the Cu/Sn mixture was intensively ground in a mortar and pressed into a pellet at a pressure of 200 bar.The HT-Li 2 CuSn reference phase was prepared from powder...

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“…Moreover, beryllium is usually used as X-ray window. 15,17,21,22 Beryllium is not only toxic, but will also dissolve in a liquid electrolyte when raised above 3 V, and hence an extra layer of conductive material is used for preventing the direct contact between the electrolyte saturated cathode and the beryllium window. 17,21 This makes the cell structure more complex and less user friendly in operation.…”

Section: Introductionmentioning

confidence: 99%

An electrochemical cell for in operando studies of lithium/sodium batteries using a conventional x-ray powder diffractometer

Shen

Pedersen

Christensen

et al. 2014

Review of Scientific Instruments

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An electrochemical cell has been designed for powder X-ray diffraction studies of lithium ion batteries (LIB) and sodium ion batteries (SIB) in operando with high time resolution using a conventional powder X-ray diffractometer. The cell allows for studies of both anode and cathode electrode materials in reflection mode. The cell design closely mimics that of standard battery testing coin cells and allows obtaining powder X-ray diffraction patterns under representative electrochemical conditions. In addition, the cell uses graphite as the X-ray window instead of beryllium, and it is easy to operate and maintain. Test examples on lithium insertion/extraction in two spinel-type LIB electrode materials (Li4Ti5O12 anode and LiMn2O4 cathode) are presented as well as first results on sodium extraction from a layered SIB cathode material (Na0.84Fe0.56Mn0.44O2).

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A Cell for In Situ X‐Ray Diffraction Based on Coin Cell Hardware and Bellcore Plastic Electrode Technology

Cited by 87 publications

References 4 publications

In Situ Synchrotron X-Ray Diffraction Studies of the Phase Transitions in Li[sub x]Mn[sub 2]O[sub 4] Cathode Materials

In Situ Synchrotron X-Ray Diffraction Studies of the Phase Transitions in Li[sub x]Mn[sub 2]O[sub 4] Cathode Materials

In Situ X-Ray Study of the Electrochemical Reaction of Li with ηʹ-Cu[sub 6]Sn[sub 5]

An electrochemical cell for in operando studies of lithium/sodium batteries using a conventional x-ray powder diffractometer

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