Physical and Electrochemical Characterization of LiCo0.8M0.2O2 （M=Ni,Zr） Cathode Films for All-solid-state Rechargeable Thin-film Lithium Batteries

LiCo0.8M0.2O2 （M=Ni,Zr） films were fabricated by radio frequency sputtering deposition combined with conventional annealing methods. The strtuctures of the films were characterized with X-ray diffraction （XRD）, Raman spectroscopy and scarming electron microscopy （SEM） techniques. It was shown that the 700 ℃- annealed LiCo0.8M0.2O2 has an α-NaFeO2 like layered structure. All-solid-state thin-film batteries （TFBs） were fabrieated with these films as the cathode and their eleetroctemical performances were evaluated. It was found that doping of electrochemically active Ni and inactive Zr has different effects on the structural and elcctrochemical properties of the LiCoO2 cathode films. Ni doping increases the discharge capacity of the film while Zr doping improves its cycling stability.

A flexible carbon nanotube@V_(2)O_(5) film as a high-capacity and durable cathode for zinc ion batteries

Aqueous zinc-ion batteries(ZIBs)are receiving a continuously increasing attention for mobile devices,especially for the flexible and wearable electronics,due to their non-toxicity,non-flammability,and low-cost features.Despite the significant progress in achieving higher capacities for electrode materials of ZIBs,to endow them with high flexibility and economic feasibility is,however,still a significant challenge remaining unsolved.Herein,we present a highly flexible composite film composed of carbon nanotube film and V_(2)O_(5)(CNTF@V_(2)O_(5))with high strength and high conductivity,which is prepared by simply impregnating a porous CNT film with an aqueous V_(2)O_(5)sol under vacuum.For this material,intimate incorporation between V_(2)O_(5)and CNTs has been achieved,successfully integrating the high zinc ion storage capability with high mechanical flexibility.As a result,this CNTF@V_(2)O_(5)film delivers a high capacity of 356.6 m Ah g^(-1)at 0.4 A g^(-1)and excellent cycling stability with 80.1%capacity retention after 500 cycles at 2.0 A g^(-1).The novel strategy and the outstanding battery performance presented in this work should shed light on the development of high-performance and flexible ZIBs.

Uniformity of TiN Films Fabricated by Hollow Cathode Discharge

Titanium nitride （TIN） films were deposited on AISI 304 stainless steel substrates using hollow cathode plasma physical vapor deposition （HC-PVD）. Titanium was introduced by eroding the Ti cathode nozzle and TiN was formed in the presence of a nitrogen plasma excited by radio frequency （RF）. The substrate bias voltage was varied from 0 to -300 V and the uniformity in film thickness, surface roughness, crystal size, microhardness and wear resistance for the film with a diameter of 20 mm was evaluated. Although the central zone of the plasma had the highest ion density, the film thickness did not vary appreciably across the sample. The results from atomic force microscopy （AFM） revealed a low surface roughness dominated by an island-like morphology with a similar crystal size on the entire surface. Higher microhardness was measured at the central zone of the sample. The sample treated at -200 V had excellent tribological properties and uniformity.

PROPERTIES OF MgB_2 FILMS FABRICATED ON COPPER CATHODES BY ELECTROCHEMICAL TECHNIQUE

An electrochemical technique has been introduced and applied to fabricate superconducting MgB2 films in molten salts. MgCl2, Mg（BO2）2, NaCl, and KCl were used as electrolyte, graphite was used as the anode, and copper was used as the cathode, respectively. X-ray diffraction （XRD） analysis was chosen to investigate the phase composition and crystallinity of the films at different electrolysis temperatures. Stan- dard four-probe technique and SQUID were applied to investigate the temperature dependence of resistance （R-T） properties and magnetic properties of the films, respectively. The results indicate that MgB2 films have been fabricated on the copper cathodes, and superconducting transition takes place close to 50 K.

Optical and electrical properties of BaSnO_(3) and In_2O_(3) mixed transparent conductive films deposited by filtered cathodic vacuum arc technique at room temperature

For the crystalline temperature of BaSnO_(3)(BTO)was above 650℃,the transparent conductive BTO-based films were always deposited above this temperature on epitaxy substrates by pulsed laser deposition or molecular beam epitaxy till now which limited there application in low temperature device process.In the article,the microstructure,optical and electrical of BTO and In_(2)O_(3) mixed transparent conductive BaInSnO_(x)(BITO)film deposited by filtered cathodic vacuum arc technique(FCVA)on glass substrate at room temperature were firstly reported.The BITO film with thickness of 300 nm had mainly In_(2)O_(3) polycrystalline phase,and minor polycrystalline BTO phase with(001),(011),(111),(002),(222)crystal faces which were first deposited at room temperature on amorphous glass.The transmittance was 70%–80%in the visible light region with linear refractive index of 1.94 and extinction coefficient of 0.004 at 550-nm wavelength.The basic optical properties included the real and imaginary parts,high frequency dielectric constants,the absorption coefficient,the Urbach energy,the indirect and direct band gaps,the oscillator and dispersion energies,the static refractive index and dielectric constant,the average oscillator wavelength,oscillator length strength,the linear and the third-order nonlinear optical susceptibilities,and the nonlinear refractive index were all calculated.The film was the n-type conductor with sheet resistance of 704.7Ω/□,resistivity of 0.02Ω⋅cm,mobility of 18.9 cm2/V⋅s,and carrier electron concentration of 1.6×10^(19) cm^(−3) at room temperature.The results suggested that the BITO film deposited by FCVA had potential application in transparent conductive films-based low temperature device process.

In-situ fabrication of dual porous titanium dioxide films as anode for carbon cathode based perovskite solar cell

We develop a dual porous （DP） TiO2 film for the electron transporting layer （ETL） in carbon cathode based perovskite solar cells （C-PSCs）. The DP TiO2 film was synthesized via a facile PS-templated method with the thickness being controlled by the spin-coating speed. It was found that there is an optimum DP TiO2 film thickness for achieving an effective ETL, a suitable perovskite]TiO2 interface, an efficient light harvester and thus a high performance C-PSC. In particular, such a DP TiO2 film can act as a scaffold for complete-filling of the pores with perovskite and for forming high-quality perovskite crystals that are seamlessly interfaced with Ti02 to enhance interracial charge injection. Leveraging the unique advantages of DP TiO2 ETL, together with a dense-packed and pinhole-free TiO2 compact layer, PCE of the C-PSCs has reached 9.81% with good stability.

Fabrication of Tungsten Carbide Films by Filtered Pulse Arc Deposition with Cemented Tungsten Carbide Cathodes

Tungsten carbide films (W-C films) were fabricated on silicon substrates by using the filtered pulse arc deposition (FPAD) method. Two types of cemented tungsten carbide (WC) were used as cathode, one containing Co and the other Ti, which were used as binders for forming the cathode shape. The films were fabricated by varying the pulse arc current and substrate bias voltage. The discharge, deposition and film properties were investigated under these deposition conditions. The cathode wear amount when using WC-Co (WC cathode containing Co) was found to be smaller than that measured when WC-Ti (WC cathode containing Ti) was used. The W-C film thickness was approximately 30 - 40 nm under all conditions, except when the pulse arc current was 50 A and the film thickness, was approximately 10 nm. Compared to the WC-Ti, the consumption of cathode material is suppressed in the WC-Co, indicating that the efficiency for film preparation of the latter is good. From the X-ray diffraction analysis, the crystalline phase of W-C films fabricated using WC-Co and WC-Ti were observed as W2C and WC1-x, respectively, indicating that different crystalline phases could be fabricated using different cathodes. From the X-ray photoelectron spectroscopy analysis, the oxidation layer formed by air exposure was observed to exclusively exist on the W-C film surface. Moreover, almost all oxygen in the oxidation layer bonded with tungsten.

Application of printed nanocrystalline diamond film for electron emission cathode

The low-cost and large area screen-printed nano-diamond film (NDF) for electronic emission was fabricated. The edges and corners of nanocrystalline diamond are natural field-emitters. The nano-diamond paste for screen-printing was fabricated of mixing nano-graphite and other inorganic or organic vehicles. Through enough disperse in isopropyl alcohol by ultrasonic nano-diamond paste was screen-printed on the substrates to form NDF. SEM images showed that the surface morphology of NDF was improved, and the nano-diamond emitters were exposed from NDF through the special thermal-sintering technique and post-treatment process. The field emission characteristics of NDF were measured under -6 all conditions with 10 Pa pressure. The results indicated that the field emission stability and emission uniformity of NDF were improved through hydrogen plasma post-treatment process. The turn-on field decreased from 1.60 V/ μm to 1.25 V/ μm . The screen-printed NDF can be applied to the displays electronic emission cathode for low-cost outdoor in large area.

Effect of pulsed bias on the properties of ZrN/TiZrN films deposited by a cathodic vacuum arc

ZrN/TiZrN multilayers are deposited by using the cathodic vacuum arc method with different substrate bias（from 0 to 800 V）,using Ti and Zr plasma flows in residual N 2 atmosphere,combined with ion bombardment of sample surfaces.The effect of pulsed bias on the structure and properties of films is investigated.Microstructure of the coating is analyzed by X-ray diffraction（XRD）,and scanning electron microscopy（SEM）.In addition,nanohardness,Young＇s modulus,and scratch tests are performed.The experimental results show that the films exhibit a nanoscale multilayer structure consisting of TiZrN and ZrN phases.Solid solutions are formed for component TiZrN films.The dominant preferred orientation of TiZrN films is（111） and（220）.At a pulsed bias of 200 V,the nanohardness and the adhesion strength of the ZrN/TiZrN multilayer reach a maximum of 38 GPa,and 78 N,respectively.The ZrN/TiZrN multilayer demonstrates an enhanced nanohardness compared with binary TiN and ZrN films deposited under equivalent conditions.

Deposition of Diamond-Like Carbon on Inner Surface by Hollow Cathode Discharge

A cylindrical hollow cathode discharge （HCD） in CH4/Ar gas mixture at pressure of 20-30 Pa was used to deposit diamond-like carbon （DLC） films on the inner surface of a stainless steel tube. The characteristics of the HCD including the voltage-current curves, the plasma im- ages and the optical emission spectrum （OES） were measured in Ar and CHn/Ar mixtures. The properties of DLC films prepared under different conditions were analyzed by means of Raman spectroscopy and scanning electron microscopy （SEM）. The results show that the electron exci- tation temperature of HCD plasma is about 2400 K. DLC films can be deposited on the inner surface of tubes. The ratio of sp3/sp2 bonds decreases with the applied voltage and the deposition time. The optimizing CH4 content was found to be around CH4/Ar =1/5 for good quality of DLC films in the present system.

Cathodic electrolysis method of depositing cerium conversion films on industrial pure aluminum

Two two-step techniques, called TS2/TS7 and TS3/TS7, respectively,have been developed to form cerium conversion films on the surface ofindustrial pure aluminum. The tested material was cathodicallyelectrolyzed in the al- kaline solution containing cerium salt, anduniform films containing cerium were obtained after the two-steptreatment. It is found that the films obtained by TS2/TS7 and TS3/TS7techniques are about 4.0 and 3.0 um in thickness, respectiv- Ely. Thematerial has better corrosion resistance in the chloride solutionafter the two-step electrolysis treatent compar- Ed with the one-steptreated and naked specimens.

Deposition of Ti-AI-N Films by Using a Cathodic Vacuum Arc with Pulsed Bias

Ti-Al-N hard films have been prepared by cathodic arc deposition by using an unipolar pulsed bias.In the present study,Ti-Al-N films were deposited on stainless steel and silicon wafers.The deposition rate,micrograph,preferred orientation and composition were systematically investigated by usingx-ray diffraction（XRD）,energy dispersive X-ray spectroscopy（EDX）, and a scanning electron microscope（SEM）.It is shown that substate bias duty cycle and frequency have a great effect on film structure.A simple explanation for the results is also presented.

Cathode Formed by Thermal Evaporation of Ba:Al Alloy and Estimations of Barrier Height in an Organic LED

It is demonstrated that barium and aluminum alloy synthesized by melting in a glass tube under low vacuum is applicable for organic laser emitting diodes(LEDs)as a thin film cathode.The alloy film obtained by the thermal evaporation of pre-synthesized alloy is used in a single-boat organic LED device with the structure:indium tin oxide(ITO)/4,4'-bis[N−(1-naphthyl)-N−phenylamino]biphenyl(NPB)/tris-(8-hydroxyquinoline)aluminum(Alq3)/barium:aluminum alloy.The experimental results show that devices with this alloy film cathode exhibit better current density-voltage-luminance characteristics than those with a conventional pure Al cathode,and more weight of barium in aluminum leads to better performance of the devices.Characteristics of current density versus voltage for the electron-only devices are fitted by the Richardson–Schottky emission model,indicating that the electron injection barrier has a decrease of about 0.3 eV by this alloy cathode.

Repassivation Behaviour of UNS S32101 and UNS S30403 Stainless Steels after Cathodic Stripping of the Native Passive Film in a CO₂-Saturated Oilfield Brine

Repassivation behaviour of the passive film formed on lean duplex stainless steel UNS S32101 and austenitic stainless steel UNS S30403 in a CO2-saturated oilfield environment has been studied. The native passive film on the alloys was thinned/removed by stepping the potential of the alloy to ﹣850 mV/Ag/AgCl for 30 minutes. Potentiostatic measurements were then taken at potentials of ﹣200, ﹣100, 0, 100 and 200 mV versus Ag/AgCl. Results show that the passive film repassivates at potentials of ﹣200 and ﹣100 mV and 0 mV for both alloys at 50°C. The current density however continues to rise for potentials of 100 and 200 mV. This shows that both alloys are susceptible to pitting at potentials above 100 mV at the test temperature of 50°C.

Mechanical Properties of Composite SiNx/DLC Films Prepared by Filtered Cathodic Arc of Graphite Incorporated with RF Sputtering of Silicon Nitride

Composite SiNx/DLC films were deposited on Si substrate by RF magnetron sputtering of silicon nitride (Si3N4) target simultaneously with filtered cathode arc (FCA) of graphite. The RF power was fixed at 100 W whereas the arc currents of FCA were 20, 40, 60 and 80 A. The effects of arc current on the structure, surface roughness, density and mechanical properties of SiNx/DLC films were investigated. The results show that the arc current in the studied range has effect on the structure, surface roughness, density and mechanical properties of composite SiNx/DLC films. The composite SiNx/DLC films show the sp3 content between 53.5% and 66.7%, density between 2.54 and2.98 g/cm3, stress between 1.7 and 2.2 GPa, and hardness between 35 and 51 GPa. Furthermore, it was found that the density, stress and hardness correlate linearly with the sp3 content for composite SiNx/DLC films.

Phosphate film free of chromate, fluoride and nitrite on AZ31 magnesium alloy and its corrosion resistance

A phosphate solution free of chromate, fluoride and nitrite was prepared and an environment-friendly film was obtained on AZ31 magnesium alloy surface via the chemical deposition method. The morphology, composition, phase structure and its corrosion resistance were studied. The effects of film-forming temperature and free acid on corrosion resistance, microstructure and electrochemical behavior of the film were discussed. The results indicate that the corrosion resistance of AZ31 with the phosphate film was better than blank AZ31 substrate, which was most attributed to the great inhibitive action on the anodic dissolution and cathodic hydrogen evolution of the film.

磁控溅射制备LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)薄膜工艺研究

目的探究了磁控溅射法制备符合化学计量比且循环性能良好的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)薄膜工艺,有利于进一步提高全固态薄膜电池能量密度。方法从溅射功率、氩氧比、衬底温度中各选取3个水平组成L9(34)正交试验,在不锈钢衬底上沉积制备NCM811薄膜。利用X射线衍射仪和扫描电子显微镜对薄膜进行表征。利用EDS和ICP对薄膜成分进行分析。利用蓝电测试系统对以NCM811为正极的电池进行循环曲线测试。结果根据极差分析结果发现,影响前50圈放电容量保持率的因素从大到小依次为:温度>功率>氩氧比。其中功率和温度对循环性能有很大的影响,极差R值分别为18.45和26.79;氩氧比对循环性能影响较小,极差R值为3.17。增大溅射功率、提高衬底加热温度、增加氩氧比中氩气的含量有利于制备出符合化学计量比的NCM811薄膜。随着溅射功率的提升,NCM811薄膜的结晶度增强,材料中Ni^(2+)/Li^(+)阳离子的混排程度降低;随着衬底温度升高,薄膜由非晶逐渐转化为晶态,表面由无序非晶形貌过渡到小三角片状晶粒,厚度变薄,且更加致密。薄膜的循环性能也随着功率和衬底温度的增加有着明显的提升。结论正交试验结果表明,薄膜制备的最优工艺条件为:溅射功率110 W,衬底温度650℃,Ar∶O_(2)=2∶1(体积流量比),验证试验表明NCM811薄膜中主元素原子数占比Ni∶Co∶Mn=79.9∶10.2∶9.9,接近理想原子数占比8∶1∶1,且前50圈放电容量保持率达到72.33%。

基于阴极沉积Mg(OH)_(2)薄膜的镁合金超疏水表面改性及其耐蚀性研究

为延长镁合金的使役寿命,通过阴极沉积和超疏水改性在ME20M稀土镁合金表面制备超疏水涂层,采用硬脂酸乙醇基溶液对阴极沉积Mg(OH)_(2)薄膜的镁合金进行化学修饰,通过单因素试验分别考察硬脂酸浓度、溶液温度、浸泡时间对表面润湿性的影响规律,确定最优修饰工艺。对典型试样,采用点滴实验、全浸腐蚀实验及现代电化学测试技术评估其耐蚀性,采用划格法评价膜/基结合力,采用SEM、FT-IR及XRD分析试样表面微观形貌及成分。结果表明:阴极沉积Mg(OH)_(2)薄膜经低浓度硬脂酸溶液短暂浸泡即可获得超疏水性,蒸馏水静态接触角SCA高达151.5°,滚动角SA低至1.0°,呈低黏性。阴极沉积/疏水改性复合处理可显著改善镁合金的耐蚀性,与空白试样相比,复合处理试样的点滴液变色时间延长近25倍,在3.5%NaCl溶液中的自腐蚀电流密度Jcorr降低3个数量级,特征阻抗模值|Z|_(0.1 Hz)提高4个数量级。经疏水处理的阴极沉积Mg(OH)_(2)薄膜呈刀片状微纳结构,试样的红外光谱中出现明显的-CH_(3)和-CH_(2)-吸收峰。

Improved cyclic stability of LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) cathode enabled by a novel CEI forming additive

The undesired side reactions at electrode/electrolyte interface as well as the irreversible phase evolution during electrochemical cycling significantly affect the cyclic performances of nickel-rich NMCs electrode materials.Electrolyte optimization is an effective approach to suppress such an adverse side reaction,thereby enhancing the electrochemical properties.Herein,a novel boron-based film forming additive,tris(2,2,2-trifluoroethyl)borate(TTFEB),has been introduced to regulate the interphasial chemistry of LiNi0.8Mn0.1Co0.1O2(NMC811)cathode to improve its long-term cyclability and rate properties.The results of multi-model diagnostic study reveal that formation lithium fluoride(LiF)-rich and boron(B)containing cathode electrolyte interphase(CEI)not only stabilizes cathode surface,but also prevents electrolyte decomposition.Moreover,homogenously distributed B containing species serves as a skeleton to form more uniform and denser CEI,reducing the interphasial resistance.Remarkably,the Li/NMC811 cell with the TTFEB additive delivers an exceptional cycling stability with a high-capacity retention of 72.8%after 350 electrochemical cycles at a 1 C current rate,which is significantly higher than that of the cell cycled in the conventional electrolyte(59.7%).These findings provide a feasible pathway for improving the electrochemical performance of Ni-rich NMCs cathode by regulating the interphasial chemistry.

高温锂离子电池用混盐电解液体系

正极电解质相界面(CEI)膜会影响锂离子电池的高温性能。商用电解液在高温下的热稳定性差,形成的CEI膜不够稳定,易导致电池失效。以热稳定性及成膜性能良好的双三氟磺酰亚胺锂(LiTFSI)和二氟草酸硼酸锂(LiODFB)为锂盐,EC+EMC(体积比3∶7)为溶剂,构建电解液体系,考察制备的LiCoO_(2)/Li半电池的电化学性能。在70℃下,LiCoO_(2)/Li半电池在0.5 mol/L LiTFSI+0.5 mol/L LiODFB基电解液体系下,以1.0 C在2.7~4.2 V循环,首次放电比容量为131.2 mAh/g,循环100次的容量保持率为90.8%。这得益于电解液体系生成了均匀、致密且具有良好离子电导率的CEI膜。