Ira Bloom - Academia.edu (original) (raw)
Papers by Ira Bloom
World Electric Vehicle Journal, 2010
The widespread introduction of electrically-propelled vehicles is currently part of many politica... more The widespread introduction of electrically-propelled vehicles is currently part of many political strategies and introduction plans. These new vehicles, ranging from limited (mild) hybrid to plug-in hybrid to fully-battery powered, will rely on a new class of advanced storage batteries, such as those based on lithium, to meet different technical and economical targets. The testing of these batteries to determine the performance and life in the various applications is a time-consuming and costly process that is not yet well developed. There are many examples of parallel testing activities that are poorly coordinated, for example, those in Europe, Japan and the US. These costs and efforts may be better leveraged through international collaboration, such as that possible within the framework of the International Energy Agency (IEA). Here, a new effort is under development that will establish standardized, accelerated testing procedures and will allow battery testing organizations to cooperate in the analysis of the resulting data. This paper reviews the present state-of-the-art in accelerated life testing procedures in Europe, Japan and the US. The existing test procedures will be collected, shortly described, compared and analyzed with the goal of defining a process and a possible working plan for the establishment of an international collaboration.
Journal of the American Chemical Society, Oct 1, 1981
The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and co... more The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and condensation reactions (with and without loss of H2 from the product ion) with olefins. Even though cyclopropenium ions [i.e., (C3H3+)] are unreactive with the propargyl halides, acetylene, and benzene, these ions are observed to react with a variety of compounds, although usually at a much lower rate than the corresponding reactions of CH2CCH+. For instance, c-C3H3+ reacts with unsaturated molecules having four or more carbon atoms by condensation. This ion also reacts with aldehydes by hydride transfer and with amines through several mechanisms including hydride transfer and condensation [ k-(1-10) X 10-Io cm3/molecule.s]. The cyclic ions do not react with linear or branched alkanes (C4-C10), even though reactions which are exothermic by as much as 10 or 15 kcal/mol can be written for these systems. Acknowledgment. We acknowledge many enlightening discussions with Dr. Kermit Smyth regarding the role of C3H3+ ion reactions in the formation of soot.
Journal of the American Chemical Society, Oct 1, 1981
The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and co... more The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and condensation reactions (with and without loss of H2 from the product ion) with olefins. Even though cyclopropenium ions [i.e., (C3H3+)] are unreactive with the propargyl halides, acetylene, and benzene, these ions are observed to react with a variety of compounds, although usually at a much lower rate than the corresponding reactions of CH2CCH+. For instance, c-C3H3+ reacts with unsaturated molecules having four or more carbon atoms by condensation. This ion also reacts with aldehydes by hydride transfer and with amines through several mechanisms including hydride transfer and condensation [ k-(1-10) X 10-Io cm3/molecule.s]. The cyclic ions do not react with linear or branched alkanes (C4-C10), even though reactions which are exothermic by as much as 10 or 15 kcal/mol can be written for these systems. Acknowledgment. We acknowledge many enlightening discussions with Dr. Kermit Smyth regarding the role of C3H3+ ion reactions in the formation of soot.
![Research paper thumbnail of Solution synthesis and crystallographic characterization of the divalent organosamarium complexes (C5Me5)2Sm(THF)2 and [(C5Me5)Sm(.mu.-I)(THF)2]2](https://attachments.academia-assets.com/107199406/thumbnails/1.jpg)
](Journal of the American Chemical Society, 1985
The reaction of Sm12 in THF solution with a slight excess of 2 equiv of KC5Me5 yields (C5Me5)2Sm(... more The reaction of Sm12 in THF solution with a slight excess of 2 equiv of KC5Me5 yields (C5Me5)2Sm(THF)2 (I) in high yield and purity. Reaction of I with an equimolar quantity of Sm12 forms [(C,Me5)sm(p-I)(THF),1, (II), which can also be prepared from the 1:l stoichiometric reaction of SmI, and KC5MeS. Both I and I1 have been characterized by spectral, chemical, and X-ray crystallographic methods. I crystallizes from THF in the triclinic space group Pi with a = 15.155 (6) A, b = 16.141 (6) A, c = 16.179 (6) A, a = 55.92 (3)O, p = 65.13 (3)O, y = 62.18 (3)O, and 0, = 1.33 g cm13 for Z = 4. Least-squares refinement on the basis of 3949 observed reflections led to a final R value of 0.061. The molecule has a bent metallocene structure in which the two cyclopentadienyl ring centroids and the two THF oxygen atoms roughly describe a tetrahedral coordination geometry. The average Sm-C(ring) distance is 2.86 (3) A. The average Sm-0 distance is 2.64 A. I1 crystallizes from THF under hexane diffusion in the monoclinic space group P2,/n with u = 12.708 (6) A, b = 13.454 (6) A, c = 14.859 (6) A, p = 112.37 (4)O, and D, = 1.57 g cm-3 for Z = 2 (dimers). Least-squares refinement on the basis of 1577 observed reflections led to a final R value of 0.053. The two (C5MeS)(THF),Sm moieties in the molecule are bridged by iodine ligands via a planar Sm2(pI), unit with the cyclopentadienyl ring on one side of the plane and the THF molecules on the other side. The two distinct Sm-(p-I) distances are 3.356 (2) and 3.459 (2) A, the average Sm-C(ring) distance is 2.81 (2) A, and the Sm-0 distances average 2.64 A. In recent years, the organometallic chemistry of the lanthanide metals in low oxidation states has been actively investigated and a variety of new complexes and reactivity patterns have been discovered.2-10 These low-valent studies have involved the zerovalent metals in the elemental state, using metal-vapor techniques, as well as the complexes of the three lanthanide metals that have divalent states readily accessible under "normaln solution reaction conditions, Le., Eu, Yb, and Sm. Although Sm(I1) is the most reactive of these divalent lanthanides [Sm(III) + e-Sm(I1):
![Research paper thumbnail of Synthesis and characterization of the samarium-cobalt complexes (C5Me5)2(THF) SmCo(CO)4 and [SmI2(THF)5][Co(CO)4]: x-ray crystal structure of a seven-coordinate samarium(III) cation complex](https://attachments.academia-assets.com/107199388/thumbnails/1.jpg)
](Inorganic Chemistry, 1985
Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSM... more Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSMes)2(THF)SmCo(CO), and [Sm12(THF)s] [Co(CO),], respectively. Co2(CO), reacts with [(CSMes)SmI(THF)2]2 to form a complex that disproportionates to (CsMes)2(THF)SmCo(CO)4 and [ S I~I~(T H F)~] [Co(CO),]. The latter complex crystallizes from T H F in the triclinic space group PI with unit cell dimensions a = 8.829 (4) A, b = 12.965 (4) A, c = 14.740 (5) A, CY = 88.48 (3)O, p = 81.63 (3)O, y = 87.51 (3)', and Z = 2 for Dcald = 1.86 g Least-squares refinement on the basis of 1559 observed reflections led to a final R value of 0.041. The complex exists as discrete Sm12(THF)st cations and Co(CO), anions with no Sm-0-C-Co isocarbonyl linkage. The coordination geometry around the samarium atom is roughly pentagonal bipyramidal with the iodide atoms at the two apical positions (Sm-I distances 3.030 (2) and 3.009 (2) A). The Sm-O(THF) distances vary from 2.44 (1) to 2.47 (1) A. The Co(CO),anion has a tetrahedral geometry. In the early 1970s, several reactions involving transition-metal carbonyl complexes and lanthanide reagents were r e p~r t e d .~-~ Typical examples included (a) ionic metathesis reactions such as reaction of CSHsMo(CO)3-Na+ with LnCI, or (CSHS)2LnC1-(THF),S (b) reactions of t h e elemental lanthanide with a transition-metal carbonyl halide such as Mn(CO)sBr,4 (c) reactions of lanthanide amalgams with mercury derivatives of transitionmetal carbonyl anions such as H~[ C O (C O)~]~,~ and (d) simple addition of tris(cyc1opentadienyI)lanthanides t o transition-metal carbonyls to form adduct^.^*^-^ Crystallographic characterization of t h e products of these reactions has proven difficult, and the precise structures remain unknown. NMR and IR spectroscopic evidence on lanthanide-transition-metal carbonyl reaction mixtures suggested that isccarbonyl linkages, Ln-0-CM (Ln = lanthanide metal, M = transition metal), may exist in complexes of this t~p e .~-~ This is consistent with the highly oxophilic nature of the lanthanides in complexes.1° Divalent organolanthanide complexes react with transition-metal carbonyl complexes by reducing them to anionic species,' 1-14 and recently, for the pentamethylcyclopentadienyl-substituted complex (CSMeS)2Yb(OEt2), X-ray crystallographic data on these mixed transition-metal-lanthanide systems have become available. Reaction of t h e ytterbium reagent with C O~(C O)~, Fe3(C0)12, and Mn2(CO)lo has given [(CSMeS)2(THF)Yb] [(pOC)Co-(CO),],12 [(CsMes)2Yb]2[(~-OC),Fe3(C0)7],13 and a mixture of [[(CsMes)zYb] [(P-OC)2Mn(CO)3II2 and [[(CsMes)2Yb] [ (P-OC),Mn(CO)2]],,14 respectively. In each product, the ytterbium exhibited t h e structural parameters of a trivalent species, t h e transition-metal carbonyl fragment was anionic, and the anions and cations were connected via Ln-O-CM isocarbonyl linkages.
Inorganic Chemistry, 1986
The synthesis and crystal and molecular structures of (C5Me5)2YC1(THF) (I), (C5Me5)2SmCI(THF) (11... more The synthesis and crystal and molecular structures of (C5Me5)2YC1(THF) (I), (C5Me5)2SmCI(THF) (11), and (C5Me5)2SmI(THF) (111) are described. (C5Me5)*YC1(THF) was isolated as a byproduct of the reaction of YC13 with KC5Me5. It crystallizes from THF/pentane at-20 OC in space group PI with unit cell dimensions a = 8.541 (2) A, b = 17.216 (6) A, c = 18.356 (6) A, CY = 63.04 (2)O, 0 = 88.83 (2)O, y = 88.36 (2)O, V = 2404.7 A', and Dald = 1.21 g cm-' for 2 = 4. (C5Me5)2SmCI(THF) was prepared by oxidation of (C5Me5)2Sm(THF)2 with r-C,H,CI. It crystallizes from toluene at-30 'C in space group Pi with unit cell dimensions a = 8.567 (5) A, b = 17.331 (6) A, c = 18.515 (6) A, a = 62.71 (3)O, p = 88.46 (4)O, y = 87.82 (4)O, V = 2441.3 A3, and Dald = 1.44 g cm-' for Z = 4. (C5Me5)2SmI(THF) was prepared from (C5Me5)2Sm(THF)2 by oxidation with ICH2CH21 and from [(C5Me5)2SmH]2 by reaction with CH31. It crystallizes from toluene at 25 OC in space group Pi with unit cell dimensions a = 8.812 (4) A, b = 17.569 (7) A, c = 18.464 (7) A, CY = 62.25 (4)O, 0 = 89.16 (4)O, y = 87.68 (4)O, V = 2625 A3, and Dcald = 1.63 g C I I-~ for 2 = 4. In each complex, the C5Me5 ring centroids, the T H F oxygen atom, and the halide ligand describe a distorted tetrahedral geometry around the metal. The synthesis of (C5Me5)2SmC12Li(THF)2 and (C5Me4Et)2SmC12Li(THF)2 is also described.
Organometallics, 1985
ABSTRACT
Journal of the American Chemical Society, 1983
1 mM FeTPP(C1) and 0, (2 mol/mol of FeTPP(C1)) and characterized by visible and 'H NMR spectra su... more 1 mM FeTPP(C1) and 0, (2 mol/mol of FeTPP(C1)) and characterized by visible and 'H NMR spectra superimposable on those of an authentic sample.,' Complex 2' is much more stable toward 0, (t l , , in aerated C6H6 = 12 h2IC) than 2. On the
h i g h l i g h t s Key gaps in lithium-based battery technology are presented viz. extremely fas... more h i g h l i g h t s Key gaps in lithium-based battery technology are presented viz. extremely fast charging. At cell level, lithium plating on anode remains an issue. At cell level, stress-induced cracking of cathode material may be an issue. Safety at pack level must be explored.
Journal of Power Sources, 2016
Two testing protocols, QC/T 743 and those used by the U.S. Advanced Battery Consortium (USABC), w... more Two testing protocols, QC/T 743 and those used by the U.S. Advanced Battery Consortium (USABC), were compared using cells based on LiFePO 4 /graphite chemistry. Differences in the protocols directly affected the data and the performance decline mechanisms deduced from the data. In all cases, the rate of capacity fade was linear with time. Overall, the testing protocols produced very similar data when the testing conditions and metrics used to define performance were similar. The choice of depth of discharge and pulse width had a direct effect on the apparent rate of resistance increased and estimated cell life. At greater percent depth of discharge (%DOD) and pulse width, the estimated life was shorter that at lower %DOD and shorter pulse width. This indicates that cells which were at the end of life based on the USABC protocol were not at end of life based on the QC/T 743 protocol by a large margin.
The Advanced Technology Development Program is currently evaluating the performance of the second... more The Advanced Technology Development Program is currently evaluating the performance of the second generation of Lithium-ion cells (i.e., Gen 2 cells). The 18650-size Gen 2 cells consist of a baseline chemistry and one variant chemistry. These cells were distributed over a matrix consisting of three states-of-charge (SOC) (60, 80, and 100% SOC), four temperatures (25, 35, 45, and 55°C), and three life tests (calendar-, cycle-, and accelerated-life). The calendar-life cells are clamped at an opencircuit voltage corresponding to 60% SOC and undergo a once-per-day pulse profile. The cycle-life cells are continuously pulsed using a profile that is centered around 60% SOC. The accelerated-life cells are following the calendar-life test procedures, but using the cycle-life pulse profile. Life testing is interrupted every four weeks for reference performance tests (RPTs), which are used to quantify changes in capacity, resistance, and power. The RPTs consist of a C 1 /1 and C 1 /25 static capacity tests, a low-current hybrid pulse power characterization test, and electrochemical impedance spectroscopy at 60% SOC. Capacity-, power-, and electrochemical impedance spectroscopy-based performance results are reported.
![Research paper thumbnail of Synthesis and characterization of the samarium-cobalt complexes (C5Me5)2(THF) SmCo(CO)4 and [SmI2(THF)5][Co(CO)4]: x-ray crystal structure of a seven-coordinate samarium(III) cation complex](https://attachments.academia-assets.com/49741746/thumbnails/1.jpg)
](Inorganic Chemistry, 1985
Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSM... more Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSMes)2(THF)SmCo(CO), and [Sm12(THF)s] [Co(CO),], respectively. Co2(CO), reacts with [(CSMes)SmI(THF)2]2 to form a complex that disproportionates to (CsMes)2(THF)SmCo(CO)4 and [ S I~I~( T H F )~] [Co(CO),]. The latter complex crystallizes from T H F in the triclinic space group PI with unit cell dimensions a = 8.829 (4) A, b = 12.965 (4) A, c = 14.740 (5) A, CY = 88.48 (3)O, p = 81.63 (3)O, y = 87.51 (3)', and Z = 2 for Dcald = 1.86 g Least-squares refinement on the basis of 1559 observed reflections led to a final R value of 0.041. The complex exists as discrete Sm12(THF)st cations and Co(CO), anions with no Sm-0-C-Co isocarbonyl linkage. The coordination geometry around the samarium atom is roughly pentagonal bipyramidal with the iodide atoms at the two apical positions (Sm-I distances 3.030 (2) and 3.009 (2) A). The Sm-O(THF) distances vary from 2.44 (1) to 2.47 (1) A. The Co(CO),anion has a tetrahedral geometry. In the early 1970s, several reactions involving transition-metal carbonyl complexes and lanthanide reagents were r e p~r t e d .~-~ Typical examples included (a) ionic metathesis reactions such as reaction of CSHsMo(CO)3-Na+ with LnCI, or (CSHS)2LnC1-(THF),S (b) reactions of t h e elemental lanthanide with a transition-metal carbonyl halide such as Mn(CO)sBr,4 (c) reactions of lanthanide amalgams with mercury derivatives of transitionmetal carbonyl anions such as H~[ C O ( C O )~]~,~ and (d) simple addition of tris(cyc1opentadienyI)lanthanides t o transition-metal carbonyls to form adduct^.^*^-^ Crystallographic characterization of t h e products of these reactions has proven difficult, and the precise structures remain unknown. NMR and IR spectroscopic evidence on lanthanide-transition-metal carbonyl reaction mixtures suggested that isccarbonyl linkages, Ln-0-C-M (Ln = lanthanide metal, M = transition metal), may exist in complexes of this t~p e .~-~ This is consistent with the highly oxophilic nature of the lanthanides in complexes.1° Divalent organolanthanide complexes react with transition-metal carbonyl complexes by reducing them to anionic species,' 1-14 and recently, for the pentamethylcyclopentadienyl-substituted complex (CSMeS)2Yb(OEt2), X-ray crystallographic data on these mixed transition-metal-lanthanide systems have become available. Reaction of t h e ytterbium reagent with C O~( C O )~, Fe3(C0)12, and Mn2(CO)lo has given [(CSMeS)2(THF)Yb] [(pOC)Co-(CO),],12 [(CsMes)2Yb]2[(~-OC),Fe3(C0)7],13 and a mixture of [[(CsMes)zYb] [(P-OC)2Mn(CO)3II2 and [[(CsMes)2Yb] [ ( P -OC),Mn(CO)2]],,14 respectively. In each product, the ytterbium exhibited t h e structural parameters of a trivalent species, t h e transition-metal carbonyl fragment was anionic, and the anions and cations were connected via Ln-O-C-M isocarbonyl linkages.
World Electric Vehicle Journal, 2010
The widespread introduction of electrically-propelled vehicles is currently part of many politica... more The widespread introduction of electrically-propelled vehicles is currently part of many political strategies and introduction plans. These new vehicles, ranging from limited (mild) hybrid to plug-in hybrid to fully-battery powered, will rely on a new class of advanced storage batteries, such as those based on lithium, to meet different technical and economical targets. The testing of these batteries to determine the performance and life in the various applications is a time-consuming and costly process that is not yet well developed. There are many examples of parallel testing activities that are poorly coordinated, for example, those in Europe, Japan and the US. These costs and efforts may be better leveraged through international collaboration, such as that possible within the framework of the International Energy Agency (IEA). Here, a new effort is under development that will establish standardized, accelerated testing procedures and will allow battery testing organizations to cooperate in the analysis of the resulting data. This paper reviews the present state-of-the-art in accelerated life testing procedures in Europe, Japan and the US. The existing test procedures will be collected, shortly described, compared and analyzed with the goal of defining a process and a possible working plan for the establishment of an international collaboration.
Journal of the American Chemical Society, Oct 1, 1981
The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and co... more The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and condensation reactions (with and without loss of H2 from the product ion) with olefins. Even though cyclopropenium ions [i.e., (C3H3+)] are unreactive with the propargyl halides, acetylene, and benzene, these ions are observed to react with a variety of compounds, although usually at a much lower rate than the corresponding reactions of CH2CCH+. For instance, c-C3H3+ reacts with unsaturated molecules having four or more carbon atoms by condensation. This ion also reacts with aldehydes by hydride transfer and with amines through several mechanisms including hydride transfer and condensation [ k-(1-10) X 10-Io cm3/molecule.s]. The cyclic ions do not react with linear or branched alkanes (C4-C10), even though reactions which are exothermic by as much as 10 or 15 kcal/mol can be written for these systems. Acknowledgment. We acknowledge many enlightening discussions with Dr. Kermit Smyth regarding the role of C3H3+ ion reactions in the formation of soot.
Journal of the American Chemical Society, Oct 1, 1981
The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and co... more The ion undergoes condensation reactions, as well as hydride transfer, with alkyl benzenes and condensation reactions (with and without loss of H2 from the product ion) with olefins. Even though cyclopropenium ions [i.e., (C3H3+)] are unreactive with the propargyl halides, acetylene, and benzene, these ions are observed to react with a variety of compounds, although usually at a much lower rate than the corresponding reactions of CH2CCH+. For instance, c-C3H3+ reacts with unsaturated molecules having four or more carbon atoms by condensation. This ion also reacts with aldehydes by hydride transfer and with amines through several mechanisms including hydride transfer and condensation [ k-(1-10) X 10-Io cm3/molecule.s]. The cyclic ions do not react with linear or branched alkanes (C4-C10), even though reactions which are exothermic by as much as 10 or 15 kcal/mol can be written for these systems. Acknowledgment. We acknowledge many enlightening discussions with Dr. Kermit Smyth regarding the role of C3H3+ ion reactions in the formation of soot.
Journal of the American Chemical Society, 1985
The reaction of Sm12 in THF solution with a slight excess of 2 equiv of KC5Me5 yields (C5Me5)2Sm(... more The reaction of Sm12 in THF solution with a slight excess of 2 equiv of KC5Me5 yields (C5Me5)2Sm(THF)2 (I) in high yield and purity. Reaction of I with an equimolar quantity of Sm12 forms [(C,Me5)sm(p-I)(THF),1, (II), which can also be prepared from the 1:l stoichiometric reaction of SmI, and KC5MeS. Both I and I1 have been characterized by spectral, chemical, and X-ray crystallographic methods. I crystallizes from THF in the triclinic space group Pi with a = 15.155 (6) A, b = 16.141 (6) A, c = 16.179 (6) A, a = 55.92 (3)O, p = 65.13 (3)O, y = 62.18 (3)O, and 0, = 1.33 g cm13 for Z = 4. Least-squares refinement on the basis of 3949 observed reflections led to a final R value of 0.061. The molecule has a bent metallocene structure in which the two cyclopentadienyl ring centroids and the two THF oxygen atoms roughly describe a tetrahedral coordination geometry. The average Sm-C(ring) distance is 2.86 (3) A. The average Sm-0 distance is 2.64 A. I1 crystallizes from THF under hexane diffusion in the monoclinic space group P2,/n with u = 12.708 (6) A, b = 13.454 (6) A, c = 14.859 (6) A, p = 112.37 (4)O, and D, = 1.57 g cm-3 for Z = 2 (dimers). Least-squares refinement on the basis of 1577 observed reflections led to a final R value of 0.053. The two (C5MeS)(THF),Sm moieties in the molecule are bridged by iodine ligands via a planar Sm2(pI), unit with the cyclopentadienyl ring on one side of the plane and the THF molecules on the other side. The two distinct Sm-(p-I) distances are 3.356 (2) and 3.459 (2) A, the average Sm-C(ring) distance is 2.81 (2) A, and the Sm-0 distances average 2.64 A. In recent years, the organometallic chemistry of the lanthanide metals in low oxidation states has been actively investigated and a variety of new complexes and reactivity patterns have been discovered.2-10 These low-valent studies have involved the zerovalent metals in the elemental state, using metal-vapor techniques, as well as the complexes of the three lanthanide metals that have divalent states readily accessible under "normaln solution reaction conditions, Le., Eu, Yb, and Sm. Although Sm(I1) is the most reactive of these divalent lanthanides [Sm(III) + e-Sm(I1):
Inorganic Chemistry, 1985
Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSM... more Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSMes)2(THF)SmCo(CO), and [Sm12(THF)s] [Co(CO),], respectively. Co2(CO), reacts with [(CSMes)SmI(THF)2]2 to form a complex that disproportionates to (CsMes)2(THF)SmCo(CO)4 and [ S I~I~(T H F)~] [Co(CO),]. The latter complex crystallizes from T H F in the triclinic space group PI with unit cell dimensions a = 8.829 (4) A, b = 12.965 (4) A, c = 14.740 (5) A, CY = 88.48 (3)O, p = 81.63 (3)O, y = 87.51 (3)', and Z = 2 for Dcald = 1.86 g Least-squares refinement on the basis of 1559 observed reflections led to a final R value of 0.041. The complex exists as discrete Sm12(THF)st cations and Co(CO), anions with no Sm-0-C-Co isocarbonyl linkage. The coordination geometry around the samarium atom is roughly pentagonal bipyramidal with the iodide atoms at the two apical positions (Sm-I distances 3.030 (2) and 3.009 (2) A). The Sm-O(THF) distances vary from 2.44 (1) to 2.47 (1) A. The Co(CO),anion has a tetrahedral geometry. In the early 1970s, several reactions involving transition-metal carbonyl complexes and lanthanide reagents were r e p~r t e d .~-~ Typical examples included (a) ionic metathesis reactions such as reaction of CSHsMo(CO)3-Na+ with LnCI, or (CSHS)2LnC1-(THF),S (b) reactions of t h e elemental lanthanide with a transition-metal carbonyl halide such as Mn(CO)sBr,4 (c) reactions of lanthanide amalgams with mercury derivatives of transitionmetal carbonyl anions such as H~[ C O (C O)~]~,~ and (d) simple addition of tris(cyc1opentadienyI)lanthanides t o transition-metal carbonyls to form adduct^.^*^-^ Crystallographic characterization of t h e products of these reactions has proven difficult, and the precise structures remain unknown. NMR and IR spectroscopic evidence on lanthanide-transition-metal carbonyl reaction mixtures suggested that isccarbonyl linkages, Ln-0-CM (Ln = lanthanide metal, M = transition metal), may exist in complexes of this t~p e .~-~ This is consistent with the highly oxophilic nature of the lanthanides in complexes.1° Divalent organolanthanide complexes react with transition-metal carbonyl complexes by reducing them to anionic species,' 1-14 and recently, for the pentamethylcyclopentadienyl-substituted complex (CSMeS)2Yb(OEt2), X-ray crystallographic data on these mixed transition-metal-lanthanide systems have become available. Reaction of t h e ytterbium reagent with C O~(C O)~, Fe3(C0)12, and Mn2(CO)lo has given [(CSMeS)2(THF)Yb] [(pOC)Co-(CO),],12 [(CsMes)2Yb]2[(~-OC),Fe3(C0)7],13 and a mixture of [[(CsMes)zYb] [(P-OC)2Mn(CO)3II2 and [[(CsMes)2Yb] [ (P-OC),Mn(CO)2]],,14 respectively. In each product, the ytterbium exhibited t h e structural parameters of a trivalent species, t h e transition-metal carbonyl fragment was anionic, and the anions and cations were connected via Ln-O-CM isocarbonyl linkages.
Inorganic Chemistry, 1986
The synthesis and crystal and molecular structures of (C5Me5)2YC1(THF) (I), (C5Me5)2SmCI(THF) (11... more The synthesis and crystal and molecular structures of (C5Me5)2YC1(THF) (I), (C5Me5)2SmCI(THF) (11), and (C5Me5)2SmI(THF) (111) are described. (C5Me5)*YC1(THF) was isolated as a byproduct of the reaction of YC13 with KC5Me5. It crystallizes from THF/pentane at-20 OC in space group PI with unit cell dimensions a = 8.541 (2) A, b = 17.216 (6) A, c = 18.356 (6) A, CY = 63.04 (2)O, 0 = 88.83 (2)O, y = 88.36 (2)O, V = 2404.7 A', and Dald = 1.21 g cm-' for 2 = 4. (C5Me5)2SmCI(THF) was prepared by oxidation of (C5Me5)2Sm(THF)2 with r-C,H,CI. It crystallizes from toluene at-30 'C in space group Pi with unit cell dimensions a = 8.567 (5) A, b = 17.331 (6) A, c = 18.515 (6) A, a = 62.71 (3)O, p = 88.46 (4)O, y = 87.82 (4)O, V = 2441.3 A3, and Dald = 1.44 g cm-' for Z = 4. (C5Me5)2SmI(THF) was prepared from (C5Me5)2Sm(THF)2 by oxidation with ICH2CH21 and from [(C5Me5)2SmH]2 by reaction with CH31. It crystallizes from toluene at 25 OC in space group Pi with unit cell dimensions a = 8.812 (4) A, b = 17.569 (7) A, c = 18.464 (7) A, CY = 62.25 (4)O, 0 = 89.16 (4)O, y = 87.68 (4)O, V = 2625 A3, and Dcald = 1.63 g C I I-~ for 2 = 4. In each complex, the C5Me5 ring centroids, the T H F oxygen atom, and the halide ligand describe a distorted tetrahedral geometry around the metal. The synthesis of (C5Me5)2SmC12Li(THF)2 and (C5Me4Et)2SmC12Li(THF)2 is also described.
Organometallics, 1985
ABSTRACT
Journal of the American Chemical Society, 1983
1 mM FeTPP(C1) and 0, (2 mol/mol of FeTPP(C1)) and characterized by visible and 'H NMR spectra su... more 1 mM FeTPP(C1) and 0, (2 mol/mol of FeTPP(C1)) and characterized by visible and 'H NMR spectra superimposable on those of an authentic sample.,' Complex 2' is much more stable toward 0, (t l , , in aerated C6H6 = 12 h2IC) than 2. On the
h i g h l i g h t s Key gaps in lithium-based battery technology are presented viz. extremely fas... more h i g h l i g h t s Key gaps in lithium-based battery technology are presented viz. extremely fast charging. At cell level, lithium plating on anode remains an issue. At cell level, stress-induced cracking of cathode material may be an issue. Safety at pack level must be explored.
Journal of Power Sources, 2016
Two testing protocols, QC/T 743 and those used by the U.S. Advanced Battery Consortium (USABC), w... more Two testing protocols, QC/T 743 and those used by the U.S. Advanced Battery Consortium (USABC), were compared using cells based on LiFePO 4 /graphite chemistry. Differences in the protocols directly affected the data and the performance decline mechanisms deduced from the data. In all cases, the rate of capacity fade was linear with time. Overall, the testing protocols produced very similar data when the testing conditions and metrics used to define performance were similar. The choice of depth of discharge and pulse width had a direct effect on the apparent rate of resistance increased and estimated cell life. At greater percent depth of discharge (%DOD) and pulse width, the estimated life was shorter that at lower %DOD and shorter pulse width. This indicates that cells which were at the end of life based on the USABC protocol were not at end of life based on the QC/T 743 protocol by a large margin.
The Advanced Technology Development Program is currently evaluating the performance of the second... more The Advanced Technology Development Program is currently evaluating the performance of the second generation of Lithium-ion cells (i.e., Gen 2 cells). The 18650-size Gen 2 cells consist of a baseline chemistry and one variant chemistry. These cells were distributed over a matrix consisting of three states-of-charge (SOC) (60, 80, and 100% SOC), four temperatures (25, 35, 45, and 55°C), and three life tests (calendar-, cycle-, and accelerated-life). The calendar-life cells are clamped at an opencircuit voltage corresponding to 60% SOC and undergo a once-per-day pulse profile. The cycle-life cells are continuously pulsed using a profile that is centered around 60% SOC. The accelerated-life cells are following the calendar-life test procedures, but using the cycle-life pulse profile. Life testing is interrupted every four weeks for reference performance tests (RPTs), which are used to quantify changes in capacity, resistance, and power. The RPTs consist of a C 1 /1 and C 1 /25 static capacity tests, a low-current hybrid pulse power characterization test, and electrochemical impedance spectroscopy at 60% SOC. Capacity-, power-, and electrochemical impedance spectroscopy-based performance results are reported.
Inorganic Chemistry, 1985
Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSM... more Co2(CO)* reacts with the divalent samarium complexes (CSMes)2Sm(THF)2 and Sm12(THF), to form (CSMes)2(THF)SmCo(CO), and [Sm12(THF)s] [Co(CO),], respectively. Co2(CO), reacts with [(CSMes)SmI(THF)2]2 to form a complex that disproportionates to (CsMes)2(THF)SmCo(CO)4 and [ S I~I~( T H F )~] [Co(CO),]. The latter complex crystallizes from T H F in the triclinic space group PI with unit cell dimensions a = 8.829 (4) A, b = 12.965 (4) A, c = 14.740 (5) A, CY = 88.48 (3)O, p = 81.63 (3)O, y = 87.51 (3)', and Z = 2 for Dcald = 1.86 g Least-squares refinement on the basis of 1559 observed reflections led to a final R value of 0.041. The complex exists as discrete Sm12(THF)st cations and Co(CO), anions with no Sm-0-C-Co isocarbonyl linkage. The coordination geometry around the samarium atom is roughly pentagonal bipyramidal with the iodide atoms at the two apical positions (Sm-I distances 3.030 (2) and 3.009 (2) A). The Sm-O(THF) distances vary from 2.44 (1) to 2.47 (1) A. The Co(CO),anion has a tetrahedral geometry. In the early 1970s, several reactions involving transition-metal carbonyl complexes and lanthanide reagents were r e p~r t e d .~-~ Typical examples included (a) ionic metathesis reactions such as reaction of CSHsMo(CO)3-Na+ with LnCI, or (CSHS)2LnC1-(THF),S (b) reactions of t h e elemental lanthanide with a transition-metal carbonyl halide such as Mn(CO)sBr,4 (c) reactions of lanthanide amalgams with mercury derivatives of transitionmetal carbonyl anions such as H~[ C O ( C O )~]~,~ and (d) simple addition of tris(cyc1opentadienyI)lanthanides t o transition-metal carbonyls to form adduct^.^*^-^ Crystallographic characterization of t h e products of these reactions has proven difficult, and the precise structures remain unknown. NMR and IR spectroscopic evidence on lanthanide-transition-metal carbonyl reaction mixtures suggested that isccarbonyl linkages, Ln-0-C-M (Ln = lanthanide metal, M = transition metal), may exist in complexes of this t~p e .~-~ This is consistent with the highly oxophilic nature of the lanthanides in complexes.1° Divalent organolanthanide complexes react with transition-metal carbonyl complexes by reducing them to anionic species,' 1-14 and recently, for the pentamethylcyclopentadienyl-substituted complex (CSMeS)2Yb(OEt2), X-ray crystallographic data on these mixed transition-metal-lanthanide systems have become available. Reaction of t h e ytterbium reagent with C O~( C O )~, Fe3(C0)12, and Mn2(CO)lo has given [(CSMeS)2(THF)Yb] [(pOC)Co-(CO),],12 [(CsMes)2Yb]2[(~-OC),Fe3(C0)7],13 and a mixture of [[(CsMes)zYb] [(P-OC)2Mn(CO)3II2 and [[(CsMes)2Yb] [ ( P -OC),Mn(CO)2]],,14 respectively. In each product, the ytterbium exhibited t h e structural parameters of a trivalent species, t h e transition-metal carbonyl fragment was anionic, and the anions and cations were connected via Ln-O-C-M isocarbonyl linkages.