Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells

Gummow, R. J.; Kock, A. De; Thackeray, M. M.

doi:10.1016/0167-2738(94)90450-2

Cited by 1,414 publications

(966 citation statements)

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“…Gummow et al [9] found that the capacity fading of spinel is due to the dissolution of Mn into the electrolyte solution. Xia et al [14] attributed the capacity fade of spinel-based Li-ion battery to transformation of unstable two-phase spinel to a more stable one-phase structure via loss of MnO.…”

Section: Half-cell Studiesmentioning

confidence: 99%

“…Thackeray and co-workers [9] was the first to mention dissolution of Mn to be one of the Journal of Power Sources 111 (2002) [210][211][212][213][214][215][216][217][218][219][220] reason for capacity fade with cycling in case of spinel-based Li-ion cells. Tarascon et al [10] detected the presence of Mn on the surface of negative electrode by Rutherford backscattering spectroscopy (RBS).…”

Section: Introductionmentioning

confidence: 99%

“…This capacity fade is caused by various mechanisms, which depend on the electrode materials and also on the protocol adopted to charge the cell. Capacity fade in Li-ion cells can be attributed to unwanted side reactions that occur during overcharge or discharge, which causes electrolyte decomposition, passive film formation, active material dissolution and other phenomena [1][2][3][4][5][6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

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Performance study of commercial LiCoO2 and spinel-based Li-ion cells

Ramadass

Haran

White

et al. 2002

Journal of Power Sources

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Section: Half-cell Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Performance study of commercial LiCoO2 and spinel-based Li-ion cells

Ramadass

Haran

White

et al. 2002

Journal of Power Sources

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“…One more reason attributed to the poor cycle life of Li x Mn 2 O 4 in the 3V plateau is the asymmetry of expansion and compression processes observed in the Li x Mn 2 O 4 lattice during cycling, due to the Jahn-Teller effect. [130][131][132][133] Traditionally, spinels are produced by annealing lithium compounds (LiOH, Li 2 CO 3 , Li 2 NO 3 , LiI) with manganese oxides, acetates or hydroxides. This annealing process, done in air at high temperature, affects both morphology and structural characteristics of the target product.…”

Section: Manganese Oxidesmentioning

confidence: 99%

Cathodes for lithium ion batteries: the benefits of using nanostructured materials

Camilo¹,

Torresi²

2006

J. Braz. Chem. Soc.

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As celas de íon lítio disponíveis comercialmente, as quais são as mais avançadas entre as baterias recarregáveis disponíveis até agora, empregam óxidos de metais de transição microcristalinos como catodos, os quais funcionam como matrizes de inserção de lítio. Em busca por uma melhor performance eletroquímica, o uso de nanomateriais no lugar dos materiais convencionais tem emergido como excelente alternativa. Nesta revisão nós apresentaremos uma breve introdução sobre as motivações de usar materiais nanoestruturados como catodos em baterias de íon-lítio. Para ilustrar tais vantagens apresentamos exemplos de pesquisas relacionadas com a preparação e dados eletroquímicos dos mais usados catodos em nanoescala, tais como LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiV 2 O 5 e LiFePO 4 .Commercially available lithium ion cells, which are the most advanced among rechargeable batteries available so far, employ microcrystalline transition metal oxides as cathodes, which function as Li insertion hosts. In search for better electrochemical performance the use of nanomaterials in place of these conventional ones has emerged as excellent alternative. In this review we present a brief introduction about the motivations to use nanostructured materials as cathodes in lithium ion batteries. To illustrate such advantages we present some examples of research directed toward preparations and electrochemical data of the most used cathodes in nanoscale, such as LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiV 2 O 5 e LiFePO 4 .Keywords: nanotechnology, lithium-ion battery, cathode, nanoparticles Initial RemarksSince Sony introduced its 18650 cell in 1990, 1 Li-ion batteries with excellent electrochemical performance have been manufactured and occupied a prime position in the market place 2 to power portable and non-portable devices. [3][4][5] The reason for this relevance is that compared to traditional rechargeable batteries such as, lead acid and Ni-Cd, the lithium-ion battery shows several advantages, such as lighter in weight, smaller in dimension and higher energy density. 1 Moreover, although capacity values may be similar to other rechargeable systems, voltages are approximately three times higher, affording higher energy. 1 In general, the commercial lithium-ion batteries use graphite-lithium composite, Li x C 6 , as anode, lithium cobalt oxide, LiCoO 2 , as cathode and a lithium-ion conducting electrolyte. When the cell is charged, lithium is extracted from the cathode and inserted at the anode. On discharge, the lithium ions are released by the anode and taken up again by the cathode (Figure 1).Owing to the importance of lithium ion batteries, these cells are still object of intense research to enhance their properties and characteristics. The searches focus on all aspects of these batteries, including improved anodes, 6-8 cathodes 9-17 and electrolytes. [18][19][20][21][22] However, most of these efforts are concentrated in new cathode materials, since the most used cathode material (LiCoO 2 ) is expensive and is somewhat toxic.The active catho...

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“…1,2 However, this material has been shown to exhibit severe capacity fading during cycling, especially in the 3 V range, due to the cooperative Jahn-Teller distortion. 1,[3][4][5][6] Many efforts have been made to resolve this capacity fading problem, e.g., preparing Li[Mn 2 ]O 4 powder via solution-based methods such as sol-gel and coprecipitation, [7][8][9][10][11][12][13][14][15] replacing Mn with other metal elements like Li, Co, Ni, or Mg, 2,5,[16][17][18][19][20] and increasing the oxygen content to make Li 2 Mn 4 O 9 . 21 Some of these efforts were successful in improving the 4 V cycle life, but only a few papers have reported a significant improvement of the 3 V cycle life of Li[Mn 2 ]O 4 .…”

mentioning

confidence: 99%

Li[Li[sub y]Mn[sub 2−y]]O[sub 4] Spinel Cathode Material Prepared by a Solution Method

Goodenough

1999

Electrochem. Solid-State Lett.

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Li[Li y Mn 2-y ]O 4 (y = 0.03, 0.07, 0.14) spinel powders were prepared from aqueous solutions of LiOH·H 2 O and Mn(CH 3 COO) 2 ·4H 2 O, which is a simpler and cheaper method than any other solution-based synthesis. The spinels thus prepared exhibited excellent capacity retention in the voltage range of 2.4-3.4 V in spite of the cooperative Jahn-Teller distortion. The cyclability in the 4 V range (3.3-4.3 V) was improved as the lithium content on the octahedral site increased while the reversible capacity was sacrificed. Cycling over the whole 2.4-4.3 V range indicates that charging in the 4 V range introduces an irreversible change that causes capacity fading in the 3 V range, but not in the 4 V range. © 2000 The Electrochemical Society. S1099-0062(00)06-096-X. All rights reserved. Lithium manganese oxide spinel is considered a promising cathode material for lithium rechargeable batteries due to its low cost and environmental harmlessness. 1,2 However, this material has been shown to exhibit severe capacity fading during cycling, especially in the 3 V range, due to the cooperative Jahn-Teller distortion. O under vigorous stirring and sonication. The solution was then heated in a beaker on a hot plate to dryness under continuous stirring. The dried powders were then ground and calcined at 500°C for 2 days in air. Phase purity was verified from powder X-ray diffraction (XRD) with a Philips APD 3520 diffractometer; the lattice constants were determined from the XRD data by iterative least-square refinements against an internal silicon standard. The morphology of the synthesized powder was observed with SEM (Hitachi S-4500). The cationic compositions were analyzed with an atomic absorption spectrometer (AAS, Perkin-Elmer 1100).Electrochemical characterization of the cathode materials was carried out with coin-type cells. Spinel powders were mixed with acetylene black and polytetrafluoroethylene (PTFE) in the weight ratio of 70:25:5. The cathode mixtures were rolled into thin sheets and cut into pellets that were typically 20-30 mg. The electrolyte was 1 M LiClO 4 in a 1:1 mixture of propylene carbonate (PC) and dimethoxyethane (DME). A lithium foil was used as anode. The coin cells were fabricated in an Ar-filled glove box. The cells thus fabricated were cycled galvanostatically in the voltage range of 2. 4-3.4, 3.3-4.3, and 2.4-4.3 V at a current density of 0.5 mA/cm 2 at room temperature with an Arbin battery tester system (ABTS).Results and Discussion The powder XRD patterns of the samples Li[Li y Mn 2-y ]O 4 (y = 0.03, 0.07, 0.14) are shown in Fig. 1. All of the samples were identified as a single-phase spinel with a space group Fd3 Figures 2a-c show the particle morphology observed with SEM. As lithium content increases, the average particle size decreases. We emphasize that these single-phase samples were obtained by a simple, inexpensive procedure.The discharge curves of the Li/Li[Li y Mn 2-y ]O 4 cells in the voltage range of 2.4-3.4 V are shown in Fig. 3 with the corresponding discharge capacities as a ...

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Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells

Cited by 1,414 publications

References 12 publications

Performance study of commercial LiCoO2 and spinel-based Li-ion cells

Performance study of commercial LiCoO2 and spinel-based Li-ion cells

Cathodes for lithium ion batteries: the benefits of using nanostructured materials

Li[Li[sub y]Mn[sub 2−y]]O[sub 4] Spinel Cathode Material Prepared by a Solution Method

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