Bacterial Cellulose/Zwitterionic Dual-network Porous Gel Polymer Electrolytes with High Ionic Conductivity

Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.

Improvement of ionic conductivity of solid polymer electrolyte based on Cu-Al bimetallic metal-organic framework fabricated through molecular grafting

A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.

Polymer dispersed ionic liquid electrolytes with high ionic conductivity for ultrastable solid-state lithium batteries

Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.

3D spiny AlF_(3)/Mullite heterostructure nanofiber as solid-state polymer electrolyte fillers with enhanced ionic conductivity and improved interfacial compatibility

Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.

Alkali Ionic Conductivity in Inorganic Glassy Electrolytes

Glassy electrolytes could be a potential candidate for all-solid-state batteries that are considered new-generation energy storage devices. As glasses are one of the potential fast ion-conducting electrolytes, progressive advances in glassy electrolytes have been undergoing to get commercial attention. However, the challenges offered by ionic conductivity at room temperature (10−5 - 10−3 S∙cm−1) in comparison to those of organic liquid electrolytes (10−2 S∙cm−1) hindered the applicability of such electrolytes. To enhance the research development on ionic conductivity, the overall picture of the ionic conductivity of glassy electrolytes is reviewed in this article with a focus on alkali oxide and sulfide glasses. We portray here the techniques applied for alkali ion conductivity enhancement, such as methods of glass preparation, host optimization, doping, and salt addition for enhancing alkali ionic conductivity in the glasses.

Oxygen ionic conductivity of a composite electrolyte SDC-LSGM prepared via glycine-nitrate process

Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction （XRD） and the scan electron microscope （SEM） are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current （DC） method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.

A collagen-based electrolyte-locked separator enables capacitor to have high safety and ionic conductivity

The conventional liquid electrolytes(LEs) have a high level of ionic conductivity;however, they often suffer from the poor processability and safety risks of potential leakage. Although solid-state electrolytes(SSEs) can solve these inherent problems of LEs, the ionic conductivity of most SSEs is several magnitudes lower than these of LEs. Herein, we report a novel strategy by building liquid ion-transport channels in a solid framework and prepared an electrolyte-locked separator(ELS) using a collagen fiber membrane(CFm). The liquid electrolyte was primarily infiltrated in the smaller voids of CFm, and its ionic conductivity could attain to 9.0×10-3 S cm-1 when the electrolyte absorption(EA) reached up to 112.0%. After centrifuging treatment, the electrolyte retentions(ER) and ionic conductivities of ELS were 108.93% and 8.37×10-3 S cm-1, respectively, which were much higher than those of commercial cellulose separator(CS), exerting excellent liquid-locking performances. In particular, the electrical double-layer capacitors(EDLC) assembled by ELS or CS were characterized and exhibited similar electrochemical performance,demonstrating the satisfactory ability and applicability of ELS for commercial use. In addition, the ELSbased EDLC exhibited favorable flexibility with relative lower loss of capacitance under different angles of bending.

Empirical decay relationship between ionic conductivity and porosity of garnet type inorganic solid-state electrolytes

Ionic conductivity is one of the crucial parameters for inorganic solid-state electrolytes.To explore the relationship between porosity and ionic conductivity,a series of Li_(6.4)Ga_(0.2)La_(3)Zr_(2)O_(12) garnet type solid-state electrolytes with different porosities were prepared via solid-state reaction.Based on the quantified data,an empirical decay relationship was summarized and discussed by means of mathematical model and dimensional analysis method.It suggests that open porosity causes ionic conductivity to decrease exponentially.The pre-exponential factor obeys the Arrhenius Law quite well with the activation energy of 0.23 eV,and the decay constant is averaged to be 2.62%.While the closed porosity causes ionic conductivity to decrease linearly.The slope and intercept of this linear pattern also obey the Arrhenius Law and the activation energies are 0.24 and 0.27 eV,respectively.Moreover,the total porosity is linearly dependent on the open porosity,and different sintering conditions will lead to different linear patterns with different slopes and intercepts.

A Valence Electron Structure Criterion of Ionic Conductivity of Sr- and Mg-doped LaGaO_3 Ceramics

The valence electron structures of Sr- and Mg-doped LaGaO3 ceramics with different compositions were calculated by Empirical Electron Theory of Solids and Molecules （EET）. A criterion for the ionic conductivity was proposed, i.e. the 1/（nAnB） increases with increasing the ionic conductivity when x or y〈20% （in molar fraction）.

The effect of oxygen fugacity on ionic conductivity in olivine

The oxygen fugacity(f_(O2)) may affect the ionic conductivity of olivine under upper mantle conditions because Mg vacancies can be produced in the crystal structure by the oxidization of iron from Fe^(2+) to Fe3+. Here we investigated olivine ionic conductivity at 4 GPa, as a function of temperature, crystallographic orientation, and oxygen fugacity, corresponding to the topmost asthenospheric conditions. The results demonstrate that the ionic conductivity is insensitive to f_(O2) under relatively reduced conditions(f_(O2) below Re-ReO_(2) buffer), whereas it has a clear f_(O2)-dependence under relatively oxidized conditions(f_(O2) around the magnetite-hematite buffer). The ionic conduction in olivine may contribute significantly to the conductivity anomaly in the topmost asthenosphere especially at relatively oxidized conditions.

Ionic Conductivity of Nano-LaF_3 Bulk Material at Room Temperature

Nanocrystalline powder of LaF3 was synthesized by a method of direct precipitation from water solution. Particle size and shape of LaF3 nanocrystalline powder was analysed with TEM. Particles were mainly spherical with narrow particle size distribution （10 20 nm）. The average particle size analysed with XRD is 16.7 nm. Nano-LaF3 bulk material was prepared by compacting the powder to 1 GPa at room temperature and a vacuum of 10^-4 Pa. The ionic conductivity of nano-LaF3 bulk material was studied with complex impedance spectra at room temperature. The ionic conductivity of nano-LaF3 bulk material （1 × 10^-5 S·cm^-1 ） at room temperature is significantly increased compared to that of single crystal LaF3 （1 × 10^-6 S·cm^-1）. A special phenomenon was observed firstly time that the ionic conductivity increased gradually with multiple testing in result of relaxation.

Organic fast ion-conductor with ordered Li-ion conductive nano-pathways and high ionic conductivity for electrochemical energy storage

Solid electrolyte(SE)is the most crucial factor to fabricate safe and high-performance all-solid-state lithium-ion batteries.However,the most commonly reported SE,including solid polymer electrolyte(SPE)and inorganic oxides and sulfides,suffer problems of low ionic conductivity at room temperature for SPE and large interfacial impedance with electrodes for inorganic electrolytes.Here we for the first time demonstrate a novel ionic plastic crystal lithium salt solid electrolyte(OLiSSE)fast ion-conductor dilithium(1,3-diethyl-4,5-dicarboxylate)imidazole bromide with ordered Li-ion conductive nanopathways and an exceptional ionic conductivity of 4.4×10^(−3)Scm^(−1)at 30℃.The prepared OLiSSE exhibits apparent characters of typical ionic plastic crystals in the temperature range of−20 to 70℃,and shows remarkable thermal stability and electrochemical stability below 150℃ and 4.7 V,respectively.No lithium dendrite or short circuit behavior is detected for the Li|OLiSSE|Li cell after the galvanostatic charge-discharge test for 500 h.The fabricated Li|OLiSSE|LiFePO_(4) all-solid-state cell without using any separator and liquid plasticizer directly delivers an initial discharge capacity of 151.4 mAh g^(−1) at the discharge rate of 0.1 C,and shows excellent charge-discharge cycle stability,implying large potential application in the next generation of safe and flexible all-solid-state lithium batteries.

Ionic conductivity study on electron beam irradiated polyacrylonitrile-polyethylene oxide gel

Different mass percent polyacrylonitrile （PAN）-polyethylene oxide （PEO） gels were prepared and irradiated by an electron beam （EB） with energy of 1.0 MeV to the dose ranging from 13 kGy to 260 kGy. The gels were analysed by using Fourier transform infrared spectrum, gel fraction and ionic conductivity （IC） measurement. The results show that the gel is crosslinked by EB irradiation, the crosslinking degree rises with the increasing EB irradiation dose （ID） and the mass percents of both PAN and PEO contribute a lot to the crosslinking; in addition, EB irradiation can promote the IC of PAN-PEO gels. There exists an optimum irradiation dose, at which the IC can increase dramatically. The IC changes of the PAN-PEO gels along with ID are divided into three regions： IC rapidly increasing region, IC decreasing region and IC balanced region. The cause of the change can be ascribed to two aspects, gel capturing electron degree and crosslinking degree. By comparing the IC-ID curves of different mass percents of PAN and PEO in gel, we found that PAN plays a more important role for gel IC promotion than PEO, since addition of PAN in gel causes the IC-ID curve sharper, while addition of PEO in gel causes the curve milder.

IONIC CONDUCTIVITY IN THE COMPLEXES OF COMB-SHAPED POLYETHER WITH LITHIUM AROMATIC SULFONATE

Complexes of comb-shaped polyether and lithium aromatic sulfonates bearing different negative charge number were prepared by in situ thermal polymerization. Their conductivity depends deeply on salt content, ambient temperature and negative charge number of the added salts. Results show that anions can be partly immobilized by increasing their negative charges at lower temperature. Against discharge time the short circuit current of the battery (Li/complex film/Li_x V_3O_8) is stabilized by increasing the anionic charge number of the complex.

Synthesis and Ionic Conductivity of Network Polymer Electrolytes with Internal Plasticizers

Network polymer electrolytes with free oligo(oxyethylene) chains as internal plasticizers were prepared by cross-linking poly(ethylene glycol) acrylates. The effects of salt concentration and properties of internal plasticizers on ionic conductivity were studied.

IONIC CONDUCTIVITY IN CROSSLINKED POLY (METHYLSILOXANE-g-ETHYLENE OXIDE) NETWORK FILMS CONTAINING LITHIUM PERCHLORATE

Polymer electrolytes based on poly (methylsiloxane-g-ethylene oxide) and LiClO_4 have been prepared. The network films crosslinked by a crosslinking agent are found to exhibit a considerably high ionic conductivity of about 10^(-4) Scm^(-1) at room temperature and have good flexibility.

IONIC CONDUCTIVITY OF EPOXY NETWORK/POLYETHYLENE GLYCOL- LITHIUM PERCHLORATE COMPLEX IPN SYSTEM

In an attempt to prepare a polymeric solid electrolyte with both high ionic conductivity at ambient temperature and adequate mechanical strength, an ionic conducting IPN composed of bisphenol A epoxy resin/polyethylene glycol containing LiClO_4 was synthesized. The dependence of conductivity was investigated as a function of salt content, composition and temperature. It has been revealed that a maximum of conductivity appeared when EO/Li=25, where EO denotes the—(CH_2CH_2O)-unit in polyethylene glycol, and that the temperature dependence of conductivity followed VTF equation, suggesting that the motion of ionic carriers resulted from the segmental motion of the polymer. When glycerol epoxy resin was used instead of bisphenol A epoxy, the ambient temperature (25℃) conductivity could somewhat further be raised up to 3×10^(-5) S/cm.

VISCOELASTICITY AND IONIC CONDUCTIVITY OF TWO-COMPONENT EPOXY NETWORK CONTAINING LITHIUM PERCHLORATE

Polymeric solid electrolyte system composed of triglycidyl ether of glycerol (TGEG), diglycidyl ether of polyethylene glycol (DGEPEG)and LiClO_4 salt were synthesized. In this' system the electrolyte has a pecularity that not merely can the LiClO_4 provide ionic carriers, but also catalyze the crosslinking reaction without adding an usual curing agent. The effect of salt content and degree of crosslinking on the viscoelasticity and ionic conductivity were studied. Both WLF and VTF equations were used to treat the experimental data in order to elucidate the mechanism of ionic conduction. It was found that the ionic conductivity of the system is carded out through the segmental motion mechanism. However, the data must be treated with care. For example, in evaluating WLF parameters, the contribution concerned with ionic carrier generation with temperature to the conductivity must be differentiated from that concerned with segmental motion. Besides, the temperature range suitable to WLF equation must also be considered. For VTF equation, it might be inapplicable ff the temperature is too low and close to the glass transition temperature of the specimen. Further study is needed in order to have a quantitative information on the limitation of these equations.

Effect of Pb Ions on the Ionic Conductivity of Some Silicate Glass Systems

Conductivity of glasses in the systems SiO2.PbO.RO, (where R=Ca, Sr or Ba) was investigated between room temperature and 530 K. The dependence of log resistivity as well as the activation energy on the PbO content has been studied. Based on the present experimental results, the possible different conduction mechanisms in such glasses are discussed. It was postulated that Pb2+ ions may represent the major charge carrying species in these glasses. This assumption was confirmed by the calculations of the mean distance between the interstitial Pb2+ ions and the effective center of the O2- ions in the glass networks. The variation in the values of the density and the molar volume with PbO content is also discussed in view of the obtained activation energies for the studied glass-systems.

IONIC CONDUCTIVITY OF POLY (β-ALKOXYCARBONYLETHYLMETHYLSILOXANE)-LiClO_4 CROSSLINKED FILMS

Poly (β-carboxyethylmethylsiloxane)-LiClO_4 and poly (β-alkoxylethylmethylsiloxane)-LiClO_4 crosslinked fllms have been prepared. The ionic conductivity of the films depends on the polymer species, concentration of lithium perchlorate, temperature and content of crosslinking agent. The effect of high polar organic solvent 1, 4-butyrolactone on the ionic conductivity and mechanical properties of poly (β-carhoxyethylmethylsiloxane )-LiClO_4 system was also investignied.