Profiling lithium distribution in Sn anode for lithium-ion batteries with neutrons

Measuring the distribution of lithium in high capacity lithium-ion battery (LIB) electrodes is essential to understanding the coulombic losses during the lithiation/delithiation processes that occur while charging and discharging the cell. In this research, two half-cell prototypes were fabricated by electrochemically lithiating Sn foil anodes in 1M LiBF₄ in a 1:1 (wt:wt) ethylene carbonate and dimethyl carbonate solutions at a constant potential of 0.50 and 0.67 V (vs. Li/Li⁺). The neutron depth profiling (NDP) technique was employed to study the Li distributions in the anodes. Li concentration profiles were resolved for the samples lithiated under different conditions for LIB studies. In addition, this paper demonstrated an in situ NDP measurement of an electrochemical cell with a thin window design, which reveals the dynamics of lithium distribution within the Sn anode.     

Substitution of Lithium for Magnesium,Zinc, and Aluminum in Li15Si4: Crystal Structures,Thermodynamic Properties,as well as 6Li and 7Li NMR Spectroscopy of Li15Si4 and Li15−xMxSi4 (M=Mg,Zn, and Al)

An investigation into the substitution effects in Li₁₅Si₄, which is discussed as metastable phase that forms during electrochemical charging and discharging cycles in silicon anode materials, is presented. The novel partial substitution of lithium by magnesium and zinc is reported and the results are compared to those obtained for aluminum substitution. The new lithium silicides Li₁₄MgSi₄ ( 1 ) and Li_14.05Zn_0.95Si₄ ( 2 ) were synthesized by high‐temperature reactions and their crystal structures were determined from single‐crystal data. The magnetic properties and thermodynamic stabilities were investigated and compared with those of Li_14.25Al_0.75Si₄ ( 3 ). The substitution of a small amount of Li in metastable Li₁₅Si₄ for more electron‐rich metals, such as Mg, Zn, or Al, leads to a vast increase in the thermodynamic stability of the resulting ternary compounds_. The ^6,7Li NMR chemical shift and spin relaxation time T₁‐NMR spectroscopy behavior at low temperatures indicate an increasing contribution of the conduction electrons to these NMR spectroscopy parameters in the series for 1 – 3 . However, the increasing thermal stability of the new ternary phases is accompanied by a decrease in Li diffusivity, with 2 exhibiting the lowest activation energy for Li mobility with values of 56, 60, and 62 kJ mol^?1 for 2 , Li_14.25Al_0.75Si₁₄, and 1 , respectively. The influence of the metastable property of Li₁₅Si₄ on NMR spectroscopy experiments is highlighted.     

Synthesis,Crystal Structure and Lithium Motion of Li8SeN2 and Li8TeN2

The compounds Li₈EN₂ with E = Se, Te were obtained in form of orange microcrystalline powders from reactions of Li₂E with Li₃N. Single crystal growth of Li₈SeN₂ additionally succeeded from excess lithium. The crystal structures were refined using single‐crystal X‐ray diffraction as well as X‐ray and neutron powder diffraction data (I4₁md, No. 109, Z = 4, Se: a = 7.048(1) Å, c = 9.995(1) Å, Te: a = 7.217(1) Å, c = 10.284(1) Å). Both compounds crystallize as isotypes with an anionic substructure motif known from cubic Laves phases and lithium distributed over four crystallographic sites in the void space of the anionic framework. Neutron powder diffraction pattern recorded in the temperature range from 3 K to 300 K and X‐ray diffraction patterns using synchrotron radiation taken from 300 K to 1000 K reveal the structural stability of both compounds in the studied temperature range until decomposition. Motional processes of lithium atoms in the title compounds were revealed by temperature dependent NMR spectroscopic investigations. Those are indicated by significant changes of the ⁷Li NMR signals. Lithium motion starts for Li₈SeN₂ above 150 K whereas it is already present in Li₈TeN₂ at this temperature. Quantum mechanical calculations of NMR spectroscopic parameters reveal clearly different environments of the lithium atoms determined by the electric field gradient, which are sensitive to the anisotropy of charge distribution at the nuclear sites. With respect to an increasing coordination number according to 2 + 1, 3, 3 + 1, and 4 for Li(3), Li(4), Li(2), and Li(1), respectively, the values of the electric field gradients decrease. Different environments of lithium predicted by quantum mechanical calculations are confirmed by ⁷Li NMR frequency sweep experiments at low temperatures.     

Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides

Lithiation of van der Waals tetrel-arsenides, GeAs and SiAs, has been investigated. Electrochemical lithiation demonstrated large initial capacities of over 950 mAh g⁻¹ accompanied by rapid fading over successive cycling in the voltage range 0.01–2 V. Limiting the voltage range to 0.5–2 V achieved more stable cycling, which was attributed to the intercalation process with lower capacities. Ex situ powder X-ray diffraction confirmed complete amorphization of the samples after lithiation, as well as recrystallization of the binary tetrel-arsenide phases after full delithiation in the voltage range 0.5–2 V. Solid-state synthetic methods produce layered phases, in which Si-As or Ge-As layers are separated by Li cations. The first layered compounds in the corresponding ternary systems were discovered, Li_0.9Ge_2.9As_3.1 and Li₃Si₇As₈, which crystallize in the Pbam (No. 55) and P2/m (No. 10) space groups, respectively. Semiconducting layered GeAs and SiAs accommodate the extra charge from Li cations through structural rearrangement in the Si-As or Ge-As layers and eventually by replacement of the tetrel dumbbells with sets of Li atoms. Ge and Si monoarsenides demonstrated high structural flexibility and a mild ability for reversible lithiation.     

7Li and 29Si solid state NMR and chemical bonding of La2Li2Si3

The ternary silicide La₂Li₂Si₃ was synthesized from the elements in a sealed niobium tube. La₂Li₂Si₃ was characterized by powder and single crystal X-ray diffraction: Ce₂Li₂Ge₃ type, Cmcm, a = 450.03(8), b = 1880.3(4), c = 689.6(1) pm, wR2 = 0.0178, 597 F² values, and 26 parameters. The La₂Li₂Si₃ structure contains two crystallographically independent silicon sites, both in slightly distorted trigonal prismatic coordination. The Si1 atoms are located in condensed La₆ prisms and form cis–trans chains (two-bonded silicon) with Si1–Si1 distances at 238 and 239 pm, indicating single bond character. The Si2 atoms are isolated within La₂Li₄ prisms. La₂Li₂Si₃ might be formally considered as an electron precise Zintl phase with an electron partition (2La³⁺)(2Li⁺)(2Si1^2–)(Si2^4–). Electronic structure calculations show a trend in this direction based on a charge density analysis with large electron localization around the Si1–Si1 chains. The compound is found weakly metallic with chemical bonding reminiscent of LaSi and additional features brought in by Li and Si2. High resolution solid state ⁷Li and ²⁹Si MAS-NMR spectra are in agreement with the crystal structural information, however, the ²⁹Si resonance shifts observed suggest strong Knight shift contributions, at variance with the Zintl concept. Variable temperature solid state ⁷Li spectra indicate the absence of motional narrowing on the kHz timescale within the temperature range 300K < T < 400 K.     

Structure and lithium mobility of Li<Subscript>4</Subscript>Pt<Subscript>3</Subscript>Si

The lithium-rich silicide Li₄Pt₃Si was synthesised from the elements by high-temperature synthesis in a sealed niobium ampoule. Its structure was refined on the basis of single-crystal X-ray diffraction data: R32, a = 693.7(2), c = 1627.1(4) pm, wR2 = 0.0762, 525 F² values and 21 variables. The striking structural motifs of the Li₄Pt₃Si structure are silicon atoms with a slightly distorted trigonal prismatic platinum coordination with short Si–Pt distances (238–246 pm). Always two trigonal prisms are condensed via a common Pt₃ triangle, and these double units built up a three-dimensional network by condensation via common corners. The channels left by this prismatic network are filled by two crystallographically independent lithium sites in a 3:1 ratio. The single crystal X-ray data were fully confirmed by neutron powder diffraction and ⁷Li magic-angle spinning (MAS)–nuclear magnetic resonance (NMR) results. The two distinct lithium sites are well differentiated by their ⁷Li isotropic chemical shift and nuclear electric quadrupolar interaction parameters. MAS-NMR spectra reveal signal coalescence effects above 300 K, indicating chemical exchange between the lithium sites on the millisecond timescale. The spectra can be simulated with a simple two-site exchange model. From the resulting temperature-dependent correlation times, an activation energy of 50 kJ/mol is extracted.     

Li/LiFePO4 batteries with room temperature ionic liquid as electrolyte

Room temperature ionic liquid (RTIL) was prepared on basis of N-methyl-N-butylpiperidinium bis(trifluoromethanesulfonyl)imide (PP₁₄TFSI), which showed a wide electrochemical window (?0.1–5.2 V vs. Li⁺/Li) and is theoretically feasible as an electrolyte for batteries with metallic Li as anodes. The addition of vinylene carbonate (VC) improved the compatibility of PP₁₄TFSI-based electrolyte towards lithium anodes and enhanced the formation of solid electrolyte interphase film to protect lithium anodes from corrosion. Accordingly, Li/LiFePO₄ cells initially delivered a discharge capacity of about 127 mAh g^?1 at a current density of 17 mA g^?1 in the ionic liquid with the addition of VC and showed better cyclability than in the neat ionic liquid. Electrochemical impedance spectroscopy disclosed that the addition of VC enhanced Li-ion diffusion and depressed interfacial resistance significantly.     

Air‐Stable Lithium Spheres Produced by Electrochemical Plating

Lithium metal is an ideal anode for next‐generation lithium batteries owing to its very high theoretical specific capacity of 3860 mAh g^?1 but very reactive upon exposure to ambient air, rendering it difficult to handle and transport. Air‐stable lithium spheres (ASLSs) were produced by electrochemical plating under CO₂ atmosphere inside an advanced aberration‐corrected environmental transmission electron microscope. The ASLSs exhibit a core–shell structure with a Li core and a Li₂CO₃ shell. In ambient air, the ASLSs do not react with moisture and maintain their core–shell structures. Furthermore, the ASLSs can be used as anodes in lithium‐ion batteries, and they exhibit similar electrochemical behavior to metallic Li, indicating that the surface Li₂CO₃ layer is a good Li⁺ ion conductor. The air stability of the ASLSs is attributed to the surface Li₂CO₃ layer, which is barely soluble in water and does not react with oxygen and nitrogen in air at room temperature, thus passivating the Li core.     

Topochemical Path in High Lithiation of MoS2

Lithiation of MoS₂/RGO (reduced graphite oxide) electrodes repeatedly reached experimental capacities larger than 1000 mA · g^–1, corresponding to at least 6 lithium equivalents per gram of MoS₂. At our best knowledge, a convincing explanation is still missing in literature. In most cases, phase separation into Li₂S and elemental Mo was assumed to occur. However, this can only explain capacities up to 669 mA · g^–1, corresponding to an exchange of four Li. Formation of LiMo alloys could resolve the problem but the Li/Mo system does not contain any binary phases. If signs for Li₂S formation were found, indeed experimental capacities were below 700 mAh · g^–1. Here we present a topochemical mechanism, which sustains multiple charge/discharge cycles at 1000 mAh · g^–1, corresponding to an exchange of at least 6 Li per formula unit MoS₂. This topochemical reaction route prevents decomposition into binary phases and thus avoids segregation of the components of MoS₂. Throughout the whole lithiation/delithiation process, distinct layers of Mo are preserved but extended or shrunk by slight movements and reshuffling of sulfur and lithium atoms. On addition of 6 Li per formula unit to MoS₂, all central sulfur atoms are hosted in mutual Mo–S layers such that formal S^2– and Mo^2– anions appear coordinated by lithium cations. Indeed, similar structures are known in the field of Zintl phases. Our first‐principles crystal structure prediction study describes this topological path through conversion reactions during the lithiation/delithiation processes. All optimized phases along the topological path exhibit a distinct Mo layering giving rise to a series of dominant scattering into pseudo 001 reflections perpendicular to these Mo planes. The mechanism we present here explains why such high capacities can be reached reversibly for MoS₂/RGO nano composites     

Transport Properties of Solid Electrolytes: Effect of the Isotope Composition of Lithium Charge Carriers

The isotope composition of lithium charge carriers is experimentally found to severely affect transport in solid electrolytes -Li₃BO₃, Li₃N, Li₃AlN₂, Li₅SiN₃, Li₆MoN₄, Li₆WN₄, and LiCl. The lithium cation conduction of these decreases with increasing content of ⁶Li or ⁷Li and reaches a minimum at [⁶Li] = [⁷Li]. The activation energy for conduction increases, reaches a maximum in the same compositions, and then diminishes. Rates of spin–lattice relaxation of ⁷Li nuclei in electrolytes are studied by an NMR method at 15–35 MHz. The calculated activation energy for short-range motion (to one interatom distance) of lithium charge carriers in crystal lattices of electrolytes is lower than that for ionic conduction by 2–3 times, which is attributed to two types of correlation (electrostatic, isotopic) of charge carriers.     

Magnetohydrodynamic Interface-Rearranged Lithium Ions Distribution for Uniform Lithium Deposition and Stable Lithium Metal Anode

Uneven lithium (Li) electrodeposition hinders the wide application of high-energy-density Li metal batteries (LMBs). Current efforts mainly focus on the side-reaction suppression between Li and electrolyte, neglecting the determinant factor of mass transport in affecting Li deposition. Herein, guided Li⁺ mass transport under the action of a local electric field near magnetic nanoparticles or structures at the Li metal interface, known as the magnetohydrodynamic (MHD) effect, are proposed to promote uniform Li deposition. The modified Li⁺ trajectories are revealed by COMSOL Multiphysics simulations, and verified by the compact and disc-like Li depositions on a model Fe₃O₄ substrate. Furthermore, a patterned mesh with the magnetic Fe−Cr₂O₃ core-shell skeleton is used as a facile and efficient protective structure for Li metal anodes, enabling Li metal batteries to achieve a Coulombic efficiency of 99.5 % over 300 cycles at a high cathode loading of 5.0 mAh cm⁻². The Li protection strategy based on the MHD interface design might open a new opportunity to develop high-energy-density LMBs.     

A Yolk–Shell Structured Silicon Anode with Superior Conductivity and High Tap Density for Full Lithium‐Ion Batteries

The poor cycling stability resulting from the large volume expansion caused by lithiation is a critical issue for Si‐based anodes. Herein, we report for the first time of a new yolk–shell structured high tap density composite made of a carbon‐coated rigid SiO₂ outer shell to confine multiple Si NPs (yolks) and carbon nanotubes (CNTs) with embedded Fe₂O₃ nanoparticles (NPs). The high tap density achieved and superior conductivity can be attributed to the efficiently utilised inner void containing multiple Si yolks, Fe₂O₃ NPs, and CNTs Li⁺ storage materials, and the bridged spaces between the inner Si yolks and outer shell through a conductive CNTs “highway”. Half cells can achieve a high area capacity of 3.6 mAh cm^?2 and 95 % reversible capacity retention after 450 cycles. The full cell constructed using a Li‐rich Li₂V₂O₅ cathode can achieve a high reversible capacity of 260 mAh g^?1 after 300 cycles.     

Solvation Structure with Enhanced Anionic Coordination for Stable Anodes in Lithium-Oxygen Batteries

Li-O₂ batteries have garnered much attention due to their high theoretical energy density. However, the irreversible lithium plating/stripping on the anode limits their performance, which has been paid little attention. Herein, a solvation-regulated strategy for stable lithium anodes in tetraethylene glycol dimethyl ether (G4) based electrolyte is attempted in Li-O₂ batteries. Trifluoroacetate anions (TFA⁻) with strong Li⁺ affinity are incorporated into the lithium bis(fluorosulfonyl)imide (LiTFSI)/G4 electrolyte to attenuate the Li⁺-G4 interaction and form anion-dominant solvates. The bisalt electrolyte with 0.5 M LiTFA and 0.5 M LiTFSI mitigates G4 decomposition and induces an inorganic-rich solid electrolyte interphase (SEI). This contributes to decreased desolvation energy barrier from 58.20 to 46.31 kJ mol⁻¹, compared with 1.0 M LiTFSI/G4, for facile interfacial Li⁺ diffusion and high efficiency. It yields extended lifespan of 120 cycles in Li-O₂ battery with a limited Li anode (7 mAh cm⁻²). This work gains comprehensive insights into rational electrolyte design for Li-O₂ batteries.     

Comparison of the electrochemical properties of metallic layered nitrides containing cobalt,nickel and copper in the 1 V–0.02 V potential range

We report the first example of an intercalation compound based on the nitrogen framework in which lithium can be intercalated and deintercalated. A comparison of the structural and electrochemical properties of the ternary lithium cobalt, nickel and copper nitrides is performed. Vacancy layered structures of ternary lithium nitridocobaltates Li_3−2xCo_xN and nitridonickelates Li_3−2xNi_xN with 0.10 ⩽ x ⩽ 0.44 and 0.20 ⩽ x ⩽ 0.60, respectively, are proved to reversibly intercalate Li ions in the 1 V–0.02 V potential range. These host lattices can accommodate up to 0.35 Li ion par mole of nitride. Results herein obtained support Li insertion in vacancies located in Li₂N⁻ layers while interlayer divalent cobalt and nickel cations are reduced to monovalent species. No structural strain is induced by the insertion–extraction electrochemical reaction which explains the high stability of the capacity in both cases. For the Li_1.86Ni_0.57N compound, a stable faradaic yield of 0.30 F/mol, i.e. 130 mAh/g, is maintained at least for 100 cycles. Conversely, the ternary copper nitrides corresponding to the chemical composition Li_3−xCu_xN with 0.10 ⩽ x ⩽ 0.40 do not allow the insertion reaction to take place due to the presence of monovalent copper combined with the lack of vacancies to accommodate Li ions. In the latter case, the discharge of the lithium copper nitrides is not reversible.     

Impedance study on the correlation between phase transition and electrochemical degradation of Si-based materials

In order to explain the relationship between physical change and electrochemical degradation of Co–Co₃O₄ coated Si, impedance spectroscopy on Co–Co₃O₄ coated Si was conducted at various states during charge or discharge. Nyquist plots during Li⁺ insertion (charge) showed a unique behavior that below 70 mV vs. Li/Li⁺, the more Li⁺’s were inserted into the electrode, the larger its comprehensive resistance was getting. During Li⁺ extraction (discharge), electrode resistance was decreased after going through 0.43 V vs Li/Li⁺. When these data were fitted with the ordinary equivalent circuit which is composed of electrolyte resistance, charge transfer resistance and contact resistance, there was an abrupt augmentation of charge transfer resistance below 70 mV vs. Li/Li⁺ during charge, whereas there was its drastic diminishment between 0.2 and 0.5 V vs. Li/Li⁺ during discharge. Because these potential regions are each related to amorphous Li_xSi-to-Li₁₅Si₄ transition and vice versa, it could be shown that the formation and decomposition of Li₁₅Si₄ is responsible for the electrochemical degradation of Co–Co₃O₄ coated Si.     

N- and S-doped ordered mesoporous carbon tubes with efficient S confinement for high-performance Li–S batteries

The insulating properties of S/Li₂S₂/Li₂S and the soluble Li₂S₄/Li₂S₆/Li₂S₈ obstruct the practical application of Li–S batteries. In this work, highly ordered N and S co-doped mesoporous carbon tubes (NSMCTBs) with high specific surface areas and large pore volume are employed to confine and improve the utilization efficiency of S species in Li–S batteries. The strong S_nLi₂?N interaction and S–S chemical bond between thiophenic S and Li₂S_n guarantee the exceptional electrochemical performance of as-prepared NSMCTBs/S cathode. A relatively high discharge capacity of 1315.2 mAh g^?1 is achieved for the first cycle at 0.5 C and maintained at 644.1 mAh g^?1 after 500 cycles. The NSMCTBs/S with high S content of up to 80%, it also delivers a discharge capacity of 1092.1 mAh g^?1 and considerable cycling performance. More importantly, the NSMCTBs/S can effectively suppress the self-discharge behavior of Li–S batteries.     

Li15Al3Si6 (Li14.6Al3.4Si6), a compound displaying a heterographite‐like anionic framework

The title compound, lithium aluminium silicide (15/3/6), crystallizes in the hexagonal centrosymmetric space group P6₃/m. The three‐dimensional structure of this ternary compound may be depicted as two interpenetrating lattices, namely a graphite‐like Li₃Al₃Si₆ layer and a distorted diamond‐like lithium lattice. As is commonly found for LiAl alloys, the Li and Al atoms are found to share some crystallographic sites. The diamond‐like lattice is built up of Li cations, and the graphite‐like anionic layer is composed of Si, Al and Li atoms in which Si and Al are covalently bonded [Si—Al = 2.4672 (4) Å].     

New NASICON type oxyanion high capacity anode, Li2Co2(MoO4)3, for lithium-ion batteries: preliminary studies

We describe in this paper the lithium insertion/extraction behavior of a new NASICON type Li₂Co₂(MoO₄)₃ at a low potential and explored the possibility of considering this new oxyanion material as anode for lithium-ion batteries for the first time. Li₂Co₂(MoO₄)₃ was synthesized by a soft-combustion glycine-nitrate low temperature protocol. Test cells were assembled using composite Li₂Co₂(MoO₄)₃ as the negative electrode material and a thin lithium foil as the positive electrode material separated by a microporous polypropylene (Celgard® membrane) soaked in aprotic organic electrolyte (1 M LiPF₆ in EC/DMC). Electrochemical discharge down to 0.001 V from OCV (～3.5 V) revealed that about 35 Li⁺ could ^possibly be inserted into Li₂Co₂(MoO₄)₃ during the first discharge (reduction) corresponding to a specific capacity amounting to 1,500 mAh g^?1. This is roughly fourfold higher compared to that of frequently used graphite electrodes. However, about 24 Li⁺ could be extracted during the first charge. It is interesting to note that the same amount of Li⁺ could be inserted during the second Li⁺ insertion process (second cycle discharge) giving rise to a second discharge capacity of 1,070 mAh g^?1. It was also observed that a major portion of lithium intake occurs below 1.0 V vs Li/Li⁺, which is typical of anodes being used in lithium-ion batteries.     

A novel anode material of antimony nitride for rechargeable lithium batteries

Antimony nitride thin film has been successfully fabricated by magnetron sputtering method and its electrochemistry with lithium was investigated for the first time. The reversible discharge capacity of Sb₃N/Li cells cycled between 0.3 V and 3.0 V was found above 600 mAh/g. By using transmission electron microscopy and selected area electron diffraction measurements, the conversion reaction of Sb₃N into Li₃Sb and Li₃N was revealed during the lithium electrochemical reaction of Sb₃N thin film electrode. The high reversible capacity and the good cycleability made Sb₃N one of promising anode materials for future rechargeable lithium batteries.     

Lithium Nitrate Regulated Sulfone Electrolytes for Lithium Metal Batteries

The electrolytes in lithium metal batteries have to be compatible with both lithium metal anodes and high voltage cathodes, and can be regulated by manipulating the solvation structure. Herein, to enhance the electrolyte stability, lithium nitrate (LiNO₃) and 1,1,2,2-tetrafuoroethyl-2′,2′,2′-trifuoroethyl(HFE) are introduced into the high-concentration sulfolane electrolyte to suppress Li dendrite growth and achieve a high Coulombic efficiency of >99 % for both the Li anode and LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) cathodes. Molecular dynamics simulations show that NO₃⁻ participates in the solvation sheath of lithium ions enabling more bis(trifluoromethanesulfonyl)imide anion (TFSI⁻) to coordinate with Li⁺ ions. Therefore, a robust LiN_xO_y−LiF-rich solid electrolyte interface (SEI) is formed on the Li surface, suppressing Li dendrite growth. The LiNO₃-containing sulfolane electrolyte can also support the highly aggressive LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) cathode, delivering a discharge capacity of 190.4 mAh g⁻¹ at 0.5 C for 200 cycles with a capacity retention rate of 99.5 %.