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1.
Langmuir ; 33(37): 9398-9406, 2017 09 19.
Artigo em Inglês | MEDLINE | ID: mdl-28636826

RESUMO

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety, stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteries with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl2. Hence, ethereal solutions of Mg(TFSI)2 salt with MgCl2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm-2 and an areal capacity of ∼0.4 mAh cm-2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI- anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.

2.
Acc Chem Res ; 48(11): 2813-21, 2015 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-26451674

RESUMO

The commercial introduction of the lithium-ion (Li-ion) battery nearly 25 years ago marked a technological turning point. Portable electronics, dependent on energy storage devices, have permeated our world and profoundly affected our daily lives in a way that cannot be understated. Now, at a time when societies and governments alike are acutely aware of the need for advanced energy solutions, the Li-ion battery may again change the way we do business. With roughly two-thirds of daily oil consumption in the United States allotted for transportation, the possibility of efficient and affordable electric vehicles suggests a way to substantially alleviate the Country's dependence on oil and mitigate the rise of greenhouse gases. Although commercialized Li-ion batteries do not currently meet the stringent demands of a would-be, economically competitive, electrified vehicle fleet, significant efforts are being focused on promising new materials for the next generation of Li-ion batteries. The leading class of materials most suitable for the challenge is the Li- and manganese-rich class of oxides. Denoted as LMR-NMC (Li-manganese-rich, nickel, manganese, cobalt), these materials could significantly improve energy densities, cost, and safety, relative to state-of-the-art Ni- and Co-rich Li-ion cells, if successfully developed.1 The success or failure of such a development relies heavily on understanding two defining characteristics of LMR-NMC cathodes. The first is a mechanism whereby the average voltage of cells continuously decreases with each successive charge and discharge cycle. This phenomenon, known as voltage fade, decreases the energy output of cells to unacceptable levels too early in cycling. The second characteristic is a pronounced hysteresis, or voltage difference, between charge and discharge cycles. The hysteresis represents not only an energy inefficiency (i.e., energy in vs energy out) but may also complicate the state of charge/depth of discharge management of larger systems, especially when accompanied by voltage fade. In 2012, the United States Department of Energy's Office of Vehicle Technologies, well aware of the inherent potential of LMR-NMC materials for improving the energy density of automotive energy storage systems, tasked a team of scientists across the National Laboratory Complex to investigate the phenomenon of voltage fade. Unique studies using synchrotron X-ray absorption (XAS) and high-resolution diffraction (HR-XRD) were coupled with nuclear magnetic resonance spectroscopy (NMR), neutron diffraction, high-resolution transmission electron microscopy (HR-TEM), first-principles calculations, molecular dynamics simulations, and detailed electrochemical analyses. These studies demonstrated for the first time the atomic-scale, structure-property relationships that exist between nanoscale inhomogeneities and defects, and the macroscale, electrochemical performance of these layered oxides. These inhomogeneities and defects have been directly correlated with voltage fade and hysteresis, and a model describing these mechanisms has been proposed. This Account gives a brief summary of the findings of this recently concluded, approximately three-year investigation. The interested reader is directed to the extensive body of work cited in the given references for a more comprehensive review of the subject.

3.
Med J Aust ; 204(2): 73, 2016 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-26821106

RESUMO

OBJECTIVE: To implement a statewide program for the early recognition and treatment of sepsis in New South Wales, Australia. SETTING: Ninety-seven emergency departments in NSW hospitals. INTERVENTION: A quality improvement program (SEPSIS KILLS) that promoted intervention within 60 minutes of recognition, including taking of blood cultures, measuring serum lactate levels, administration of intravenous antibiotics, and fluid resuscitation. MAIN OUTCOME MEASURES: Time to antibiotics and fluid resuscitation; mortality rates and length of stay. RESULTS: Data for 13 567 patients were entered into the database. The proportion of patients receiving intravenous antibiotics within 60 minutes of triage increased from 29.3% in 2009-2011 to 52.2% in 2013. The percentage for whom a second litre of fluid was started within 60 minutes rose from 10.6% to 27.5% (each P < 0.001). The proportion of patients classed as Australasian Triage Scale (ATS) 1 increased from 2.3% in 2009-2011 to 4.2% in 2013, and the proportion classed as ATS 2 rose from 40.7% in 2009-2011 to 60.7% in 2013 (P < 0.001). There was a linear decrease in mortality from 19.3% in 2009-2011 to 14.1% in 2013; there was also a significant decline in time in intensive care and total length of stay (each P < 0.0001). The mortality rate for patients with severe sepsis (serum lactate ≥ 4 mmol/L or systolic blood pressure [SBP] < 90 mmHg) was 19.7%. The mortality rates for patients with severe sepsis admitted to intensive care and for those admitted to a ward did not change significantly over time. The proportion of patients with uncomplicated sepsis (SBP ≥ 90 mmHg, serum lactate < 4 mmol/L) transferred to a ward increased, and the mortality rate after transfer increased from 3.2% in 2009-2011 to 6.2% in 2013 (P < 0.05). The survival benefit was greatest for patients with evidence of haemodynamic instability (SBP < 90 mmHg) but normal lactate levels (P = 0.03). CONCLUSIONS: The SEPSIS KILLS program has improved the process of care for patients with sepsis in NSW hospitals. The program has focused attention on sepsis management in the wards.


Assuntos
Antibacterianos/uso terapêutico , Bacteriemia/diagnóstico , Bacteriemia/terapia , Sangue/microbiologia , Ácido Láctico/sangue , Idoso , Bacteriemia/mortalidade , Bacteriemia/prevenção & controle , Biomarcadores/sangue , Diagnóstico Precoce , Serviço Hospitalar de Emergência , Hidratação , Guias como Assunto , Humanos , Incidência , Tempo de Internação/estatística & dados numéricos , Pessoa de Meia-Idade , New South Wales/epidemiologia , Estudos Prospectivos , Estudos Retrospectivos , Fatores de Risco , Taxa de Sobrevida , Fatores de Tempo
4.
J Am Chem Soc ; 137(9): 3411-20, 2015 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-25668289

RESUMO

In this work we uncover a novel effect between concentration dependent ion pair formation and anion stability at reducing potentials, e.g., at the metal anode. Through comprehensive calculations using both first-principles as well as well-benchmarked classical molecular dynamics over a matrix of electrolytes, covering solvents and salt anions with a broad range in chemistry, we elucidate systematic correlations between molecular level interactions and composite electrolyte properties, such as electrochemical stability, solvation structure, and dynamics. We find that Mg electrolytes are highly prone to ion pair formation, even at modest concentrations, for a wide range of solvents with different dielectric constants, which have implications for dynamics as well as charge transfer. Specifically, we observe that, at Mg metal potentials, the ion pair undergoes partial reduction at the Mg cation center (Mg(2+) → Mg(+)), which competes with the charge transfer mechanism and can activate the anion to render it susceptible to decomposition. Specifically, TFSI(-) exhibits a significant bond weakening while paired with the transient, partially reduced Mg(+). In contrast, BH4(-) and BF4(-) are shown to be chemically stable in a reduced ion pair configuration. Furthermore, we observe that higher order glymes as well as DMSO improve the solubility of Mg salts, but only the longer glyme chains reduce the dynamics of the ions in solution. This information provides critical design metrics for future electrolytes as it elucidates a close connection between bulk solvation and cathodic stability as well as the dynamics of the salt.

5.
Inorg Chem ; 52(7): 3969-75, 2013 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-23477474

RESUMO

The structures of a series of tetracoordinate beryllium(II) complexes with ligands derived from tertiary-substituted amines have been computationally modeled and their (9)Be magnetic shielding values determined using the gauge-including atomic orbital (GIAO) method at the 6-311++g(2d,p) level. A good correlation was observed between calculated (9)Be NMR chemical shifts when compared to experimental values in polar protic solvents, less so for the values recorded in polar aprotic solvents. A number of alternative complex structures were modeled, resulting in an improvement in experimental versus computational (9)Be NMR chemical shifts, suggesting that in some cases full encapsulation on the beryllium atom was not occurring. Several of the synthesized complexes gave rise to unexpected fluorescence, and inspection of the calculated molecular orbital diagrams associated with the electronic transitions suggested that the rigidity imparted by the locking of certain conformations upon Be(II) coordination allowed delocalization across adjacent aligned aromatic rings bridged by Be(II).

6.
BMC Health Serv Res ; 13: 380, 2013 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-24088360

RESUMO

BACKGROUND: In the intensive care unit (ICU), checklists can be used to support the delivery of quality and consistent clinical care. While studies have reported important benefits for clinical checklists in this context, lack of formal validity testing in the literature prompted the study aim; to develop relevant 'process-of-care' checklist statements, using rigorously applied and reported methods that were clear, concise and reflective of the current evidence base. These statements will be sufficiently instructive for use by physicians during ICU clinical rounds. METHODS: A dual-method approach was utilized; semi-structured interviews with local clinicians; and rounds of surveys to an expert Delphi panel. The interviews helped determine checklist item inclusion/exclusion prior to the first round Delphi survey. The panel for the modified-Delphi technique consisted of local intensivists and a state-wide ICU quality committee. Minimum standards for consensus agreement were set prior to the distribution of questionnaires, and rounds of surveys continued until consensus was achieved. RESULTS: A number of important issues such as overlap with other initiatives were identified in interviews with clinicians and integrated into the Delphi questionnaire, but no additional checklist items were suggested, demonstrating adequate checklist coverage sourced from the literature. These items were verified by local clinicians as being relevant to ICU and important elements of care that required checking during ward rounds. Two rounds of Delphi surveys were required to reach consensus on nine checklist statements: nutrition, pain management, sedation, deep vein thrombosis and stress ulcer prevention, head-of-bed elevation, blood glucose levels, readiness to extubate, and medications. CONCLUSIONS: Statements were developed as the most clear, concise, evidence-informed and instructive statements for use during clinical rounds in an ICU. Initial evidence in support of the checklist's construct validity was established prior to further prospective evaluation in the same ICU.


Assuntos
Lista de Checagem/métodos , Unidades de Terapia Intensiva/organização & administração , Lista de Checagem/normas , Cuidados Críticos/métodos , Cuidados Críticos/normas , Técnica Delphi , Humanos , Unidades de Terapia Intensiva/normas , Entrevistas como Assunto , Reprodutibilidade dos Testes , Inquéritos e Questionários
7.
ACS Appl Mater Interfaces ; 15(41): 48085-48095, 2023 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-37787440

RESUMO

Increasing the energy density of lithium-ion batteries, and thereby reducing costs, is a major target for industry and academic research. One of the best opportunities is to replace the traditional graphite anode with a high-capacity anode material, such as silicon. However, Si-based lithium-ion batteries have been widely reported to suffer from a limited calendar life for automobile applications. Heretofore, there lacks a fundamental understanding of calendar aging for rationally developing mitigation strategies. Both open-circuit voltage and voltage-hold aging protocols were utilized to characterize the aging behavior of Si-based cells. Particularly, a high-precision leakage current measurement was applied to quantitatively measure the rate of parasitic reactions at the electrode/electrolyte interface. The rate of parasitic reactions at the Si anode was found 5 times and 15 times faster than those of LiNi0.8Mn0.1Co0.1O2 and LiFePO4 cathodes, respectively. The imbalanced charge loss from parasitic reactions plays a critical role in exacerbating performance deterioration. In addition, a linear relationship between capacity loss and charge consumption from parasitic reactions provides fundamental support to assess calendar life through voltage-hold tests. These new findings imply that longer calendar life can be achieved by suppressing parasitic reactions at the Si anode to balance charge consumption during calendar aging.

8.
Crit Care Med ; 40(2): 388-93, 2012 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-22020239

RESUMO

OBJECTIVE: Identify the longest period a central line remains free from central line-associated bloodstream infection during an 18-month insertion-bundle project. DESIGN: Prospective cohort. SETTING: New South Wales adult intensive care units at university teaching hospitals between July 2007 and December 2008. PATIENTS: Intensive care unit adult patients whose central line was inserted in the intensive care unit. INTERVENTION: Compliance with the insertion bundle for central lines during the first 12-month roll-out period and the last 6 months. MAIN OUTCOMES: The cumulative line days that remained close to infection-free before the lowest probability of central line-associated bloodstream infection, 1 in 100 chances, was identified using conditional probability modeling. An adjusted central line-associated bloodstream infection rate was calculated for these cumulated line days and thereafter where the probability for infection increased with additional dwell time. RESULTS: The lowest probability identified for central line-associated bloodstream infection was 1 in 100 chances regardless of the phase of the project or central line type. During the first 12 months of the project, the close to infection-free period finished by the end of day 7 giving an adjusted central line-associated bloodstream infection rate of 1.8 (95% confidence interval 0.9-3.3)/1000 line days. By the last 6 months of the project the close to infection-free period was extended by 2 additional line days to the end of day 9, giving an adjusted central line-associated bloodstream infection rate of 0.9 (95% confidence interval 0.5-1.5)/1,000 line days. For dialysis and unspecified central line types, the close to infection-free period was extended by 5 additional line days, from day 2 with a rate of 4.3 (95% confidence interval 0.9-12.5)/1,000 line days to day 7, giving a rate of 0.6 (95% confidence interval 0.2-2.4)/1,000 line days. CONCLUSION: The success of the insertion bundle was identified by improved analysis that identified that the safest dwell time was extended to the first 9 days for centrally inserted lines and up to day 7 for dialysis, peripherally inserted central catheters, and unspecified central line types. Given that three quarters of intensive care unit patients have their central line removed by day 7, zero risk for central line-associated bloodstream infection should be achievable in the majority of patients where clinicians comply with the clinician and patient insertion bundles.


Assuntos
Bacteriemia/prevenção & controle , Patógenos Transmitidos pelo Sangue/isolamento & purificação , Cateterismo Venoso Central/efeitos adversos , Infecção Hospitalar/prevenção & controle , Unidades de Terapia Intensiva , Adulto , Austrália , Bacteriemia/etiologia , Cateterismo Venoso Central/normas , Cateteres de Demora/efeitos adversos , Estudos de Coortes , Cuidados Críticos/normas , Hospitais Universitários , Humanos , Controle de Infecções , Masculino , Segurança do Paciente , Estudos Prospectivos , Medição de Risco , Gestão de Riscos , Fatores de Tempo , Gestão da Qualidade Total
9.
Inorg Chem ; 51(5): 2728-30, 2012 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-22339585

RESUMO

The promotion for hydrogen release from ammonia-borane (AB) was observed in the presence of ZIF-8. Even at concentrations of ZIF-8 as low as 0.25 mol %, a reduction of the onset temperature for dehydrogenation accompanies an increase in both the rate and amount of hydrogen released from AB.

10.
J Am Chem Soc ; 133(51): 20735-7, 2011 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-22126391

RESUMO

The synthesis of pure δ-MoN with desired superconducting properties usually requires extreme conditions, such as high temperature and high pressure, which hinders its fundamental studies and applications. Herein, by using a chemical solution method, epitaxial δ-MoN thin films have been grown on c-cut Al(2)O(3) substrates at a temperature lower than 900 °C and an ambient pressure. The films are phase pure and show a T(c) of 13.0 K with a sharp transition. In addition, the films show a high critical field and excellent current carrying capabilities, which further prove the superior quality of these chemically prepared epitaxial thin films.

11.
Med J Aust ; 194(11): 583-7, 2011 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-21644871

RESUMO

OBJECTIVE: To reduce the rate of central line-associated bacteraemia (CLAB). DESIGN: A collaborative quality improvement project in intensive care units (ICUs) to promote aseptic insertion of central venous lines (CVLs). A checklist was used to record compliance with all aspects of aseptic CVL insertion, with maximal sterile barrier precautions for clinicians ("clinician bundle") and patients ("patient bundle"). CLAB was identified and reported using a standard surveillance definition. PARTICIPANTS AND SETTING: Patients and clinicians in 37 ICUs in New South Wales, July 2007-December 2008. MAIN OUTCOME MEASURES: Compliance with aseptic CVL insertion; rates of CLAB. RESULTS: 10 890 CVL checklists were reviewed for compliance with the clinician and patient bundles: compliance with aseptic CVL insertion improved significantly (P < 0.001). The CLAB rate dropped from 3.0 to 1.2 per 1000 line-days (P < 0.001). Regardless of CVL type, the relative risk (RR) of CLAB in patients with CVLs inserted by clinicians not compliant with the clinician bundle was 1.62 times greater (95% CI, 1.1-2.4; P = 0.018) than the RR with CVLs inserted by clinicians compliant with both bundles. Compliance with both the bundles was associated with a 50% reduction in risk of CLAB (RR, 0.5; 95% CI, 0.4-0.8; P = 0.004). CONCLUSIONS: Compliance with all aspects of aseptic CVL insertion significantly reduces the risk of CLAB. A difficulty we experienced was that most ICUs lacked the organisation and staff to support quality improvement and audit.


Assuntos
Bacteriemia/prevenção & controle , Cateterismo Venoso Central/efeitos adversos , Cateteres de Demora/microbiologia , Controle de Infecções/métodos , Melhoria de Qualidade , Austrália/epidemiologia , Bacteriemia/epidemiologia , Bacteriemia/etiologia , Lista de Checagem , Auditoria Clínica , Cuidados Críticos , Humanos , Controle de Infecções/normas , Unidades de Terapia Intensiva , Padrões de Prática Médica
13.
J Am Chem Soc ; 132(34): 11836-7, 2010 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-20687546

RESUMO

Potassium(I) amidotrihydroborate (KNH(2)BH(3)) is a newly developed potential hydrogen storage material representing a completely different structural motif within the alkali metal amidotrihydroborate group. Evolution of 6.5 wt % hydrogen starting at temperatures as low as 80 degrees C is observed and shows a significant change in the hydrogen release profile, as compared to the corresponding lithium and sodium compounds. Here we describe the synthesis, structure, and hydrogen release characteristics of KNH(2)BH(3).


Assuntos
Boranos/química , Hidrogênio/química , Boranos/síntese química , Cristalografia por Raios X , Modelos Moleculares , Estrutura Molecular
14.
J Am Chem Soc ; 132(8): 2516-7, 2010 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-20136140

RESUMO

Carbide films exhibit many unique properties. The development of a versatile and simple technique for the deposition of carbide films will enable a wide range of technological applications. Here we report a cost-effective chemical solution deposition or polymer-assisted deposition method for growing epitaxial carbide (including TiC, VC, and TaC) films. These epitaxial carbide films exhibit structural and physical properties similar to the films grown by vapor deposition methods.

15.
Aust Crit Care ; 23(3): 109-29, 2010 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-20083413

RESUMO

BACKGROUND: To achieve improvement in healthcare quality and safety, all four domains (outcome, process, structure and culture) must be considered in conjunction with the best available clinical evidence to improve patient care and reduce harm. A range of improvement initiatives have targeted processes of care in recognition of: (1) complexities of patient care and (2) evidence that a large portion of adverse events are preventable, occur during ongoing care, and result in poorer patient outcomes. PURPOSE: The aims of this paper are to: (1) outline national and international quality and safety initiatives; (2) identify evidence-based processes of care applicable to the general adult ICU patient population; (3) summarise the literature on relevant quality improvement strategies. METHODS: An integrative literature review was conducted by: (1) database search of Ovid Medline, CINAHL, EMBASE and Cochrane for articles published between 1996 and October 2009; (2) identification of additional studies from articles obtained; (3) purposive internet search identifying relevant quality and safety initiatives. FINDINGS: Quality improvement initiatives across the globe were identified, with ensuing focus on how the development, implementation and evaluation of evidence-based processes of care can lead to improvements in the delivery and outcomes of intensive care practice. Variation in practice and methodological limitations of existing studies were also noted, highlighting the need for innovative approaches to improving processes in the ICU. CONCLUSION: This integrative review has outlined potential for achieving practice improvements in intensive care and highlighted the need for further evaluative research to improve patient care at the bedside.


Assuntos
Cuidados Críticos/normas , Garantia da Qualidade dos Cuidados de Saúde , Gestão da Segurança/normas , Medicina Baseada em Evidências , Humanos , Cultura Organizacional , Avaliação de Processos e Resultados em Cuidados de Saúde
16.
ACS Appl Mater Interfaces ; 12(37): 42236-42247, 2020 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-32877167

RESUMO

High-energy-density systems with fast charging rates and suppressed dendrite growth are critical for the implementation of efficient and safe next-generation advanced battery technologies such as those based on Li metal. However, there are few studies that investigate reliable cycling of Li metal electrodes under high-rate conditions. Here, by employing a superconcentrated ionic liquid (IL) electrolyte, we highlight the effect of Li salt concentration and applied current density on the resulting Li deposit morphology and solid electrolyte interphase (SEI) characteristics, demonstrating exceptional deposition/dissolution rates and efficiency in these systems. Operation at higher current densities enhanced the cycling efficiency, e.g., from 64 ± 3% at 1 mA cm-2 up to 96 ± 1% at 20 mA cm-2 (overpotential <±0.2 V), while resulting in lower electrode resistance and dendrite-free Li morphology. A maximum current density of 50 mA cm-2 resulted in 88 ± 3% cycling efficiency, displaying tolerance for high overpotentials at the Ni working electrode (0.5 V). X-ray photoelectron microscopy (XPS), time-of-flight secondary-ion mass spectroscopy (ToF-SIMS), and scanning electron microscopy (SEM) surface measurements revealed that the formation of a stable SEI, rich in LiF and deficient in organic carbon species, coupled with nondendritic and compact Li morphologies enabled enhanced cycling efficiency at higher currents. Reduced dendrite formation at high current is further highlighted by the use of a highly porous separator in coin cell cycling (1 mAh cm-2 at 50 °C), sustaining 500 cycles at 10 mA cm-2.

17.
ACS Appl Mater Interfaces ; 12(9): 10496-10502, 2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-32043855

RESUMO

LiNi0.5Co0.2Mn0.3O2 (NCM523), as a cathode material for rechargeable lithium-ion batteries, has attracted considerable attention and been successfully commercialized for decades. NCM is also a promising electrocatalyst for the oxygen evolution reaction (OER), and the catalytic activity is highly correlated to its structure. In this paper, we successfully obtain NCM523 with three different structures: spinel NCM synthesized at low temperature (LT-NCM), disordered NCM (DO-NCM) with lithium deficiency obtained at high temperature, and layered hexagonal NCM at high temperature (HT-NCM). By introducing lithium deficiency to tune the valence state of transition metals in NCM from Ni2+ to Ni3+, DO-NCM exhibits the best catalytic activity with the lowest onset potential (∼1.48 V) and Tafel slope (∼85.6 mV dec-1), whereas HT-NCM exhibits the worst catalytic activity with the highest onset potential (∼1.63 V) and Tafel slope (∼241.8 mV dec-1).

18.
J Phys Chem Lett ; 11(1): 286-291, 2020 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-31845806

RESUMO

We present a novel spectroscopic technique for in situ Raman microscopy studies of battery electrodes. By creating nanostructures on a copper mesh current collector, we were able to utilize surface-enhanced Raman spectroscopy (SERS) to monitor the evolution of the silicon anode-electrolyte interphase. The spectra show reversible Si peak intensity changes upon lithiation and delithiation. Moreover, an alkyl carboxylate species, lithium propionate, was detected as a significant SiEI component. Our experimental setup showed reproducible and stable performance over multiple cycles in terms of both electrochemistry and spectroscopy.

19.
ACS Appl Mater Interfaces ; 12(44): 49563-49573, 2020 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-33094999

RESUMO

A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. Thus, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li+). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at ∼1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.

20.
ACS Appl Mater Interfaces ; 12(23): 26593-26600, 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32412232

RESUMO

A stable solid electrolyte interphase (SEI) has been proven to be a key enabler to most advanced battery chemistries, where the reactivity between the electrolyte and the anode operating beyond the electrolyte stability limits must be kinetically suppressed by such SEIs. The graphite anode used in state-of-the-art Li-ion batteries presents the most representative SEI example. Because of similar operation potentials between graphite and silicon (Si), a similar passivation mechanism has been thought to apply on the Si anode when using the same carbonate-based electrolytes. In this work, we found that the chemical formation process of a proto-SEI on Si is closely entangled with incessant SEI decomposition, detachment, and reparation, which lead to continuous lithium consumption. Using a special galvanostatic protocol designed to observe the SEI formation prior to Si lithiation, we were able to deconvolute the electrochemical formation of such dynamic SEI from the morphology and mechanical complexities of Si and showed that a pristine Si anode could not be fully passivated in carbonate-based electrolytes.

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