燕山南北地区发现的史前石容器及相关问题

石容器作为我国史前考古的一种重要遗存,集中发现于燕山南北地区。本文认为,燕山南北地区含石容器的考古遗存基本属于筒形罐文化系统;石容器不是一般的器皿,应该是祭祀或行巫术的辅助工具;我国石容器的出现,并不晚于陶器,探索其起源与文化传承,将有助于燕山南北地区史前考古的分期研究。

殷墟地区出土石容器研究

殷墟地区所出土的石容器,数量较多,制作精美,器形多样,包括鬲、簋、豆、碗、盒、尊、罐、罍、瓿、壶等常见器形,也包括有调色碟、舟形容器、椭圓形四足容器等特殊器形。这些石容器多为大理岩制作而成,主要发现于殷墟时期高等级贵族墓葬中,尤以侯家庄西北冈王陵区内出土石容器最为精美。石容器器物形态与陶器特别是青铜器极为相似,可能为仿青铜而制,部分容器可能具有礼器功能。

Flexible free-standing graphene-like film electrode for supercapacitors by electrophoretic deposition and electrochemical reduction

Electrophoretic deposition in conjunction with electrochemical reduction was used to make flexible free-standing graphene-like films. Firstly, graphene oxide （GO） film was deposited on graphite substrate by electrophoretic deposition method, and then reduced by subsequent electrochemical reduction of GO to obtain reduced GO （ERGO） film with high electrochemical performance. The morphology, structure and electrochemical performance of the prepared graphene-like film were confirmed by SEM, XRD and FT-IR. These unique materials were found to provide high specific capacitance and good cycling stability. The high specific capacitance of 254 F/g was obtained from cyclic voltammetry measurement at a scan rate of 10 mV/s. When the current density increased to 83.3 A/g, the specific capacitance values still remained 132 F/g. Meanwhile, the high powder density of 39.1 kW/kg was measured at energy density of 11.8 W-h/kg in 1 mol/L H2SO4 solution. Furthermore, at a constant scan rate of 50 mV/s, 97.02% of its capacitance was retained for 1000 cycles. These promising results were attributed to the unique assembly structure of graphene film and low contact resistance, which indicated their potential application to electrochemical capacitors.

Preparation and capacitance properties of Ni foam@graphene@Co_(3)O_(4)composite electrode materials

Graphene under high temperature was prepared and loaded on Ni foam.Then,cobalt tetroxide precursor was grown on Ni foam in situ by the hydrothermal method.Finally,the sample was burned at high temperature to obtain Co_(3)O_(4)+graphene@Ni.The hydrothermal method used in this paper is easy to operate,with low-risk factors and environmental protection.The prepared Co_(3)O_(4)+graphene@Ni electrode exhibits superior electrochemical performance than Co_(3)O_(4)@Ni electrode.At a current density of 1 A/g,the specific capacitance of the Co_(3)O_(4)+graphene@Ni electrode calculated by a charge-discharge test is 935 F/g,which is much larger than that of Co_(3)O_(4)@Ni electrode of 340 F/g.

Electrochemical Preparation of Polypyrrole/Graphene Films on Titanium Mesh as Active Materials for Supercapacitors

Films of polypyrrole/graphene on titanium mesh were prepared by electrochemical reduction of the fresh dried foam films of graphene oxide followed by an electrochemical polymerization of pyrrole. The as-obtained composite had highly surface area, conductivity, and could be used as the electrode for supercapacitors, especially directly used as the active materials in free of binders while the Ti mesh worked as the collector. Plenty of polypyrrole nanoparticles formed on the surface of reduced graphene film, and some fiber-like aggregates could be formed during the polymerization, which worked as the material for pseudo-capacitance. The specific capacitance of the supercapacitor reached 400 F/g and showed high stability with retaining capacitance of 82% after 5000 cycles, indicating that the nanocomposite is a suitable active material for supercapacitors.

One-step strategy to graphene/Ni（OH）2 composite hy- drogels as advanced three-dimensional supercapacitor electrode materials

Graphene-based three-dimensional （3D） macroscopic materials have recently attracted increasing interest by virtue of their exciting potential in electrochemical energy conversion and storage. Here we report a facile one-step strategy to prepare mechanically strong and electrically conductive graphene/Ni（OH）2 composite hydrogels with an interconnected porous network. The composite hydrogels were directly used as 3D supercapacitor electrode materials without adding any other binder or conductive additives. An optimized composite hydrogel containing -82 wt.% Ni（OH）2 exhibited a specific capacitance of -1,247 F/g at a scan rate of 5 mV/s and -785 F/g at 40 mV/s （-63% capacitance retention） with excellent cycling stability. The capacity of the 3D hydrogels greatly surpasses that of a physical mixture of graphene sheets and Ni（OH）2 nanoplates （-309 F/g at 40 mV/s）. The same strategy was also applied to fabricate graphene-carbon nanotube/Ni（OH）2 ternary composite hydrogels with further improved specific capacitances （-1,352 F/g at 5 mV/s） and rate capability （-66% capacitance retention at 40 mV/s）. Both composite hydrogels obtained here can deliver high energy densities （-43 and -47 Wh/kg, respectively） and power densities （-8 and -9 kW/kg, respectively）, making them attractive electrode materials for supercapacitor applications. This study opens a new pathway to the design and fabrication of functional 3D graphene composite materials, and can significantly impact broad areas including energy storage and beyond.

Supercapacitors based on high-surface-area graphene

Exfoliated graphite oxide was prepared by an improved Hummers method and was then reduced to graphene with hydrazine in the presence of ammonium hydroxide.N2adsorption–desorption measurement showed that graphene so obtained had a specific surface area as high as 818 m2/g.Galvanostatic charge/discharge curves demonstrated that the as-prepared graphene exhibited a specific capacitance of 186.9 F/g at a current density of 0.1 A/g and that about 96%of the specific capacitance was retained after 2000 cycles at a current density of 5 A/g.

Electron-electron interactions in monolayer graphene quantum capacitors

We demonstrate the effects of electron-electron （e-e） interactions in monolayer graphene quantum capacitors. Ultrathin yttrium oxide showed excellent per-formance as the dielectric layer in top-gate device geometry. The structure and dielectric constant of the yttrium oxide layers have been carefully studied. The inverse compressibility retrieved from the quantum capacitance agreed fairly well with the theoretical predictions for the e--e interactions in monolayer graphene at different temperatures. We found that electron-hole puddles played a significant role in the low-density carrier region in graphene. By considering the temperature-dependent charge fluctuation, we established a model to explain the round-off effect originating from the e-e interactions in monolayer graphene near the Dirac point.

Facile synthesis of T-Nb_2O_5 nanosheets/nitrogen and sulfur co-doped graphene for high performance lithium-ion hybrid supercapacitors

Li-ion hybrid supercapacitors（Li-HSCs） have attracted increasing attention as a promising energy storage device with both high power and energy densities. We report a facile two-step hydrothermal method to prepare the orthorhombic niobium oxide（T-Nb2O5） nanosheets supported on nitrogen and sulfur co-doped graphene（T-Nb205/NS-G） as anode for Li-HSCs. X-ray diffraction and morphological analysis show that the T-Nb2O5 nano sheets successfully and uniformly distributed on the NS-G sheets. The T-Nb2O5/NS-G hybrid exhibits great rate capability（capacity retention of63.1% from 0.05 to 5 A g^-1） and superior cycling stability（a low capacity fading of ～6.4% after 1000 cycles at 0.5 A g^-1）.The full-cell consisting of T-Nb2O5/NS-G and active carbon（AC） results in high energy density（69.2 W h kg^-1 at0.1 A g^-1）, high power density（9.17 kW kg^-1） and excellent cycling stability（95% of the initial energy after 3000 cycles）.This excellent performance is mainly attributed to the highly conductive NS-G sheets, the uniformly distributed T-Nb2O5 nano sheets and the synergetic effects between them. These encouraging performances confirm that the obtained TNb2O5/NS-G has promising prospect as the anode for Li-HSCs.

Wet-spinning assembly of nitrogen-doped graphene film for stable graphene-polyaniline supercapacitor electrodes with high mass loading

Graphene-polyaniline(GP)composites are promising electrode materials for supercapacitors but possessing unsatisfied stability,especially under high mass loading,due to the low ion transmission efficiency and serious pulverization effect.To address this issue,we propose a scalable method to achieve highly wettable GP electrodes,showing excellent stability.In addition,our results demonstrate that the performance of electrodes is nearly independent of the mass loading,indicating the great potential of such GP electrodes for practical devices.We attribute the remarkable performance of GP to the delicate precursor of nitrogen doped graphene film assembled by wet-spinning technology.This report provides a strategy to promote the ion penetrating efficiency across the electrodes and deter the pulverization effect,aiming at the practical GP supercapacitor electrodes of high mass loading.

Advanced Asymmetrical Supercapacitors Based on Graphene Hybrid Materials

Supercapacitors operating in aqueous solutions are low cost energy storage devices with high cycling stability and fast charging and discharging capabilities, but generally suffer from low energy densities. Here, we grow Ni（OH）2 nanoplates and RuO2 nanoparticles on high quality graphene sheets in order to maximize the specific capacitances of these materials. We then pair up a Ni（OH）2/graphene electrode with a RuO2/graphene electrode to afford a high performance asymmetrical supercapacitor with high energy and power density operating in aqueous solutions at a voltage of -1.5 V. The asymmetrical supercapacitor exhibits significantly higher energy densities than symmetrical RuO2-RuO2 supercapacitors or asymmetrical supercapacitors based on either RuO2- carbon or Ni（OH）2-carbon electrode pairs. A high energy density of -48 W.h/kg at a power density of -0.23 kW/kg, and a high power density of -21 kW/kg at an energy density of N14 W-h/kg have been achieved with our Ni（OH）2/graphene and RuO2/graphene asymmetrical supercapacitor. Thus, pairing up metal-oxide/graphene and metal-hydroxide/graphene hybrid materials for asymmetrical supercapacitors represents a new approach to high performance energy storage.

Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO_2 and reduced graphene oxide via electrochemical deposition

Flexible and micro-sized energy conversion/storage components are extremely demanding in portable and multifunctional electronic devices, especially those small,flexible, roll-up and even wearable ones. Here in this paper, a two-step electrochemical deposition method has been developed to coat Ni fibers with reduced graphene oxide and MnO2 subsequently, giving rise to Ni@reduced-graphene-oxide@MnO2 sheath-core flexible electrode with a high areal specific capacitance of 119.4 mF cm^-2 at a current density of 0.5 mA cm^-2 in 1 mol L^-1 Na2SO4 electrolyte. Using polyvinyl alcohol（PVA）-LiCl as a solid state electrolyte, two Ni@reduced-grapheneoxide@Mn02 flexible electrodes were assembled into a freestanding, lightweight, symmetrical fiber-shaped micro-supercapacitor device with a maximum areal capacitance of26.9 mF cm^-2. A high power density of 0.1 W cm^-3 could be obtained when the energy density was as high as0.27 mW h cm^-3. Moreover, the resulting micro-supercapacitor device also demonstrated good flexibility and high cyclic stability. The present work provides a simple, facile and low-cost method for the fabrication of flexible, lightweight and wearable energy conversion/storage micro-devices with a high-performance.

A generalized one-step in situ formation of metal sulfide/reduced graphene oxide nanosheets toward high-performance supercapacitors

Metal sulfides are promising candidates for supercapacitors,but their slow reaction kinetics hinders their electrochemical performance.Large electrochemical surface area and combination with conductive carbon are potential methods to improve their capacitive performance.However,seeking for a generalized and simple approach to prepare two-dimensional composites of metal sulfide and conductive carbon for supercapacitors is challengeable.Herein,a generalized and facile one-step pyrolysis method was designed for in situ growth of cobalt nickel sulfides(CoNi2S4)on reduced graphene oxide(rGO)nanosheets(CoNi2S4/rGO)under mild conditions.The as-prepared CoNi2S4/rGO materials possess the nanoparticles-on-nanosheets structure,which is effective to provide a myriad of active sites and optimized electron/ion diffusion pathway.Benefiting from those advantages,the resultant CoNi2S4/rGO electrodes exhibit impressed specific capacitances of 1526 and 988 F g^−1 at 2 and 20 A g^−1,respectively.The supercapacitors based on CoNi2S4/rGO showcase an operation potential window of 1.6 V,and energy density of 54.8 W h kg^−1 at the power density of 798 W kg^−1.The capacitance retention of the supercapacitor is about 93.7%after 8000 cycles at 3 A g^−1.Moreover,a series of metal sulfide/rGO hybrids are obtained by this generalized strategy,which could be extended to construct electrode materials for various energy devices.