Comparing the Ion-Conducting Polymers with Sulfonate and Ether Moieties as Cathode Binders for High-Power Lithium-Ion Batteries.

Two types of ion-conducting polyimides with sulfonate or ether functional groups were synthesized as ion-type or coordination-type cathode binders for lithium-ion batteries (LIBs), respectively. Although superior ion transport abilities have been reported for both types of ion-conducting polymers, their electrochemical performances are significantly different and the corresponding transport mechanisms at the electrolyte/electrode interface remain elusive. Here, we combine experimental and computational techniques to investigate the cathode interface in the presence of both functional polymer binders in comparison with the poly(vinylidene fluoride) (PVDF) binder as reference. A broad shoulder in the cyclic voltammogram accompanied by a poor rate performance of battery tests was observed for a LiFePO4 cathode with coordination-type ether-based polyimide (EPI) binder. In contrast, a LiFePO4 cathode with ion-type sulfonated polyimide (SPI) binder exhibits smaller concentration polarization, achieving satisfactory capacity at high current density. Simulations show that the ether-based binder strongly coordinates Li ions and thus slows the diffusion of Li ions. This leads to the reduction of the LIB electrochemical performance at a high C-rate. In contrast, the negative moiety of the SPI binder leads to less localization of Li ions, allowing a slightly higher Li-ion mobility. Conventional PVDF shows no affinity to Li ions, leading to less Li-ion accumulation at the electrode/electrolyte interface. Yet, the cathode surface covered with PVDF shows the lowest Li-ion diffusivity compared to those with the two types of Li-ion-conducting binders. Therefore, cathodes with SPI and PVDF binders show less polarization at the electrode interface and allow higher C-rate performance of LIBs. The combined results provide a comprehensive understanding of the mechanism of ion conduction in ion- and coordination-type Li-ion-conducting polymer binders. This gives valuable insight into the design of next-generation polymer materials for high-power LIBs.

Stable Lithium Deposition Generated from Ceramic-Cross-Linked Gel Polymer Electrolytes for Lithium Anode.

In this work, a composite gel electrolyte comprising ceramic cross-linker and poly(ethylene oxide) (PEO) matrix is shown to have superior resistance to lithium dendrite growth and be applicable to gel polymer lithium batteries. In contrast to pristine gel electrolyte, these nanocomposite gel electrolytes show good compatibility with liquid electrolytes, wider electrochemical window, and a superior rate and cycling performance. These silica cross-linkers allow the PEO to form the lithium ion pathway and reduce anion mobility. Therefore, the gel not only features lower polarization and interfacial resistance, but also suppresses electrolyte decomposition and lithium corrosion. Further, these nanocomposite gel electrolytes increase the lithium transference number to 0.5, and exhibit superior electrochemical stability up to 5.0 V. Moreover, the lithium cells feature long-term stability and a Coulombic efficiency that can reach 97% after 100 cycles. The SEM image of the lithium metal surface after the cycling test shows that the composite gel electrolyte with 20% silica cross-linker forms a uniform passivation layer on the lithium surface. Accordingly, these features allow this gel polymer electrolyte with ceramic cross-linker to function as a high-performance lithium-ionic conductor and reliable separator for lithium metal batteries.

Immobilization of Anions on Polymer Matrices for Gel Electrolytes with High Conductivity and Stability in Lithium Ion Batteries.

This study reports on a high ionic-conductivity gel polymer electrolyte (GPE), which is supported by a TiO2 nanoparticle-decorated polymer framework comprising poly(acrylonitrile-co-vinyl acetate) blended with poly(methyl methacrylate), i.e. , PAVM: TiO2. High conductivity GPE-PAVM: TiO2 is achieved by causing the PAVM:TiO2 polymer framework to swell in 1 M LiPF6 in carbonate solvent. Raman analysis results demonstrate that the poly(acrylonitrile) (PAN) segments and TiO2 nanoparticles strongly adsorb PF6(-) anions, thereby generating 3D percolative space-charge pathways surrounding the polymer framework for Li(+)-ion transport. The ionic conductivity of GPE-PAVM: TiO2 is nearly 1 order of magnitude higher than that of commercial separator-supported liquid electrolyte (SLE). GPE-PAVM: TiO2 has a high Li(+) transference number (0.7), indicating that most of the PF6(-) anions are stationary, which suppresses PF6(-) decomposition and substantially enlarges the voltage that can be applied to GPE-PAVM: TiO2 (to 6.5 V vs Li/Li(+)). Immobilization of PF6(-) anions also leads to the formation of stable solid-electrolyte interface (SEI) layers in a full-cell graphite|electrolyte|LiFePO4 battery, which exhibits low SEI and overall resistances. The graphite|electrolyte|LiFePO4 battery delivers high capacity of 84 mAh g(-1) even at 20 C and presents 90% and 71% capacity retention after 100 and 1000 charge-discharge cycles, respectively. This study demonstrates a GPE architecture comprising 3D space charge pathways for Li(+) ions and suppresses anion decomposition to improve the stability and lifespan of the resulting LIBs.

Design of poly(acrylonitrile)-based gel electrolytes for high-performance lithium ion batteries.

The use of polyacrylonitrile (PAN) as a host for gel polymer electrolytes (GPEs) commonly produces a strong dipole-dipole interaction with the polymer. This study presents a strategy for the application of PAN in GPEs for the production of high performance lithium ion batteries. The resulting gel electrolyte GPE-AVM comprises a poly(acrylonitrile-co-vinyl acetate) copolymer blending poly(methyl methacrylate) as a host, which is swelled using a liquid electrolyte (LE) of 1 M LiPF6 in carbonate solvent. Vinyl acetate and methacrylate groups segregate the PAN chains in the GPE, which produces high ionic conductivity (3.5 × 10 (-3) S cm(-1) at 30 °C) and a wide electrochemical voltage range (>6.5 V) as well as an excellent Li(+) transference number of 0.6. This study includes GPE-AVM in a full-cell battery comprising a LiFePO4 cathode and graphite anode to promote ion motion, which reduced resistance in the battery by 39% and increased the specific power by 110%, relative to the performance of batteries based on LE. The proposed GPE-based battery has a capacity of 140 mAh g(-1) at a discharge rate of 0.1 C and is able to deliver 67 mAh g(-1) of electricity at 17 C. The proposed GPE-AVM provides a robust interface with the electrodes in full-cell batteries, resulting in 93% capacity retention after 100 charge-discharge cycles at 17 C and 63% retention after 1000 cycles.

High performance of transferring lithium ion for polyacrylonitrile-interpenetrating crosslinked polyoxyethylene network as gel polymer electrolyte.

A polyacrylonitrile (PAN)-interpenetrating cross-linked polyoxyethylene (PEO) network (named XANE) was synthesized acting as separator and as gel polymer electrolytes simultaneously. SEM images show that the surface of the XANE membrane is nonporous, comparing to the surface of the commercial separator to be porous. This property results in excellent electrolyte uptake amount (425 wt %), and electrolyte retention for XANE membrane, significantly higher than that of commercial separator (200 wt %). The DSC result indicates that the PEO crystallinity is deteriorated by the cross-linked process and was further degraded by the interpenetration of the PAN. The XANE membrane shows significantly higher ionic conductivity (1.06-8.21 mS cm(-1)) than that of the commercial Celgard M824 separator (0.45-0.90 mS cm(-1)) ascribed to the high electrolyte retention ability of XANE (from TGA), the deteriorated PEO crystallinity (from DSC) and the good compatibility between XANE and electrode (from measuring the interfacial-resistance). For battery application, under all charge/discharge rates (from 0.1 to 3 C), the specific half-cell capacities of the cell composed of the XANE membrane are all higher than those of the aforementioned commercial separator. More specifically, the cell composed of the XANE membrane has excellent cycling stability, that is, the half-cell composed of the XANE membrane still exhibited more than 97% columbic efficiency after 100 cycles at 1 C. The above-mentioned advantageous properties and performances of the XANE membrane allow it to act as both an ionic conductor as well as a separator, so as to work as separator-free gel polymer electrolytes.

Poly(ethylene oxide)-co-poly(propylene oxide)-based gel electrolyte with high ionic conductivity and mechanical integrity for lithium-ion batteries.

Using gel polymer electrolytes (GPEs) for lithium-ion batteries usually encounters the drawback of poor mechanical integrity of the GPEs. This study demonstrates the outstanding performance of a GPE consisting of a commercial membrane (Celgard) incorporated with a poly(ethylene oxide)-co-poly(propylene oxide) copolymer (P(EO-co-PO)) swelled by a liquid electrolyte (LE) of 1 M LiPF6 in carbonate solvents. The proposed GPE stably holds LE with an amount that is three times that of the Celgard-P(EO-co-PO) composite. This GPE has a higher ionic conductivity (2.8×10(-3) and 5.1×10(-4) S cm(-1) at 30 and -20 °C, respectively) and a wider electrochemical voltage range (5.1 V) than the LE-swelled Celgard because of the strong ion-solvation power of P(EO-co-PO). The active ion-solvation role of P(EO-co-PO) also suppresses the formation of the solid-electrolyte interphase layer. When assembling the GPE in a Li/LiFePO4 battery, the P(EO-co-PO) network hinders anionic transport, producing a high Li+ transference number of 0.5 and decreased the polarization overpotential. The Li/GPE/LiFePO4 battery delivers a discharge capacity of 156-135 mAh g(-1) between 0.1 and 1 C-rates, which is approximately 5% higher than that of the Li/LE/LiFePO4 battery. The IR drop of the Li/GPE/LiFePO4 battery was 44% smaller than that of the Li/LE/LiFePO4. The Li/GPE/LiFePO4 battery is more stable, with only a 1.2% capacity decay for 150 galvanostatic charge-discharge cycles. The advantages of the proposed GPE are its high stability, conductivity, Li+ transference number, and mechanical integrity, which allow for the assembly of GPE-based batteries readily scalable to industrial levels.

Benzylamine-assisted noncovalent exfoliation of graphite-protecting Pt nanoparticles applied as catalyst for methanol oxidation.

A novel method has been developed to physically exfoliate graphite and uniformly disperse Pt nanoparticles on graphite nanoplates without damaging the graphene structures. A stable aqueous suspension of graphite nanoplates was achieved by benzylamine-assisted noncovalent fuctionalization to graphite and characterized by transmission electron microscopy, X-ray diffraction and Raman spectroscopy. A uniform dispersion of Pt nanoparticles was then prepared on the graphite nanoplates, where the benzylamine acts as a stabilizer. These Pt loaded graphite nanoplates were then prepared as an electrode, which significantly increased catalytic activity toward the methanol oxidation reaction, resulting in a 60% increment in mass activity compared to that of E-TEK.

Stabilization of embedded Pt nanoparticles in the novel nanostructure carbon materials.

An extremely durable and highly active Pt catalyst has been successfully prepared by embedding Pt(0) nanoparticles inside the pores of the nitrogen-dotted porous carbon layer surrounding carbon nanotubes (Pt@NC-CNT). The Pt@NC-CNT catalyst has a high BET surface area of 271 m(2) g(-1) (62 m(2) g(-1) for Pt/XC-72) and comparably high electrochemically active surface area of 64.3 m(2) g(-1) (68.2 m(2) g(-1) for Pt/XC-72). The prepared Pt nanoparticles are small in size (2.8 ± 1.3 nm) and have a strong interaction of nitrogen to platinum, as evidenced by the binding energy observed at 399.5 eV. The maximum current densities (I(f)) during methanol oxidation observed for Pt@NC-CNT (13.2 mA cm(-1)) is 1.2 times higher than that of Pt/XC-72 (10.8 mA cm(-1)) catalysts. Remarkably, in the long term durability test, the I(f) after 1000 cycles for Pt@NC-CNT decreased to 10.6 mA cm(-1) compared with Pt/XC-72, which decreased to 2.6 mA cm(-2). This means that the Pt@NC-CNT catalyst has a tremendously stable electrocatalytic activity for MOR because of the unique structure of Pt@NC-CNT formed in this novel synthesis technique.

Excellent performance of Pt0 on high nitrogen-containing carbon nanotubes using aniline as nitrogen/carbon source, dispersant and stabilizer.

Novel high nitrogen-containing carbon nanotubes (NC-CNT) (14% N) as catalyst support have been successfully prepared using aniline as a dispersant to CNT and as a source for both carbon and nitrogen coated on the surface of the CNT.

Spherical aggregates composed of gold nanoparticles.

Alkylated triethylenetetramine (C12E3) was synthesized and used as both a reductant in the preparation of gold nanoparticles by the reduction of HAuCl(4) and a stabilizer in the subsequent self-assembly of the gold nanoparticles. In acidic aqueous solution, spherical aggregates (with a diameter of about 202 +/- 22 nm) of gold nanoparticles (with the mean diameter of approximately 18.7 nm) were formed. The anion-induced ammonium adsorption of the alkylated amines on the gold nanoparticles was considered to provide the electrostatic repulsion and steric hindrance between the gold nanoparticles, which constituted the barrier that prevented the individual particles from coagulating. However, as the amino groups became deprotonated with increasing pH, the ammonium adsorption was weakened, and the amino groups were desorbed from the gold surface, resulting in discrete gold particles. The results indicate that the morphology of the reduced gold nanoparticles is controllable through pH-'tunable' aggregation under the mediation of the amino groups of alkylated amine to create spherical microstructures.

Effects of alkylated polyethylenimines on the formation of gold nanoplates.

Mono- and dialkylated polyethylenimines (PEI-1R and PEI-2R) were used for the facile synthesis of gold nanoplates with a preferential growth direction along the Au (111) plane. It was found that polymer hydrophobicity greatly influenced the nanoparticle morphology. PEI-1R in the acidic aqueous solution with a smaller degree of alkylation effectively adsorbed on the surface of gold nanoplates with the protonated ethylenimine groups rather than being aggregated in the bulk aqueous phase to form polymer aggregates as compared to the situation for PEI-2R. Loose alkylated PEI aggregates in acidic solution promote the formation of gold nanoplates by means of the anion-induced cation adsorption on certain crystallographic facets during the growth of gold particles. Without incorporating alkyl groups, however, the TEM image of the gold colloid solution with PEI showed only the formation of spherical gold nanoparticles by the same process. The morphology of gold nanoparticles was tuned not only by varying the degree of alkylation of PEI samples but also by the solvent type and pH value of the solution. By utilizing differently alkylated PEIs as reducing agents, this facile synthetic procedure can selectively result in the formation of gold nanoplates at room temperature without an extra inducing process.

Generation of gold thread from Au(III) and triethylamine.

Gold threads were spontaneously generated at room temperature from a combined solution of aqueous HAuCl4 and triethylamine. Initially, some reduced gold nanoparticles were self-organized into one-dimensional (1D) nanowires, which then developed into three-dimensional (3D) microscale threads of gold. After aging, the self-organized gold thread grew spontaneously, accompanied by the generation of new buds to start new branches. TEM images show that the gold thread is composed of elastic materials; in which, colloidal gold nanoparticles reduced by triethylamine serve as the bricks, whereas elastic substances formed during the reaction serve as the mortar, which holds together the gold particles. The results of IR and 1H NMR spectroscopy demonstrate that the elastic materials consist mainly of alkane-like substances. Examination of the 1H NMR spectrum of triethylamine under the conditions of the reaction shows evidence of the occurrence of oxidative N dealkylation. The observed isotope effect demonstrates the existence of O-D cleavage resulting from the degradation of carbinolamine, which is the reported oxidation route of amines. Triethylamine acts here not only acts as a stabilizer and a reducing agent, but also as a precursor to build the alkane-like material upon which the gold thread is formed.

Enhanced stabilization and deposition of Pt nanocrystals on carbon by dumbbell-like polyethyleniminated poly(oxypropylene)diamine.

Pseudo-dendritic polyethyleniminated poly(oxypropylene)diamine (D400(EI)(20)) was used as a stabilizer and promoter to prepare Pt nanoparticles in aqueous solution, which was then deposited on carbon surface followed by calcination. After being deposited on carbon surface, no Pt(0) could be detected in the solution phase. In all steps, the increasing molar ratio of the amino groups of D400(EI)(20) to H(2)PtCl(6) ([N]/[Pt]) drastically reduced the size and the polydispersity and kept a constant low value after [N]/[Pt] = 20. Under a [N]/[Pt] ratio of 20, the particle sizes obtained from transmission electron microscopy (TEM) were very small in solution (2.7-2.4 nm) and remained the same after being deposited on carbon surface (2.7-2.4 nm), and were only slightly increased to 3.6-3.0 nm after calcination. The stabilizing ability of D400(EI)(20) to Pt on carbon surface before and after calcination can be interpreted by the existence of binding energy between Pt and amine nitrogen. The X-ray diffraction (XRD) pattern together with the TEM image reveals that the obtained Pt nanoparticles exist in single-crystal form. The results of photoelectron spectroscopy (XPS) evidence that the metallic Pt(0) rather than the oxidized Pt is the predominant species in the Pt/C catalysts. The electrochemical active surface (EAS) area of the Pt/C catalyst is only slightly higher than that of the E-TEK Pt/C catalyst, but the utilization factor (93.4%) is remarkably higher than the latter (62.8%). The increasing time of thermal treatment increases the crystallinity of Pt(0) on carbon, accompanied by the increasing EAS areas, which corresponds to its enhanced electrocatalytic performance to methanol oxidation.

Stabilizing effect of pseudo-dendritic polyethylenimine on platinum nanoparticles supported on carbon.

A new type of surfactant with a hydrophile of dendritic polyethylenimine (C(12)(EI)(7)) was synthesized by a cationic polymerization of dodecylamine with aziridine and was used as a stabilizer to prepare Pt colloid, which is then used in situ to prepare carbon-supported Pt nanoparticles. The effects of supporting carbon, surfactant concentration, and calcination time on the nanoparticle size and catalytic performance were determined from the transmission electron microscopic analyses and cyclic voltammograms. In the presence of carbon, the Pt particle size increased slightly with lower C(12)(EI)(7) content, while those with higher C(12)(EI)(7) concentrations remained unchanged. For the heat-treated Pt/C catalyst, the molar ratio of C(12)(EI)(7) to H(2)PtCl(6) ([N]/[Pt] ratio) dominated the growth of Pt nanoparticles. The size decreased from 7.6 nm for a [N]/[Pt] ratio of 5 to 3.8 nm for a [N]/[Pt] ratio of 40. X-ray photoelectron spectroscopy revealed that metallic Pt(0) (81.6%) predominated the Pt species in the heat-treated catalyst, which is more than the commercial E-TEK catalyst. The data show clearly that thermal treatment had successively removed the stabilizing shells; moreover, it did not cause serious aggregation of particles in the presence of C(12)(EI)(7) and thus enhanced the catalytic activity. The interaction between Pt and C(12)(EI)(7) were studied and were explained in terms of a mechanism of dual-functional stabilization both on carbon and in the thermal treatment.

Gold nanoparticles prepared using polyethylenimine adsorbed onto montmorillonite.

Polyethylenimine-modified montmorillonite (N-MMT) was used to prepare gold nanoparticles, where the montmorillonite (MMT) acted as a solid support to retain the conformation of polyethylenimine (PEI), and the amino groups of PEI were used simultaneously to both complex and reduce the gold ions. From the results of X-ray diffraction, it is apparent that the reduction of gold ions occurs primarily on the MMT surface. In the presence of MMT, the formation of a flattened configuration on the clay instead of stretched-out ethylenimine segments of PEI results in the formation of smaller gold particles. With a higher acidification ratio, the recharging of the MMT surface with positive ammonium ionic sites of PEI is likely to prevent the flocculation of clay and thus facilitate the reduction of gold. The rate of gold reduction with N-MMT is faster at low pH values, this being in contrast to the usual trend observed for the reduction of gold ions. The use of PEI adsorbed onto MMT has been shown to be able to act simultaneously as both a protective template and as a reducing agent, thereby greatly simplifying the process for preparing gold nanoparticles.

Preparation of platinum nanoparticles in salt-induced micelles of dumbbell-shaped ABA copolymer.

The interaction of a water-soluble ABA type of dumbbell-shaped polyethyleniminated copolymers (D400(EI)8) with H2PtCl6 in aqueous medium is studied by means of UV-visible absorption spectra, dynamic light scattering (DLS) measurements, and transmission electron microscopy (TEM). From TEM images of the stained polymer, it is evident that the spherical and well-structured polymer micelles are formed by the introduction of H2PtCl6, and totally nonstructured micelles are formed from D400(EI)8 itself. These findings coincide with the results obtained from DLS measurements, where the narrowly distributed polymer aggregates are remarkably observed. Moreover, it is directly evidenced from TEM that the reduced Pt(0) nanoparticles are embedded in the polyethylenimine (PEI) block at the exterior of micelles, whereas the polyoxypropylene (PPO) block is surrounded by the PEI block. Additionally, the resulting Pt(0) colloids are very stable for at least 4 months.

Self-assembly of gold nanoparticles induced by poly(oxypropylene)diamines.

A series of poly(oxypropylene)diamines D230, D400, D2000, and D4000, having molecular weights of hydrophobic segments of 230, 400, 2000, and 4000, were used as ligands to synthesize self-organized gold nanocrystals. Ligand exchange significantly reduced the average particle size and the polydispersity of nanocrystals, and this effect was more remarkable as the molar ratio of amine groups to Au3+ ions ([N]/[Au3+] ratio) was increased. Under the same [N]/[Au3+] ratio of 100, D2000 generated an ordered 2D-monolayer; however, D230 and D400 colloids formed mainly a densely packed 3D structure with minor 2-D layers, and D4000 presented disordered 3D and 2D structures. The gap among the nanoparticles was found to be increased with the increasing molecular weight of the hydrophobic segment of ligands, accompanied by the decreasing wavelength of UV-vis absorption bands. This increased gap can be interpreted as the ligand thickness calculated from the equation of steric force increasing with increasing molecular weight of the hydrophobic segment. The potential energies obtained from the calculated ligand thickness according to the soft sphere model show more steep potential wells for D230 and D400 colloids than that for the D2000 colloid. This explains why the aggregation hardly occurred for the gold nanoparticles obtained under D2000, where the nanoparticles are single crystals having face center crystal structure with a lattice constant of 2.36 A and have grain sizes close to the average particle sizes, evidenced from the results of transmission electron microscopy and X-ray diffraction spectroscopy.

Study of microstructural characterization and ionic conductivity of a chemical-covalent polyether-siloxane hybrid doped with LiClO4.

The chemical-covalent polyether-siloxane hybrids (EDS) doped with various amounts of LiClO4 salt were characterized by FT-IR, DSC, TGA, and solid-state NMR spectra as well as impedance measurements. These observations indicate that different types of complexes by the interactions of Li+ and ClO4- ions are formed within the hybrid host, and the formation of transient cross-links between Li+ ions and ether oxygens results in the increase in T(g) of polyether segments and the decrease in thermal stability of hybrid electrolyte. Initially a cation complexation dominated by the oxirane-cleaved cross-link site and PEO block is present, and after the salt-doped level of O/Li+ = 20, the complexation through the PPO block becomes more prominent. Moreover, a significant degree of ionic association is examined in the polymer-salt complexes at higher salt uptakes. A VTF-like temperature dependence of ionic conductivity is observed in all of the investigated salt concentrations, implying that the diffusion of charge carrier is assisted by the segmental motions of the polymer chains. The behavior of ion transport in these hybrid electrolytes is further correlated with the interactions between ions and polymer host.

Effects of polymer micelles of alkylated polyethylenimines on generation of gold nanoparticles.

Mono- and di-alkylated polyethylenimines (PEI-1R, PEI-2R) were synthesized and used as both reductants, by exploiting the functionality of the polyethylenimine's (PEI) amino groups, and stabilizers able to protect nascent gold nanoparticles generated from hydrogen tetrachloroaurate (HAuCl4). From TEM images of the stained polymers, it is clear that the polymer micelles are round and well-structured when formed from PEI-2R, fused and less well-structured when formed from PEI-1R, and totally nonstructured when formed from PEI. These findings coincide with the results found by using pyrene as a probe to investigate aggregation behavior, where PEI-2R with a fluorescence intensity ratio (I1/I3) of 1.48 forms the more closely packed polymer micelles than PEI-1R (I1/I3 = 1.64) and PEI (I1/I3 = 1.72). The use of the highly alkylated polymer micelle (PEI-2R) results in the fastest reduction of HAuCl4, and gives the most effective protection to the generated gold nanoparticles. When used at higher polymer concentrations than required for micelle formation, it was found that polymer hydrophobicity was highly influential in directing the nanoparticle's morphology, i.e., the resulting polymer micelles were labeled with perfect and round necklace-like gold nanoparticles when PEI-2R was used, and imperfect and less round gold nanoparticles when PEI-1R was employed. These structures were totally absent when PEI was used. The use of alkylated PEI, being able to act simultaneously as both a reductant and as a very effective protective agent, greatly simplifies the process used for preparing gold nanoparticles.