A study on lithium/air secondary batteries—Stability of NASICON-type glass ceramics in acid solutions

The stability of a NASICON-type lithium ion conducting solid electrolyte, Li_1+x+yTi_2−xAl_xP_3−ySi_yO₁₂ (LTAP), in acetic acid and formic acid solutions was examined. XRD patterns of the LTAP powders immersed in 100% acetic acid and formic acid at 50 °C for 4 months showed no change as compared to the pristine LTAP. However, the electrical conductivity of LTAP drastically decreased. On the other hand, no significant electrical conductivity change of LTAP immersed in lithium formate saturated formic acid-water solution was observed, and the electrical conductivity of LTAP immersed in lithium acetate saturated acetic acid-water increased. Cyclic voltammogram tests suggested that acetic acid was stable up to a high potential, but formic acid decomposed under the decomposition potential of water. The acetic acid solution was considered to be a candidate for the active material in the air electrode of lithium-air rechargeable batteries. The cell reaction was considered as 2Li + 2 CH₃COOH + 1/2O₂ = 2CH₃COOLi + H₂O. The energy density of this lithium-air system is calculated to be 1477 Wh kg⁻¹ from the weights of Li and CH₃COOH, and an observed open-circuit voltage of 3.69 V.     

Study on lithium/air secondary batteries—Stability of NASICON-type lithium ion conducting glass–ceramics with water

The water stability of the fast lithium ion conducting glass–ceramic electrolyte, Li_1+x+yAl_xTi_2−xSi_yP_3−yO₁₂ (LATP), has been examined in distilled water, and aqueous solutions of LiNO₃, LiCl, LiOH, and HCl. This glass–ceramics are stable in aqueous LiNO₃ and aqueous LiCl, and unstable in aqueous 0.1 M HCl and 1 M LiOH. In distilled water, the electrical conductivity slightly increases as a function of immersion time in water. The Li–Al/Li_3−xPO_4−yN_y/LATP/aqueous 1 M LiCl/Pt cell, where lithium phosphors oxynitrides Li_3−xPO_4−yN_y (LiPON) are used to protect the direct reaction of Li and LATP, shows a stable open circuit voltage (OCV) of 3.64 V at 25 °C, and no cell resistance change for 1 week. Lithium phosphors oxynitride is effectively used as a protective layer to suppress the reaction between the LATP and Li metal. The water-stable Li/LiPON/LATP system can be used in Li/air secondary batteries with the air electrode containing water.     

Lithium insertion into manganese dioxide electrode in MnO2/Zn aqueous battery: Part III. Electrochemical behavior of γ-MnO2 in aqueous lithium hydroxide electrolyte

The electrochemical behavior of γ-MnO₂ in lithium hydroxide (LiOH) and potassium hydroxide (KOH) aqueous media has been studied using slow-scan cyclic voltammetry (25 μV s⁻¹) in conjunction with X-ray analysis (XRD) and scanning electron microscopy (SEM). The reduction of γ-MnO₂ in aqueous LiOH results in intercalation of Li⁺ forming a new phase of lithium intercalated MnO₂ (Li_xMnO₂). The process is found to be reversible. In this regard, the reduction of γ-MnO₂ in LiOH is quite different from that in aqueous KOH, which is irreversible and no lithium intercalation occurs. This difference in behavior is explained in terms of the relative ionic sizes of Li ⁺ and K⁺. The Li_xMnO₂ lattice is stable only for Li⁺ because Li⁺ and Mn⁴⁺ are of approximately the same size whereas K_xMnO₂ is not stable because K⁺ has almost double the size.     

Gallium (III) sulfide as an active material in lithium secondary batteries

In an attempt to identify an active material for use in lithium secondary batteries with high energy density, we investigated the electrochemical properties of gallium (III) sulfide (Ga₂S₃) at 30 °C. Ga₂S₃ shows two sloping plateaus in the potential range between 0.01 V and 2.0 V vs. (Li/Li⁺). The specific capacity of the Ga₂S₃ electrode in the first delithiation is ca. 920 mAh g⁻¹, which corresponds to 81% of the theoretical capacity (assuming a 10-electron reaction). The capacity in the 10th cycle is 63% of the initial capacity. Ex situ X-ray diffraction and X-ray absorption fine structure analyses revealed that the reaction of the Ga₂S₃ electrode proceeds in two steps: Ga₂S₃ + 6Li⁺ + 6e⁻ ? 2Ga + 3Li₂S and Ga + xLi⁺ + xe⁻ ? Li_xGa.     

Layered lithium cobalt nitrides: A new class of lithium intercalation compounds

Lithium cobalt nitrides Li_3−2xCo_xN (0.1 ≤ x ≤ 0.44) have been prepared and investigated as negative electrode in the 1/0.02 V potential window. The evolution of the unit cell parameters and unit cell volume with the Co content show a solid solution behaviour. Whatever the Co content, all these nitrides are electroactive with a single step around 0.6 V/0.7 V for the discharge and charge processes, respectively. The electrochemical behaviour observed is typical of a Li intercalation compound and involves the Co²⁺/Co⁺ redox couple in the interlayer plane combined with the reversible accommodation of Li⁺ ions in the cation vacancies located in Li₂N⁻ layers. XRD experiments performed after discharge, charge and cycling tests clearly indicate the hexagonal layered structure of the host lattice is maintained. This intercalation process explains the excellent capacity retention found after 50 cycles. A specific capacity of 180 mAh g⁻¹ at C/20 and 130 mAh g⁻¹ at C/5 rate (100 mA cm⁻²) is achieved for Li_2.23Co_0.39N. ac impedance measurements have allowed to characterize the kinetics of the reaction.     

Electrochemical properties of doped lithium titanate compounds and their performance in lithium rechargeable batteries

Several substituted titanates of formula Li_4−xMg_xTi_5−xV_xO₁₂ (0 ≤ x ≤ 1) were synthesized (and investigated) as anode materials in rechargeable lithium batteries. Five samples labeled as S1–S5 were calcined (fired) at 900 °C for 10 h in air, and slowly cooled to room temperature in a tube furnace. The structural properties of the synthesized products have been investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transmission infrared (FTIR). XRD explained that the crystal structures of all samples were monoclinic while S1 and S3 were hexagonal. The morphology of the crystal of S1 was spherical while the other samples were prismatic in shape. SEM investigations explained that S4 had larger grain size diameter of 15–16 μm in comparison with the other samples. S4 sample had the highest conductivity 2.452 × 10⁻⁴ S cm⁻¹. At a voltage plateau located at about 1.55 V (vs. Li ⁺), S4 cell exhibited an initial specific discharge capacity of 198 mAh g⁻¹. The results of cyclic voltammetry for Li_4−xMg_xTi_5−xV_xO₁₂ showed that the electrochemical reaction was based on Ti⁴⁺/Ti³⁺ redox couple at potential range from 1.5 to 1.7 V. There is a pair of reversible redox peaks corresponding to the process of Li⁺ intercalation and de-intercalation in the Li–Ti–O oxides.     

A new lithium salt with dihydroxybenzene and lithium tetrafluoroborate for lithium battery electrolytes

A new unsymmetrical lithium salt containing F⁻, C₆H₄O₂²⁻ [dianion of 1,2-benzenediol], lithium difluoro(1,2-benzene-diolato(2-)-o,o′)borate (LDFBDB) is synthesized and characterized. Its thermal decomposition in nitrogen begins at 170 °C. The cyclic voltammetry study shows that the LDFBDB solution in propylene carbonate (PC) is stable up to 3.7 V versus Li⁺/Li. It is soluble in common organic solvents. The ionic dissociation properties of LDFBDB are examined by conductivity measurements in PC, PC+ ethyl methyl carbonate (EMC), PC + dimethyl ether (DME), PC + ethylene carbonate (EC) + EMC solutions. The conductivity values of the 0.564 mol dm⁻³ LDFBDB electrolyte in PC + DME solution is 3.90 mS cm⁻¹. All these properties of the new lithium salt including the thermal characteristics, electrochemical stabilities, solubilities, ionic dissociation properties are studied and compared with those of its derivatives, lithium difluoro(3-fluoro-1,2-benzene-diolato(2-)-o,o′)borate (FLDFBDB), lithium [3-fluoro-1,2-benzenediolato(2-)-o,o′ oxalato]borate (FLBDOB), and lithium bis(oxalate)borate (LBOB).     

Electrolytic Sn/Li2O coatings for thin-film lithium ion battery anodes

Sn/Li₂O composite coatings on stainless steel substrate, as anodes of thin-film lithium battery are carried out in SnCl₂ and LiNO₃ mixed solutions by using cathodic electrochemical synthesis and subsequently annealed at 200 °C. Through cathodic polarization tests, three major regions are verified: (I) O₂ + 4H⁺ + 4e⁻ → 2H₂O (∼0.25 to −0.5 V), (II) 2H⁺ + 2e⁻ → H₂, Sn²⁺ + 2e⁻ → Sn, and NO₃⁻ + H₂O + 2e⁻ → NO₂⁻ + 2OH⁻ (−0.5 to −1.34 V), and (III) 2H₂O + 2e⁻ → H₂ + 2OH⁻ (−1.34 to −2 V vs. Ag/AgCl). The coated specimens are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and charge/discharge tests. The nano-sized Sn particles embedded in Li₂O matrix are obtained at the lower part of region II such as −1.2 V, while the micro-sized Sn with little Li₂O at the upper part, such as −0.7 V. Charge/discharge cycle tests elucidated that Sn/Li₂O composite film showed better cycle performance than Sn or SnO₂ film, due to the retarding effects of amorphous Li₂O on the further aggregation of Sn particles. On the other hand, the one tested for cut-off voltage at 0.9 V (vs. Li/Li⁺) is better than those at 1.2 and 1.5 V since the incomplete de-alloy at lower cut-off voltage may inhibit the coarsening of Sn particles, revealing capacity 587 mAh g⁻¹ after 50 cycle, and capacity retention ratio C50/C2 81.6%, higher than 63.5% and 49.1% at 1.2 and 1.5 V (vs. Li/Li⁺), respectively.     

Electrical conductivity and reaction with lithium of LiFe1−yMnyPO4 olivine-type cathode materials

Structural, electrical and electrochemical properties of Mn-substituted phospho-olivines LiFe_1−yMn_yPO₄ were investigated and compared to those of LiFePO₄. Rietvield refined XRD patterns taken in the course of delithiation process showed apparent difference between phase compositions of these cathode materials upon lithium extraction. Contrary to the LiFePO₄ and LiMnPO₄ compositions for which a two-phase mechanism of electrochemical lithium extraction/insertion is observed, in case of Mn-substituted LiFe_1−yMn_yPO₄ samples a single-phase mechanism of deintercalation was observed in the studied range of lithium concentration. Electrochemical characterization of the cathode materials were performed in Li/Li⁺/Li_xFe_1−yMn_yPO₄-type cells for y = 0.0, 0.25, 0.55, 0.75 and 1.0 compositions. Voltammery studies showed low reversibility of the lithium extraction process in the high-voltage “manganese” range, while in the “iron” range the reversibility of lithium extraction is high. Impedance measurements of the LiFe_1−yMn_yPO₄ cathode materials, which enabled separation of the ionic and electronic components of their entire electrical conductivity, showed distinct influence of Mn content on the electronic part of conductivity. EIS measurements performed at different states of cell charge revealed that the charge-transfer impedance in Li_xFe_1−yMn_yPO₄ is much lower than that of Li_xFePO₄.     

Development of non-flammable lithium secondary battery with room-temperature ionic liquid electrolyte: Performance of electroplated Al film negative electrode

The negative electrode performance of the electroplated Al film electrode in the LiCl saturated AlCl₃–1-ethyl-3-methylimizadolium chloride (EMIC) + SOCl₂ melt as the electrolyte for use in non-flammable lithium secondary batteries was evaluated. In the cyclic voltammogram of the electroplated Al film electrode in the melt, the oxidation and reduction waves corresponding to the electrochemical insertion/extraction reactions of the Li⁺ ion were observed at 0–0.80 V vs. Li⁺/Li, which suggested that the electroplated Al film electrode operated well in the electrolyte. The almost flat potential profiles at about 0.40 V vs. Li⁺/Li on discharging were shown. The discharge capacity and charge–discharge efficiency was 236 mAh g⁻¹ and 79.2% for the 1st cycle and it maintained 232 mAh g⁻¹ and 77.9% after the 10th cycle. In addition, the initial charge–discharge efficiencies of the electroplated Al film electrode were higher than that of carbon electrodes. The main cathodic polarization reaction was the insertion of Li⁺ ions, and side reactions hardly occurred due to the decomposition reaction of the melt because the Li content corresponding to the electricity was almost totally inserted into the film after charging.     

Formation of the high lithium ion conducting phase from mechanically milled amorphous Li2S-P2S5 system

The fast ionic conducting structure similar to thio-Lithium Super Ionic Conductor (LISICON) phase is synthesized in the Li₂S-P₂S₅ system. The Li₂S-P₂S₅ glass-ceramics with the composition of xLi₂S·(100−x)P₂S₅ (75 ≤ x ≤ 80) are prepared by the heat-treatment of mechanically milled amorphous sulfide powders. In the binary Li₂S-P₂S₅ system, 78.3Li₂S·21.7P₂S₅ glass ceramic prepared by mechanical milling and subsequent heat-treatment at 260 °C for 3 h shows the highest conductivity of 6.3 × 10⁻⁴ S cm⁻¹ at room temperature and the lowest activation energy for conduction of 30.5 kJ mol⁻¹. The enhancement of conductivity with increasing x up to 78.3 is probably caused by the introduction of interstitial lithium ions at the Li sites which affects the Li ion distribution. The prepared electrolyte exhibits the lithium ion transport number of almost unity and voltage stability of 5 V vs. Li at room temperature.     

Electrochemical behavior of Li3−xM′xV2−yM″y(PO4)3 (M′ = K, M″ = Sc, Mg + Ti)/C composite cathode material for lithium-ion batteries

Composites of monoclinic Li_3−xM′_xV_2−yM″_2y(PO₄)₃ (M′ = K, M″ = Sc, Mg + Ti) with carbon were synthesized by solid-state reaction using oxalic acid or 6% H₂/Ar gas mixture as reducing agents at sintering temperature of 850 °C. The samples were characterized by X-ray diffraction (XRD), voltammetry and electrochemical galvanostatic cycling. The capacity of Li₃V₂(PO₄)₃ synthesized using hydrogen as the reducing agent was 127 mA h g⁻¹ and decreased to 120 mA h g⁻¹ after 20 charge-discharge cycles. The substitution of lithium and vanadium for other ions did not result in the improvement of the electrochemical characteristics of the samples.     

High-throughput studies of Li1−xMgx/2FePO4 and LiFe1−yMgyPO4 and the effect of carbon coating

A two-dimensional sample array synthesis has been used to screen carbon-coated Li_(1−x)Mg_x/2FePO₄ and LiFe_(1−y)Mg_yPO₄ powders as potential positive electrode materials in lithium ion batteries with respect to x, y and carbon content. The synthesis route, using sucrose as a carbon source as well as a viscosity-enhancing additive, allowed introduction of the Mg dopant from solution into the sol–gel pyrolysis precursor. High-throughput XRD and cyclic voltammetry confirmed the formation of the olivine phase and percolation of the electronic conduction path at sucrose to phosphate ratios between 0.15 and 0.20. Measurements of the charge passed per discharge cycle showed that the capacity deteriorated on increasing magnesium in Li_(1−x)Mg_x/2FePO₄, but improved with increasing magnesium in LiFe_(1−y) Mg_yPO₄, especially at high scan rates. Rietveld-refined XRD results on samples of LiFe_(1−y)Mg_yPO₄ prepared by a solid-state route showed a single phase up to y = 0.1 according to progressive increases in unit cell volume with increases in y. Carbon-free samples of the same materials showed conductivity increases from 10⁻¹⁰ to 10⁻⁸ S cm⁻¹ and a decrease of activation energy from 0.62 to 0.51 eV. Galvanostatic cycling showed near theoretical capacity for y = 0.1 compared with only 80% capacity for undoped material under the same conditions.     

2LiH + M (M = Mg, Ti): New concept of negative electrode for rechargeable lithium-ion batteries

xLiH + M composites, where M = Mg or Ti, are suggested as new candidates for negative electrode for Li-ion batteries. For this purpose, the xLiH + M electrode is prepared using the mechanochemical reaction: MH_x + xLi → xLiH + M or by simply grinding a xLiH + M mixture. The most promising electrochemical behaviour is obtained with the (2LiH + Mg) composite prepared via a mechanochemical reaction between MgH₂ and metallic Li leading to a very divided composite in which Mg crystallites of 20 nm size are embedded in a LiH matrix. Reversible capacities of 1064 mAh g⁻¹ (three times as much as the one of graphite) and 600 mAh g⁻¹ are reached for these phase mixtures after 1 and 28 h of grinding in vertical and planetary mill, respectively. The (2LiH + Ti) mixture prepared via the mechanochemical reaction between TiH₂ and Li exhibits a reversible capacity of 428 mAh g⁻¹. From X-ray diffraction measurements, the performances of the electrodes are attributed to the electrochemical conversion reaction: M + xLiH ↔ MH_x + xLi⁺ + xe⁻ (M = Mg, Ti) followed for M = Mg by an alloying process where M reacts with lithium ions to form Mg_1−xLi_x alloys.     

Preparation of Li2S-GeSe2-P2S5 electrolytes by a single step ball milling for all-solid-state lithium secondary batteries

Glass-ceramic and glass Li₂S-GeSe₂-P₂S₅ electrolytes were prepared by a single step ball milling (SSBM) process. Various compositions of Li_4−xGe_1−xP_xS_2(1+x)Se_2(1−x) with/without heat treatment (HT) from x = 0.55 to x = 1.00 were systematically investigated. Structural analysis by X-ray diffraction (XRD) showed gradual increase of the lattice constant followed by significant phase change with increasing GeSe₂. HT also affected the crystallinity. Incorporation of GeSe₂ in Li₂S-P₂S₅ kept high conductivity with a maximum value of 1.4 × 10⁻³ S cm⁻¹ at room temperature for x = 0.95 in Li_4−xGe_1−xP_xS_2(1+x)Se_2(1−x) without HT. All-solid-state LiCoO₂/Li cells using Li₂S-GeSe₂-P₂S₅ as solid-state electrolytes (SE) were tested by constant-current constant-voltage (CCCV) charge-discharge cycling at a current density of 50 μA cm⁻² between 2.5 and 4.3 V (vs. Li/Li⁺). In spite of the extremely high conductivity of the SE, LiCoO₂/Li cells showed a large irreversible reaction especially during the first charging cycle. LiCoO₂ with SEs heat-treated at elevated temperature exhibited a capacity over 100 mAh g⁻¹ at the second cycle and consistently improved cycle retention, which is believed to be due to the better interfacial stability.     

High lithium ionic conductivity in the garnet-type oxide Li7−X La3(Zr2−X, NbX)O12 (X = 0-2)

Lithium garnet-type oxides Li_7−XLa₃(Zr_2−X, Nb_X)O₁₂ (X = 0-2) were synthesized by a solid-state reaction, and their lithium ion conductivity was measured using an AC impedance method at temperatures ranging from 25 to 150 °C in air. The lithium ion conductivity increased with increasing Nb content, and reached a maximum of ∼0.8 mS cm⁻¹ at 25 °C. By contrast, the activation energy reached a minimum of ∼30 kJ mol⁻¹ at the same point with X = 0.25. The potential window was examined by cyclic voltammetry (CV), which showed lithium deposition and dissolution peaks around 0 V vs. Li⁺/Li, but showed no evidence of other reactions up to 9 V vs. Li⁺/Li.     

A new lithium salt with 3-fluoro-1,2-benzenediolato and lithium tetrafluoroborate for lithium battery electrolytes

A new unsymmetrical lithium salt containing F⁻, C₆H₃O₂F²⁻ [dianion of 3-fluoro-1,2-benzenediol], lithium difluoro(3-fluoro-1,2-benzene-diolato(2-)-o,o′)borate (FLDFBDB) is synthesized and characterized. The thermal characteristics of it, and its derivatives, lithium bis[3-fluoro-1, 2-benzenediolato(2-)-o,o]borate (FLBBB), and lithium fluoroborate (LiBF₄) are examined by thermogravimetric analysis (TG). The thermal decomposition in air begins at 256 °C, 185 °C, and 162 °C for FLBBB, FLDFBDB and LiBF₄, respectively. The order of the stability toward the oxidation of these organoborates is LiBF₄ > FLDFBDB > FLBBB. The cyclic voltammetry study shows that the FLDFBDB solution in propylene carbonate (PC) is stable up to 3.9 V vs. Li⁺/Li. It is soluble in common organic solvents. Ionic dissociation properties of FLDFBDB and its derivatives are examined by conductivity measurements in PC, PC + ethyl methyl carbonate (EMC), PC + dimethyl ether (DME), PC + ethylene carbonate (EC) + DME, PC + EC + EMC solutions. The conductivity values of the 0.10 mol dm⁻³ FLDFBDB electrolyte in these solutions are higher than those of FLBBB, but lower than those of LiBF₄ electrolytes.     

Synthesis and electrochemical performance of Li2CoSiO4 as cathode material for lithium ion batteries

Li₂CoSiO₄ has been prepared successfully by a solution route or hydrothermal reaction for the first time, and its electrochemical performance has been investigated primarily. Reversible extraction and insertion of lithium from and into Li₂CoSiO₄ at 4.1 V versus lithium have shown that this material is a potential candidate for the cathode in lithium ion batteries. At this stage reversible electrochemical extraction was limited to 0.46 lithium per formula unit for the Li₂CoSiO₄/C composite materials, with a charge capacity of 234 mAh g⁻¹ and a discharge capacity of 75 mAh g⁻¹.     

Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material

Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂ layered materials were synthesized by the co-precipitation method with different Li/M molar ratios (M = Ni + Mn + Co). Elemental titration evaluated by inductively coupled plasma spectrometry (ICP), structural properties studied by X-ray diffraction (XRD), Rietveld analysis of XRD data, scanning electron microscopy (SEM) and magnetic measurements carried out by superconducting quantum interference devices (SQUID) showed the well-defined α-NaFeO₂ structure with cationic distribution close to the nominal formula. The Li/Ni cation mixing on the 3b Wyckoff site of the interlayer space was consistent with the structural model [Li_1−yNi_y]_3b[Li_x+yNi_{(1−x)/3−y}Mn_(1−x)/3Co_(1−x)/3]_3aO₂ (x = 0.02, 0.04) and was very small. Both Rietveld refinements and magnetic measurements revealed a concentration of Ni²⁺-3b ions lower than 2%; moreover, for the optimized sample synthesized at Li/M = 1.10, only 1.43% of nickel ions were located into the Li sublattice. Electrochemical properties were investigated by galvanostatic charge-discharge cycling. Data obtained with Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂ reflected the high degree of sample optimization. An initial discharge capacity of 150 mAh g⁻¹ was delivered at 1 C-rate in the cut-off voltage of 3.0-4.3 V. More than 95% of its initial capacity was retained after 30 cycles at 1 C-rate. Finally, it is demonstrated that a cation mixing below 2% is considered as the threshold for which the electrochemical performance does not change for Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂.     

Surface structural disordering in graphite upon lithium intercalation/deintercalation

We report on the origin of the surface structural disordering in graphite anodes induced by lithium intercalation and deintercalation processes. Average Raman spectra of graphitic anodes reveal that cycling at potentials that correspond to low lithium concentrations in Li_xC (0 ≤ x < 0.16) is responsible for most of the structural damage observed at the graphite surface. The extent of surface structural disorder in graphite is significantly reduced for the anodes that were cycled at potentials where stage-1 and stage-2 compounds (x > 0.33) are present. Electrochemical impedance spectra show larger interfacial impedance for the electrodes that were fully delithiated during cycling as compared to electrodes that were cycled at lower potentials (U < 0.15 V vs. Li/Li⁺). Steep Li⁺ surface-bulk concentration gradients at the surface of graphite during early stages of intercalation processes, and the inherent increase of the Li_xC d-spacing tend to induce local stresses at the edges of graphene layers, and lead to the breakage of C-C bonds. The exposed graphite edge sites react with the electrolyte to (re)form the SEI layer, which leads to gradual degradation of the graphite anode, and causes reversible capacity loss in a lithium-ion battery.