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1.
Sci Rep ; 10(1): 59, 2020 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-31919368

RESUMO

Electrochemical deposition is a viable approach to develop novel catalyst structures, such as Pt thin films on conductive support materials. Most studies, reaching out to control electrochemical deposition of Pt to monolayer quantities focus on noble metal substrates (e.g., Au). In contrast, conductive oxides, such as antimony doped tin oxide (ATO), are considered as support material for different applications, e.g., as fuel cell catalysts. Herein, we investigate the deposition process of Pt on Sn, used as a model system for the electrochemical deposition of Pt on non-noble metal oxide supports. Doing so, we shade some light on the differences of a metallic Sn surface and surface oxide species in electrochemical deposition processes. With respect to a borate buffer solution, containing K2PtCl4 as Pt precursor, we report for the first time that surface oxides have the capability to fully inhibit the electrochemical deposition of Pt. Furthermore, direct alloying of the deposited Pt with the Sn support during the electrodeposition process yielded a catalyst with a high activity for the oxidation of CO.

2.
Angew Chem Int Ed Engl ; 59(14): 5665-5674, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-31825547

RESUMO

Solid electrolyte materials are crucial for the development of high-energy-density all-solid-state batteries (ASSB) using a nonflammable electrolyte. In order to retain a low lithium-ion transfer resistance, fast lithium ion conducting solid electrolytes are required. We report on the novel superionic conductor Li9 AlP4 which is easily synthesised from the elements via ball-milling and subsequent annealing at moderate temperatures and which is characterized by single-crystal and powder X-ray diffraction. This representative of the novel compound class of lithium phosphidoaluminates has, as an undoped material, a remarkable fast ionic conductivity of 3 mS cm-1 and a low activation energy of 29 kJ mol-1 as determined by impedance spectroscopy. Temperature-dependent 7 Li NMR spectroscopy supports the fast lithium motion. In addition, Li9 AlP4 combines a very high lithium content with a very low theoretical density of 1.703 g cm-3 . The distribution of the Li atoms over the diverse crystallographic positions between the [AlP4 ]9- tetrahedra is analyzed by means of DFT calculations.

3.
J Am Chem Soc ; 141(36): 14200-14209, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31403777

RESUMO

Solid electrolytes with superionic conductivity are required as a main component for all-solid-state batteries. Here we present a novel solid electrolyte with three-dimensional conducting pathways based on "lithium-rich" phosphidosilicates with ionic conductivity of σ > 10-3 S cm-1 at room temperature and activation energy of 30-32 kJ mol-1 expanding the recently introduced family of lithium phosphidotetrelates. Aiming toward higher lithium ion conductivities, systematic investigations of lithium phosphidosilicates gave access to the so far lithium-richest compound within this class of materials. The crystalline material (space group Fm3m), which shows reversible thermal phase transitions, can be readily obtained by ball mill synthesis from the elements followed by moderate thermal treatment of the mixture. Lithium diffusion pathways via both tetrahedral and octahedral voids are analyzed by temperature-dependent powder neutron diffraction measurements in combination with maximum entropy method and DFT calculations. Moreover, the lithium ion mobility structurally indicated by a disordered Li/Si occupancy in the tetrahedral voids plus partially filled octahedral voids is studied by temperature-dependent impedance and 7Li NMR spectroscopy.

4.
J Phys Chem A ; 122(45): 8828-8839, 2018 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-30354136

RESUMO

High degrees of delithiation of layered transition metal oxide cathode active materials (NCMs and HE-NCM) for lithium-ion batteries (LIBs) was shown to lead to the release of singlet oxygen, which is accompanied by enhanced electrolyte decomposition. Here, we study the reactivity of chemically produced singlet oxygen with the commonly used cyclic and linear carbonate solvents for LIB electrolytes. On-line gassing analysis of the decomposition of ethylene carbonate (EC) and dimethyl carbonate (DMC) reveals different stability toward the chemical attack of singlet oxygen, which is produced in situ by photoexcitation of the Rose Bengal dye. Ab initio calculations and on-the-fly simulations reveal a possible reaction mechanism, confirming the experimental findings. In the case of EC, hydrogen peroxide and vinylene carbonate (VC) are found to be the products of the first reaction step of EC with singlet oxygen in the reaction cascade of the EC chemical decomposition. In contrast to EC, simulations suggested DMC to be stable in the presence of singlet oxygen, which was also confirmed experimentally. Hydrogen peroxide is detrimental for cycling of a battery. For all known cathode active materials, the potential where singlet oxygen is released is found to be already high enough to electrochemically oxidize hydrogen peroxide. The formed protons and/or water both react with the typically used LiPF6 salt to HF that then leads to transition metal dissolution from the cathode active materials. This study shows how important the chemical stability toward singlet oxygen is for today's battery systems and that a trade-off will have to be found between chemical and electrochemical stability of the solvent to be used.

5.
Langmuir ; 33(47): 13615-13624, 2017 11 28.
Artigo em Inglês | MEDLINE | ID: mdl-29083194

RESUMO

The reduction of metal precursors during the polyol synthesis of metal nanoparticles was monitored by ex situ ionic conductivity measurements. Using commonly used platinum precursors (K2PtCl6, H2PtCl6, and K2PtCl4) as well as iridium and ruthenium precursors (IrCl3 and RuCl3), we demonstrate that their reduction in ethylene glycol at elevated temperatures is accompanied by a predictable change in ionic conductivity, enabling a precise quantification of the onset temperature for their reduction. This method also allows detecting the onset temperature for the further reaction of ethylene glycol with HCl produced by the reduction of chloride-containing metal precursors (at ≈120 °C). On the basis of these findings, we show that the conversion of the metal precursor to reduced metal atoms/clusters can be precisely quantified, if the reaction occurs below 120 °C, which also enables a distinction between the stages of metal particle nucleation and growth. The latter is demonstrated by the reduction of H2PtCl6 in ethylene glycol, comparing ionic conductivity measurements with transmission electron microscopy analysis. In summary, ionic conductivity measurements are a simple and straightforward tool to quantify the reduction kinetics of commonly used metal precursors in the polyol synthesis.

6.
J Phys Chem Lett ; 8(19): 4820-4825, 2017 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-28910111

RESUMO

We compare the stability of alkyl carbonate electrolyte on NMC111, -622, and -811, LNMO, and conductive carbon electrodes. We prove that CO2 and CO evolution onset potentials depend on the electrode material and increase in the order NMC811 < NMC111 ≈ NMC622 < conductive carbon ≈ LNMO, which we rationalize by two fundamentally different oxidation mechanisms, the chemical and the electrochemical electrolyte oxidation. Additionally, in contrast to the widespread understanding that transition metals in cathode active materials catalyze the electrolyte oxidation, we will prove that such a catalytic effect on the electrochemical electrolyte oxidation does not exist.

7.
Materials (Basel) ; 10(6)2017 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-28773022

RESUMO

In this experimental study, we investigate various transition-metal silicides as platinum-group-metal-(PGM)-free electrocatalysts for the hydrogen oxidation reaction (HOR), and for the hydrogen evolution reaction (HER) in acidic environment for the first time. Using cyclic voltammetry in 0.1 M HClO4, we first demonstrate that the tested materials exhibit sufficient stability against dissolution in the relevant potential window. Further, we determine the HOR and HER activities for Mo, W, Ta, Ni and Mo-Ni silicides in rotating disk electrode experiments. In conclusion, for the HOR only Ni2Si shows limited activity, and the HER activity of the investigated silicides is considerably lower compared to other PGM-free HER catalysts reported in the literature.

8.
Chemistry ; 22(49): 17635-17645, 2016 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-27786395

RESUMO

The need to improve electrodes and Li-ion conducting materials for rechargeable all-solid-state batteries has drawn enhanced attention to the investigation of lithium-rich compounds. The study of the ternary system Li-Si-P revealed a series of new compounds, two of which, Li8 SiP4 and Li2 SiP2 , are presented. Both phases represent members of a new family of Li ion conductors that display Li ion conductivity in the range from 1.15(7)×10-6 Scm-1 at 0 °C to 1.2(2)×10-4 Scm-1 at 75 °C (Li8 SiP4 ) and from 6.1(7)×10-8 Scm-1 at 0 °C to 6(1)×10-6 Scm-1 at 75 °C (Li2 SiP2 ), as determined by impedance measurements. Temperature-dependent solid-state 7 Li NMR spectroscopy revealed low activation energies of about 36 kJ mol-1 for Li8 SiP4 and about 47 kJ mol-1 for Li2 SiP2 . Both compounds were structurally characterized by X-ray diffraction analysis (single crystal and powder methods) and by 7 Li, 29 Si, and 31 P MAS NMR spectroscopy. Both phases consist of tetrahedral SiP4 anions and Li counterions. Li8 SiP4 contains isolated SiP4 units surrounded by Li atoms, while Li2 SiP2 comprises a three-dimensional network based on corner-sharing SiP4 tetrahedra, with the Li ions located in cavities and channels.

9.
Angew Chem Int Ed Engl ; 55(24): 6892-5, 2016 06 06.
Artigo em Inglês | MEDLINE | ID: mdl-27145532

RESUMO

Aprotic lithium-oxygen (Li-O2 ) batteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density. A major challenge is their poor reversibility caused by degradation reactions, which mainly occur during battery charge and are still poorly understood. Herein, we show that singlet oxygen ((1) Δg ) is formed upon Li2 O2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through a reaction with a spin trap to form a stable radical that was observed by time- and voltage-resolved in operando EPR spectroscopy in a purpose-built spectroelectrochemical cell. According to our estimate, a lower limit of approximately 0.5 % of the evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long-overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li-O2 cells.

10.
Phys Chem Chem Phys ; 15(27): 11478-93, 2013 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-23748698

RESUMO

The instability of currently used electrolyte solutions and of the carbon support during charge-discharge in non-aqueous lithium-oxygen cells can lead to discharge products other than the desired Li2O2, such as Li2CO3, which is believed to reduce cycle-life. Similarly, discharge in an O2 atmosphere which contains H2O and CO2 impurities would lead to LiOH and Li2CO3 discharge products. In this work we therefore investigate the rechargeability of model cathodes pre-filled with four possible Li-air cell discharge products, namely Li2O2, Li2CO3, LiOH, and Li2O. Using Online Electrochemical Mass Spectrometry (OEMS), we determined the charge voltages and the gases evolved upon charge of pre-filled electrodes, thus determining the reversibility of the formation/electrooxidation reactions. We show that Li2O2 is the only reversible discharge product in ether-based electrolyte solutions, and that the formation of Li2CO3, LiOH, or Li2O is either irreversible and/or reacts with the electrolyte solution or the carbon during its oxidation.


Assuntos
Fontes de Energia Elétrica , Éteres/química , Lítio/química , Oxigênio/química , Técnicas Eletroquímicas , Eletrodos , Eletrólitos/química , Espectrometria de Massas , Oxirredução , Soluções
11.
Phys Chem Chem Phys ; 15(28): 11830-9, 2013 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-23760527

RESUMO

Glyme-based electrolytes were studied for the use in lithium-air batteries because of their greater stability towards oxygen reduction reaction intermediates (e.g., superoxide anion radicals (O2˙(-))) produced upon discharge at the cathode compared to previously employed carbonate-based electrolytes. However, contradictory results of glyme stability tests employing KO2 as an O2˙(-) source were reported in the literature. For clarification, we investigated the reaction of KO2 with glymes of various chain lengths qualitatively using (1)H NMR and FTIR spectroscopy as well as more quantitatively using UV-Vis spectroscopy. During our experiments we found a huge impact of small quantities of impurities on the stability of the solvents. Therefore, we studied further the influence of impurities in the glymes on the cycling behavior of Li-O2 cells, demonstrating the large effect of electrolyte impurities on Li-O2 cell performance.

12.
J Am Chem Soc ; 135(21): 7985-91, 2013 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-23646922

RESUMO

The ability to direct bimetallic nanoparticles to express desirable surface composition is a crucial step toward effective heterogeneous catalysis, sensing, and bionanotechnology applications. Here we report surface composition tuning of bimetallic Au-Pt electrocatalysts for carbon monoxide and methanol oxidation reactions. We establish a direct correlation between the surface composition of Au-Pt nanoparticles and their catalytic activities. We find that the intrinsic activities of Au-Pt nanoparticles with the same bulk composition of Au0.5Pt0.5 can be enhanced by orders of magnitude by simply controlling the surface composition. We attribute this enhancement to the weakened CO binding on Pt in discrete Pt or Pt-rich clusters surrounded by surface Au atoms. Our finding demonstrates the importance of surface composition control at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles and opens up strategies for the development of highly active bimetallic nanoparticles for electrochemical energy conversion.


Assuntos
Monóxido de Carbono/química , Eletroquímica , Ouro/química , Nanopartículas Metálicas/química , Metanol/química , Platina/química , Propriedades de Superfície , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Oxirredução
13.
J Am Chem Soc ; 133(47): 19048-51, 2011 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-22044022

RESUMO

We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO(4) 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li(+)-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a "volcano-type" trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O(2) cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li(+)-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications.


Assuntos
Fontes de Energia Elétrica , Lítio/química , Oxigênio/química , Ar , Catálise , Oxirredução
14.
Science ; 334(6061): 1383-5, 2011 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-22033519

RESUMO

The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.

15.
Nat Chem ; 3(7): 546-50, 2011 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-21697876

RESUMO

The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ-orbital (e(g)) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) displacement and OH(-) regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

16.
J Am Chem Soc ; 132(35): 12170-1, 2010 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-20527774

RESUMO

PtAu nanoparticles (NPs) were shown to strongly enhance the kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Li-O(2) cells. Li-O(2) cells with PtAu/C were found to exhibit the highest round-trip efficiency reported to date. During ORR via xLi(+) + O(2) + xe(-) --> Li(x)O(2), the discharge voltage with PtAu/C was considerably higher than that of pure carbon and comparable to that of Au/C. During OER via Li(x)O(2) --> xLi(+) + O(2) + xe(-), the charge voltages with PtAu/C fell in the range from 3.4 to 3.8 V(Li), which is slightly lower than obtained with Pt. It is hypothesized that PtAu NPs exhibit bifunctional catalytic activity, having surface Au and Pt atoms primarily responsible for ORR and OER kinetics in Li-O(2) cells, respectively.


Assuntos
Fontes de Energia Elétrica , Ouro/química , Lítio/química , Nanopartículas Metálicas/química , Platina/química , Ar , Carbono/química , Catálise , Cinética , Oxigênio/química , Tamanho da Partícula , Propriedades de Superfície
17.
Science ; 324(5923): 48-9, 2009 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-19342578
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