Hydroxyl terminated Poly(dimethylsiloxane) as an electrolyte additive to enhance the cycle performance of lithium-ion batteries

Hydroxyl terminated poly(dimethylsiloxane) (PDMS-HT) is used as an electrolyte additive in electrolyte systems containing 1 M LiPF₆ in EC:DMC (ratios 1:9; 3:7; 4:6 and 1:1 v/v) to enhance the cycle performance of lithium-ion batteries. Adding a small amount of PDMS-HT to the standard LIB electrolyte leads to improved specific capacity as well as improved capacity retention over prolonged cycles. There is also a slight increase in Li⁺ ion conductivity when PDMS-HT is added. Also, the PDMS-HT additive allows the formation of a more stable solid electrolyte interface (SEI) layer that enables the LIB cells to be cycled for longer cycles with minimal capacity fading. This combination of improved ionic conductivity and stable SEI layer formation due to the PDMS-HT additive, makes it an excellent candidate for an electrolyte additive for lithium ion batteries.     

Blended lithium ion conducting polymer electrolytes based on boroxine polymers

A new series of blended polymer electrolytes based on a boroxine polymer (BP) with poly(ethylene oxide) (PEO), an ethylene oxide–propylene oxide copolymer or poly(methyl methacrylate) were prepared. Good room temperature mechanical properties were exhibited by electrolytes containing in excess of 30% PEO. Cationic transference number measurements indicated that a slight improvement in lithium ion conductivity could be achieved by using a mixture of LiCF₃SO₃ and LiN(CF₃SO₂)₂ as the electrolyte salt. Electrolytes incorporating significant proportions of BP exhibited reduced lithium–polymer electrolyte interfacial resistance.     

Characterization of solid electrolytes prepared from ionic glass and ionic liquid for all-solid-state lithium batteries

Glassy solid electrolytes were prepared by combining the 50Li₂SO₄·50Li₃BO₃ (mol%) ionic glass and the 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([EMI]BF₄) ionic liquid. High-energy ball milling was carried out for the mixture of the inorganic ionic glass and the organic ionic liquid. The ambient temperature conductivity of the glass electrolyte with 10 mol% [EMI]BF₄ was 10⁻⁴ S cm⁻¹, which was three orders of magnitude higher than that of the 50Li₂SO₄·50Li₃BO₃ glass. The addition of [EMI]BF₄ to the ionic glass decreased glass transition temperature (T_g) of the glass and the decrease of T_g is closely related to the enhancement of conductivity of the glass. Morphology and local structure of the glass electrolyte was characterized. The dissolution of an ionic liquid in an ionic glass with Li⁺ ion conductivity is a novel way to developing glass electrolytes for all-solid-state lithium secondary batteries.     

Effects of cobalt metal addition on sintering and ionic conductivity of Sm(Y)-doped ceria solid electrolyte for SOFC

The effects of cobalt addition (0.5 and 1 wt.%) on densification and ionic conductivity of Ce_0.9Sm_0.1O_1.95 (10SDC) and Ce_0.9Sm_0.075Y_0.025O_1.95 (2.5Y-SDC) have been studied. X-ray diffraction (XRD) showed that Co had changed to Co₃O₄ and Co₃O₄ + CoO after firing at 900 °C and 1300 °C respectively. The addition of Co promoted densification to occur at lower temperatures with a more uniform grain growth and greatly improved both grain boundary and bulk conductivity for 10SDC. Significant improvement of grain boundary for the 2.5Y-SDC samples was obtained, even at 1300 °C sintering, while bulk conductivity was slightly improved. Rapid grain growth along with improvement of ionic conductivity was observed when the samples were sintered further at higher temperature. Superior ionic conductivity of the 2.5Y-SDC samples with Co addition to that of the bare 10SDC suggested the potential use of Co as the co-dopant in this system to reduce the content of costly rare earth usage.     

Comblike polymer electrolyte with main chain glass transition near room temperature

A new amorphous comblike polymer (CBP) based on methylvinyl ether/maleic anhydride altering copolymer backbone and on oligooxyethylene side chain was synthesized. The dynamic mechanical properties of CBP and its Li salt complexes were investigated by means of DDV-ll-EA type viscoelastic spectrometry. Results showed that there were two glass transitions (-transition and β-transition) in the temperature range from − 100 to 100 °C. The β-transition was assigned to oligo-PEO side chains and the temperature of β-transition increases with increasing Li salt content. The -transition was assigned to the main chain of CBP. The temperature of the -transition (T) is also dependent upon the Li-salt content, but not monotonie. The value of T lies between 30–45 °C in the Li salt concentration range studied, near room temperature. It was found that the CBP-Li salt complexes showed an unusual dependence of ionic conductivity on Li salt content. There are two peaks in the plot of the ionic conductivity vs. Li salt concentration, which has been ascribed to the movability of the CBP main chain at ambient temperature. The temperature dependence of the ionic conductivity indicated that the Arrhenius relationship was not obeyed, and the plot of log σ against 1/(T − T₀) showed the unusual dual VTF behavior when using side chain glass transition temperature (T_β) as T₀.     

Effects of plasticizer and nanofiller on the dielectric dispersion and relaxation behaviour of polymer blend based solid polymer electrolytes

Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF₃SO₃) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li⁺ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF₃SO₃ electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10⁻⁵ S cm⁻¹, confirming their use in preparation of all-solid-state ion conducting devices.     

Preparation and characterizations of PMMA-PVDF based polymer composite electrolyte materials for dye sensitized solar cell

Blend polymer composite gel electrolytesare prepared using thepoly vinyledene fluoride (PVDF), polymethyl methacrylate (PMMA) with alumina (Al₂O₃) in variance of alkali metal iodide saltsystem. The alumina doped blend polymer electrolytes characterized by the XRD diffraction and FT-IR spectra. This is supportive to the conformation of the crystallinity behaviour and the composite formation.The high-resolution scanning electron microscopy (HR-SEM) have used to find the composite electrolyte membrane porous size (10 μm) and it has support to understand the morphological structure of the membrane. To analyze the ionic conductivity of the potassium iodide based composite polymer electrolyte by the impedance measurements, which is 4.62 × 10⁻³ Scm⁻¹ at room temperature. Finally, different alkali metal iodide based dye-sensitized solar cells (DSSCs) fabricated and monitored an energy conversion efficiency.     

Effect of fillers on magnesium–poly(ethylene oxide) solid polymer electrolyte

A solid polymer electrolyte (SPE) film consisting of poly(ethylene oxide) (PEO) with magnesium chloride as electrolytic salt and B₂O₃ as the filler has been prepared by solution casting technique. The polymeric film was flexible and self-standing with proper mechanical strength and studied for application in a solid-state rechargeable magnesium battery. The interactions between the filler and PEO chains are studied by differential scanning calorimeter and Fourier transform infrared techniques. Composition of SPE is optimized, and maximum conductivity is obtained at 2 wt% B₂O₃. Filler seems to increase the number of free magnesium cations by decoordinating the bond between magnesium cations and ether oxygen of PEO. Cyclic voltammetry results show the reversible capability of magnesium electrode. Solid-state magnesium cell employing magnesium anode, SPE, and manganese oxide was assembled, and its open circuit voltage is found to be 1.9 V.     

Effect of monocationic ionic liquids as electrolyte additives on the electrochemical and thermal properties of Li-ion batteries

The conventional electrolyte system has been compared with the ionic liquid (IL) additive containing electrolyte system at room temperature as well as elevated temperature. In this work, two types of monocationic ILs such as 1-butyl-3-methylpyrrolidinium hexafluorophosphate (Pyr IL) and 1-ethyl-3-methylimidazolium hexafluorophosphate (IMI IL) are added as an additive at two different weight ratios in 1.15 M LiPF₆ (EC/EMC = 3/7 v/v) electrolyte solution, the structural, electrochemical and thermal characteristics of LiNi_0.80Co_0.15Al_0.05O₂ (NCA)/carbon full-cell in different electrolyte formulations have been reconnoitered. X-ray diffraction (XRD) studies have proved that IL as an electrolyte additive does not alter the structural stability of cathode materials after cycling. Under room temperature, Pyr IL additives at 1 wt% and 3 wt% deliver better cycleability than others, with the retention ratios of 93.62% and 92.8%, respectively. At elevated temperature, only 1 wt% Pyr IL additive is giving stable capacity retention ratio of 80.74%. Ionic conductivity and self-extinguishing time (SET) values are increasing with respect to the amount of additive added to the electrolyte. Thermal studies reveal that 3 wt% Pyr IL is favorable regarding the safety of the battery as it shows shifting of peak to higher temperature of 272.10 °C. Among the IL additives evaluated in this study, addition of 1 wt% Pyr IL is the most desirable additive for achieving the best cycling performance as well as thermal behavior of Li-ion batteries.     

3-D microbattery electrolyte by self-assembly of oligomers

This paper reports the preparation and characterization of novel thin film electrolytes by UV cross-linking of poly(propylene glycol) diacrylate in the presence of polyetheramine (glyceryl poly(oxypropylene)triamine) and LiTFSI. The oligomeric surfactant polyetheramine facilitates self-assembly of the electrolyte, enabling it to be applied conformally onto a complex substrate which is necessary for 3D-microbatteries, while the acrylate network supplies mechanical stability. Conformal coatings onto LiFePO₄ electrodes and Cu nanopillars were confirmed by SEM. Ionic conductivities of 3.5 × 10^− 6 and 5.8 × 10^− 5 S/cm were measured at room temperature and 60 °C, respectively, at Li:O = 1:20 and PEA:PPGDA = 2:1 ratios. The electrochemical stability window test showed that the electrolyte is stable above 5.0 V vs. Li/Li⁺. Thermal analyses by TGA and DSC demonstrated that the polymer electrolyte is amorphous and thermally stable up to 300 °C.     

Synthesis and characterization of apatite-type La9.67Si6-xAlxO26.5-x/2 electrolyte materials and compatible cathode materials

Apatite silicates have recently been reported as promising electrolyte materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this work, a series of apatite-type compounds La_9.67Si_6-xAl_xO_26.5-x/2 (LSAO) with x = 0-2 are synthesized by the sol-gel process at calcining temperature of 800-900 °C. Thermal expansion coefficient, relative density and electrical conductivity of these samples with different Al doped contents are investigated. A symmetrical cell, which is composed of La_9.67Si₅AlO₂₆ electrolyte and (La_0.74Bi_0.10Sr_0.16)MnO_3+δ (LBSM) cathode, is fabricated and electrochemically characterized. LBSM cathode shows a good electrochemical performance, which proves LBSM to be a promising candidate cathode for LSAO-based electrolyte.     

Computational screening of lactam molecules as solid electrolyte interphase forming additives in lithium-ion batteries

N-Substituted acetyl ε-caprolactam is known as a novel solid electrolyte interphase (SEI)-forming additive for improving the cycle performance of LiCoO₂/graphite lithium-ion batteries. We suggest four lactam derivatives as promising candidates for SEI-forming additives with a higher performance than N-acetyl ε-caprolactam as determined via first-principles density functional calculations of oxidation potentials, reduction potentials, and Li⁺ binding affinities. This computational screening protocol provides a shortcut for development of new SEI-forming electrolyte additives in lithium-ion batteries.     

Design and synthesis of a novel 3D hierarchical mesocarbon microbead as anodes for lithium ion batteries and sodium ion batteries

This work presents a feasible route for the facile synthesis of three-dimensional (3D) hierarchical mesocarbon microbead (MCMB) as anodes for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). The MCMB is oxidized by modified hummers method, and then the precursor is treated by hydrogen reduction to form the HMCMB. The HMCMB with graphene-like architecture has high specific surface, sufficient pore volume, and increased interlayer spacing, which can provide more active insertion/extraction sites and reduce the Li⁺/Na⁺ diffusion resistance. When employed as anode materials for LIBs and SIBs, HMCMB anodes exhibit improved lithium and sodium storage capability. The HMCMB delivers a higher reversible capacity (471.1 and 177.5 mAh g^?1 at 100 mA g^?1 after 100 cycles) and a good rate performance (250 and 121 mAh g^?1 even at 1000 mA g^?1) for LIBs and SIBs, respectively.     

Influence of the lithium salt nature over the surface film formation on a graphite electrode in Li-ion batteries: An XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium-ion cells using different salts (LiBF₄, LiPF₆, LiTFSI, LiBETI) in carbonate solvents as electrolyte was investigated by X-ray photoelectron spectroscopy (XPS). The analyzes were carried out at different potential stages of the first cycle, showing the potential-dependent character of the surface film species formation and the specificity of each salt. At 3.8 V, for all salts, we have mainly identified carbonated species. Beyond this potential, the specific behavior of LiPF₆ was identified with a high LiF deposit, whereas for other salts, the formation process of the SEI appears controlled by the solvent decomposition of the electrolyte.     

Investigation on PVDF-HFP microporous membranes prepared by TIPS process and their application as polymer electrolytes for lithium ion batteries

Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) microporous membranes were prepared via thermally induced phase separation (TIPS) process. Then they were immersed in a liquid electrolyte to form polymer electrolytes. The effects of polymer content in casting solution on the morphology, crystallinity, and porosity of the membranes were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and a mercury porosimeter, respectively. Ionic conductivity, lithium-ion transference number, and electrochemical stability window of corresponding polymer electrolytes were characterized by AC impedance spectroscopy, DC polarization/AC impedance combination method, and linear sweep voltammetry, respectively. The results showed that spherulites and “net-shaped” structure coexisted for the membranes. Polymer content had no effect on crystal structure of the membranes. The maximum transference number was 0.55. The temperature dependence of ionic conductivity followed the Vogel–Tammann–Fulcher (VTF) relation. The maximum ionic conductivity was 2.93 × 10⁻³ Scm⁻¹ at 20 °C. Electrochemical stability window was stable up to 4.7 V (vs. Li⁺/Li).     

Effect of microstructure on the conductivity of a NASICON-type lithium ion conductor

Sintering temperature is used to control the microstructure of Li_{1 + x + y}Al_xTi_2 − xSi_yP_3 − yO₁₂ (x = 0.3, y = 0.2), a NASICON-type glass-ceramic. Scanning Electron Microscope imaging, X-Ray Diffraction, and Electrochemical Impedance Spectroscopy are employed to show that increase in sintering temperature increases conductivity while generating secondary crystalline phases. Total conductivity is as high as 3.81 × 10⁻⁴ S cm⁻¹ for sintering temperatures above 1000 °C. Crystallization of dielectric phases places the optimal sintering temperature in the 900 °C to 1000 °C range. Thermal analysis of the glass precursor reveals the glass transition, and crystallization temperatures.     

Conductivity and applications of Li-biphenyl-1,2-dimethoxyethane solution for lithium ion batteries

The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution(Li_xBp(DME)_(9.65), Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00) is measured by impedance spectroscopy at a temperature range from 0℃ to 40℃. The Li_(1.50)Bp(DME)_(9.65) has the highest total conductivity 10.7 m S/cm. The conductivity obeys Arrhenius law with the activation energy(E_(a(x=0.50))= 0.014 eV, E_(a(x=1.00))= 0.046 eV). The ionic conductivity and electronic conductivity of Li_xBp(DME)_(9.65) solutions are investigated at 20℃ using the isothermal transient ionic current(ITIC) technique with an ion-blocking stainless steal electrode. The ionic conductivity and electronic conductivity of Li_(1.00)Bp(DME)_(9.65) are measured as 4.5 mS/cm and 6.6 mS/cm, respectively. The Li_(1.00)Bp(DME)_(9.65) solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity. The lithium iron phosphate(LFP) and Li_(1.5)Al_(0.5)Ti_(1.5)(PO_4)_3(LATP) are chosen to be the counter electrode and electrolyte, respectively. The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g. The potential of Li_(1.00)Bp(DME)_(9.65) solution is about 0.3 V vs. Li~+/Li, which indicates the solution has a strong reducibility. The Li_(1.00)Bp(DME)_(9.65) solution is also used to prelithiate the anode material with low first efficiency, such as hard carbon, soft carbon and silicon.     

Lithium ion transport and ion-polymer interaction in PEO based polymer electrolyte plasticized with ionic liquid

The polyethylene oxide (PEO) based lithium ion conducting polymer electrolytes complexed with lithium trifluoromethanesulfonate (LiCF₃SO₃ or LiTf) plasticized with an ionic liquid 1-ethyl 3-methyl imidazolium trifluoromethanesulfonate (EMITf) have been reported. Morphological, spectroscopic, thermal and electrochemical investigations demonstrate promising characteristics of the polymer films, suitable as electrolyte in various energy storage/conversion devices. Significant structural changes have been observed in the polymer electrolyte due to the ionic liquid addition, investigated by X-ray diffraction (XRD) and optical microscopy. The ion-polymer interaction, particularly the interaction of imidazolium cation with PEO chains, has been evidenced by IR and Raman spectroscopic studies. The optimized composition of the polymer electrolyte i.e. PEO_25.LiTf + 40 wt.% EMITf offer room temperature ionic conductivity of ~ 3 × 10^− 4 S cm^− 1 with wide electrochemical stability window and excellent thermal stability. The ‘σ versus 1/T’ curves show apparent Arrhenius behavior below and above melting temperature. The ionic conductivity has been observed due to Li⁺ ions, as confirmed from ⁷Li-NMR studies, though the component ions of ionic liquid and anions also contribute significantly to the overall conductivity.     

Effect of hot pressing on the ionic conductivity of the PEO/LiCF3SO3 based electrolyte membranes

PEO/LiCF₃SO₃ (LiTFS) /Ethylene carbonate (EC) polymer electrolyte membranes were prepared with a solution casting method followed by a hot pressing process. The effect of the hot pressing process on the in-plane conductivity of the PEO electrolyte membranes was evaluated using a four-electrode AC impedance method. The composition, morphology, and microstructure of the composite polymer electrolyte were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The AC impedance measurement results indicate that the hot pressing process can increase the room temperature conductivity of the membranes 14 times to 1.7 × 10^− 3 S cm^− 1 depending upon the duration of the hot pressing process. The SEM, FTIR, XRD, and DSC results indicate that the hot pressing process could increase the amorphous part of the polymer electrolyte membrane or convert large spherulite crystals into nano-sized crystals.