Nonflammable Trimethyl Phosphate Solvent-Containing Electrolytes for Lithium-Ion Batteries: I. Fundamental Properties

Wang, Xianming; Yasukawa, Eiki; Kasuya, Shigeaki

doi:10.1149/1.1397773

Cited by 372 publications

(312 citation statements)

References 23 publications

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“…1,[13][14][15][16]20 A solution to this co-intercalation problem was devised by Takeuchi et al That is, the compatibility of TMP with graphite was improved by introducing a salt composed of stronger Lewis acids than Li + , such as Ca 2+ . 16 Moreover, the charge-discharge efficiency in the case of TMP in graphite was improved by adding calcium bis(trifluoromethanesulfonyl) amide (Ca(TFSA) 2 ) to an electrolyte containing TMP.…”

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confidence: 99%

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Effect of Lewis Acids on Graphite-Electrode Properties in EC-Based Electrolyte Solutions with Organophosphorus Compounds

Tsubouchi

Suzuki

Nishimura

et al. 2018

J. Electrochem. Soc.

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Compatibility of self-extinguishing property and electrochemical stability of electrolyte solutions containing organophosphorus compounds as flame retardants has been required for practical application of electrolyte solutions to lithium-ion batteries. By adding a Lewis acid, Ca 2+ , Mg 2+ , or Na + , to ethylene carbonate (EC)-based electrolyte solutions containing 50 vol.% trimethylphosphate or dimethyl methylphosphonate, the electrolyte solutions are able to suppress the co-intercalation of the organophosphorus compounds with Li + into graphite. However, the coulombic efficiency in the first charge-discharge in a graphite/Li metal half-cell with an electrolyte solution depends on the species of the added Lewis acid and organophosphorus compound. The difference between the chemical-shift changes of the oxygen of the C=O bond in EC and the oxygen of the P=O bond in organophosphorus compounds in the oxygen-17 nuclear magnetic resonance ( 17 O NMR) spectra of the electrolyte solutions was investigated. The investigation revealed that the difference in the acidities of the Lewis acids, electron-donating abilities of the organophosphorus compounds, and solvated structures with a Lewis acid affect the electrochemical stability of self-extinguishing electrolyte solutions. Safety, specifically concerning flammability, is still an important concern with lithium-ion batteries, especially as they are now widely used in high-power and -energy applications such as electric-load leveling and electric-vehicle systems. Organophosphorus compounds, such as phosphate, 1-5 phosphonate, 6,7 and phosphazene, 8,9 are widely known as excellent flame retardants. These organophosphorus compounds are used either as co-solvents or additives in the conventional alkyl-carbonate-based electrolyte solution used in lithium-ion batteries. Trimethylphosphate (TMP) suppresses the flammability of electrolyte solutions because of its self-extinguishing property; that is, it can selectively scavenge the active hydrogen and oxygen radicals that contribute to the combustible chain reaction.1,10,11 However, TMP, which has a higher electron-donating ability than ethylene carbonate (EC), 12 tends to co-intercalate with Li + into the graphite negative electrode, resulting in continuous decomposition of the electrolyte solution and large, irreversible capacity loss during the initial chargedischarge of a lithium-ion battery. 1,[13][14][15][16]20 A solution to this co-intercalation problem was devised by Takeuchi et al. That is, the compatibility of TMP with graphite was improved by introducing a salt composed of stronger Lewis acids than Li + , such as Ca 2+ . 16 Moreover, the charge-discharge efficiency in the case of TMP in graphite was improved by adding calcium bis(trifluoromethanesulfonyl) amide (Ca(TFSA) 2 ) to an electrolyte containing TMP. This suppression of co-intercalation is derived from the solvation structure of Li + being altered by the stronger Lewis acid, namely, Ca 2+ . Fluorinated alkyl phosphates, such as tris(2,2,2-trifluoroethyl) pho...

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“…Organophosphorus compounds, such as phosphate, [1][2][3][4][5] phosphonate, 6,7 and phosphazene, 8,9 are widely known as excellent flame retardants. These organophosphorus compounds are used either as co-solvents or additives in the conventional alkyl-carbonate-based electrolyte solution used in lithium-ion batteries.…”

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confidence: 99%

Effect of Lewis Acids on Graphite-Electrode Properties in EC-Based Electrolyte Solutions with Organophosphorus Compounds

Tsubouchi

Suzuki

Nishimura

et al. 2018

J. Electrochem. Soc.

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“…Flame retardant (FR) additives aim to reduce this threat while maintaining good ionic conductivity and cycling characteristics. Most FRs act by chemical radical scavenging, which terminates the radical chain combustion reaction (Wang et al 2001). Ideally, the amount of FR should be kept below 20 vol.%, to minimize the deleterious effects on battery performance (Arai 2003); however, ignition under high pressure of oxygen or other kinds of abuse conditions is still possible with the highly flammable linear carbonate solvents in this range.…”

Section: Additives For Aprotic Liquid Electrolytesmentioning

confidence: 99%

Electrolytes for high-energy lithium batteries

et al. 2011

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From aqueous liquid electrolytes for lithiumair cells to ionic liquid electrolytes that permit continuous, high-rate cycling of secondary batteries comprising metallic lithium anodes, we show that many of the key impediments to progress in developing next-generation batteries with high specific energies can be overcome with cleaver designs of the electrolyte. When these designs are coupled with as cleverly engineered electrode configurations that control chemical interactions between the electrolyte and electrode or by simple additives-based schemes for manipulating physical contact between the electrolyte and electrode, we further show that rechargeable battery configurations can be facilely designed to achieve desirable safety, energy density and cycling performance.

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“…The searches focus on all aspects of these batteries, including improved anodes, [6][7][8] cathodes [9][10][11][12][13][14][15][16][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.…”

Section: Initial Remarksmentioning

confidence: 99%

“…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 cathode material of a secondary lithium ion battery is a host compound, where lithium ions can be inserted and extracted reversibly during the cycling process. The main requirements for cathode materials are: (i) the transition metal ion in the insertion compound cathode should have a large work function to maximize the cell voltage, (ii) the insertion compound should allow an insertion/extraction of a large amount of lithium to maximize the cell capacity, (iii) the lithium insertion/extraction process should be reversible with no or minimal changes in the host structure over the entire range of lithium insertion/ extraction, (iv) chemical stability for both redox forms of cathode couple, (v) the insertion compound should support good electronic and Li + conductivities to minimize cell polarizations and, (vi) the voltage profile should be relatively continuous, without large voltage steps that can complicate power managements in devices.…”

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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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Nonflammable Trimethyl Phosphate Solvent-Containing Electrolytes for Lithium-Ion Batteries: I. Fundamental Properties

Cited by 372 publications

References 23 publications

Effect of Lewis Acids on Graphite-Electrode Properties in EC-Based Electrolyte Solutions with Organophosphorus Compounds

Effect of Lewis Acids on Graphite-Electrode Properties in EC-Based Electrolyte Solutions with Organophosphorus Compounds

Electrolytes for high-energy lithium batteries

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

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