With the rapid development of wearable/portable electronics,there is considerable demand in developing energy storage systems[1-3]having superior functionity and shape versatility.Among all the power sources,micro-supercapacitors[4-9]exhibit ultrahigh power densities and superior cycling lifetime,which could be several times higher than those of traditional batteries and supercapacitors.However,most state-of-the-art micro-supercapacitors are still limited with monotonous layout and a low mass loading of active material,which could hardly meet the need of mini-power sources with a high capacitive level.

The exploration of active materials in micro-supercapacitors mainly concerns highly reversible capacitance,environmental friendliness,mechanical flexibility and compositional stability[10-12].Recently,carbon-based micro-supercapacitors utilizing graphene[13],carbon nanotubes[14],carbide-derived carbon[15]and onion-like carbon[16]has been widely used.These advanced electrochemical double layer capacitors(EDLCs)present a high power density,but generally exhibit low volumetric capacitance.To overcome this constraint,a series of pseudocapacitive electrode materials,such as Mn O2[17,18],VS2[19],Cu O[20]and PEDOT:PSS[21]have been used.These achievements have provided elaborate insights into the technological development of micro-supercapacitors.Among them,manganese oxides have been proven an excellent pseudocapactive electrode material for high-performance micro-supercapacitors[17],owing to their high theoretical specific capacity(1380 F/g)[22],large operating potential window,low material cost,and environmental friendliness.Recently,the ultrathin δ-Mn O2 nanosheets with large surface areas and porous structure have been proven as a competitive active material for energy storage application.While the intrinsic flaw s of manganese oxides still exist.Especially,the poor electrical conductivity(10-5-10-6 S/cm)would deteriorate rate capability and shorten the cycle life of the electrodes,which limits the electrochemical performance.To solve this problem,conductive additives,for example carbon nanotubes,with the properties of high surface area,remarkable conductivity and mechanical stability[23,24],have been explored to incorporate with Mn O2 to enhance the performance of electrode materials.How ever,how to further increase the mass loading of the active material,so as to improve the specific capacitance per area,still remains a challenge.

With the rise of wearable electronics,demands not only concern about energy storage functionality,but also include cultural and fashion aspects.Shi et al.recently presented a visual and aesthetic property(i.e.,letter,word,pattern or picture)of supercapacitors through screen printing method[25].Lin et al.demonstrated a high performance planar supercapacitor,in which the pattern of interdigitated metal finger arrays was inkjet printed on flexible substrates[26].These works pioneered the energy storage devices to meet the specific demand of the consumer electronics[27].Apart from the aesthetical pleasure,consumers also expect the portable devices to be physically small.For example,devices with amazing patterns can be attached to necklaces or fingernails while maintaining the function of energy storage.How ever,screen printing with relatively low precision and inkjet printing with the limitation of thicker electrode films pose challenges for high-performance aesthetic micro-devices.In recent years,the laser scribing technique,which enables practicable and meticulous fabrication[13,28],has prompted increasing research interests on graphical fabrication of various functional electronic devices[29].

Herein,we introduce a laser processed micro-supercapacitors(LPMS)based on carbon nanotubes/manganese dioxide nanosheets(CNTs/δ-Mn O2)composite electrode.This composite with excellent electrochemical performance was synthesized through facile and scalable method.In such a device,the pattern of interdigitated active material finger arrays was finely fabricated through laser scribing technique.Most interestingly,this LPMS can be designed to show desirably aesthetic property and shape diversity.For example,a device with a vivid pattern can stick on a necklace while maintaining the function of energy storage.Overall,our technology reported here opens up opportunities for facile and meticulous fabrication of energy devices with shape diversity and a meaning of art.These energy devices can be broadly used in future wearable components.

Typically,200 m L aqueous suspension of CNTs(NTP2021,Shen Zhen Nanotech Port) with different concentrations(1 mg/m L,2.5 mg/m L,6 mg/m L,12 mg/m L,18 mg/m L)was added into a three-necked flask and heated to 90°C with magnetic stirring.Pumping through a multi-channel peristaltic pump(Longerpump,BT100-1L)at a speed of 0.5 m L/min,KMn O4(0.05 mol/L,100 m L)and Mn(Ac)2(0.05 mol/L,100 m L)solutions were added into the flask simultaneously.With this method,the δ-Mn O2 nanosheets can grow on the surface of CNTs and thus form a composite in the flask with a high surface area.After reaction,the flask was cooled down to room temperature,and the as-obtained solution was then centrifuged(Bioridge,DD-5 M)at the speed of 5000 r/min and w ashed several times by deionized water.Finally,the precipitate was freeze-dried(BMH Instruments,Alpha 1-2 LD plus).In this way,different CNTs/δ-Mn O2 composite samples with the Mn O2 mass percentages of 21.5%,27.3%,41.5%,66.5%,and 81.4%can be obtained.

Fig.1.Schematic of the electrode fabrication process.

微泡排气阀综合利用多项物理原理，有效地使气泡从水中分离并积聚在排气舱内，并最终通过自动排气阀排出。微泡排气阀的口径从DN15至DN150，可以满足一般系统的要求。该阀有水平安装和垂直安装两种类型，应用于冷水管路上的阀门可选用带保温壳的产品，以防止表面结露。

The cycling performance of this electrode was studied by repeating the CV test at a scan rate of 100 m V/s,as shown in Fig.2c.It is noteworthy that,the capacitance retention of CNTs/δ-Mn O2 composite can still remain at 87.2%even after 4,000 cycles,with the Cm value decreased from 257 F/g to 224 F/g,indicating excellent stability.In Fig.2d,the frequency response analysis,in the frequency range between 10 m Hz and 100 k Hz with amplitude of 5 m V at an open-circuit potential,was conducted to study the alternating current impedance property of the CNTs/δ-Mn O2 electrode.The charge transfer resistance(Rct),caused by Faradic reactions and the double-layer capacitance on the grain surface was extremely small.It suggests that the electrode exhibited excellent conductivity,which also contributed to the negligible voltage drop in the beginning of the GCD curve.The superior performance of the CNTs/δ-Mn O2 composite can be attributed to the following three aspects[31]:1)The interactions among the electrode composite can form a uniform porous nanostructure,which reducesthe diffusion length of the ions and electrons within the electrode material;2)The CNT with a high conductivity provides abundant transport channels for electrons;3)The slurry dispensing process can render a face-to-face assembly of the materials,which helps provide superior electrochemical properties along the in-plane direction.

Optical images of the LPMS are shown in Fig.4a.The planar electrode con figurations could be conveniently modulated by altering the geometric parameters of the electrodes.Based on the laser processing technique,the LPMS could be fabricated in large scale precisely.

1158分段1#盘区三分层上盘界限以外的贫矿资源属于东部贫矿开发项目范围内，但考虑到1158分段1#盘区三分层回采结束后就转入978分段，中段接替过程中未知因素较多，如果发生突发问题，则可考虑将上盘贫矿作为临时过渡时期完成全年计划的矿石来源。1158分段1#盘区围岩条件较好，地应力稳定，可以考虑采用边缘进路作为临时沿脉道进行施工。该部分矿石回采结束后，也是为以后1#盘区以上贫矿回收做好了人工假底。如中段衔接顺利，则该部分矿体依旧根据东部贫矿项目设计方案进行回采。

集成学习的两个主要工作一般可以划分到训练和检验两个阶段。训练阶段是训练形成集成模型，主要针对训练样本数据集，划分多个弱分类器按照一定的融合集成规则形成一个强分类器；检验阶段是验证调整集成模型，主要针对测试样本数据集，对多个弱分类器的预测结果按照一定的集成整合规则形成集成预测结果。其中，多分类器融合的集成模型是我们研究的重点。

The CNTs/δ-Mn O2 composite was prepared by a redox reaction,w here KMn O4 was used as the oxidizing agent and Mn(Ac)2 as the reducing agent.CNTs functioned as a nucleation site for the formation the Mn O2 nanosheets[30].To evaluate the electrochemical performance of CNTs/δ-Mn O2 composite electrode,CV,GCD and EIS studies were conducted using a three-electrode con figuration.0.5 mol/L aqueous Na2SO4 electrolyte was used and the working potential window was selected between 0 V and 0.8 V(vs.Ag/AgCl).As is shown in Fig.S1(Supporting information),the dramatic enhanced electrochemical performance of CNTs/δ-Mn O2 composite compared with pure CNTs film is attributed to the good synergetic effect between two components.CV curves of CNTs/δ-Mn O2 with varying Mn O2 ratios(21.5%,27.3%,46.5%,66.5%,and 81.4%)at the scan rate of 20 m V/s are presented in Fig.S2(Supporting information).As the CNTs/δ-Mn O2-41.5%showed a much better capacitance performance,the following results are presented based on this ratio.We take CNTs/δ-Mn O2 as the abbreviation for the CNTs/δ-Mn O2-41.5%in the following results for brief expression.

To evaluate the performance characteristic of the LPMS device with[C2MIm]BF4 electrolyte in practical application,the energy density E and the power density P were calculated from equations S4 and S5(Supporting information).Typical figure of merits include maximum energy density of 6.83 m Wh/cm3 at power density of 154.3 m W/cm 3,and of 2.71 m Wh/cm 3 at the maximum power density of 2557.5 m W/cm 3.Compared with the devices that were tested in aqueous electrolytes[26,34],non-aqueous electrolyte can remarkably enlarge the working potential window and optimize the energy density.As a consequence,our LPMS presents an excellent energy density and a competitive power density.

While in most cases,a high Cm value(～700 F/g)could be obtained when the film of the electrode material is very thin and the material needs to be loaded onto a current collector with high surface area,which is not included when calculating the specific capacitance value.With the increase of the current density,the Cm value decreased correspondingly,but still exhibited a value of 163 F/g at the scan rate of 2 A/g,which con firmed relatively excellent rate performance of the CNTs/δ-Mn O2 composite electrode.

鉴于此，本研究针对纸浆洗涤过程的特点，充分利用生产过程长期运行积累的工业数据，基于两步神经网络法得到残碱和黑液波美度的预测模型，通过这两大指标构建纸浆洗涤质量评价模型，对工业运行数据进行聚类、模式匹配，构建出优化模式库。以最优生产为目标，对优化模式库进行操作模式寻优，匹配出最优操作模式。通过实验验证该方法能有效预测纸浆洗涤过程的状态参数，达到优化生产的效果。

Fig.2.Electrochemical characterizations of the CNTs/δ-MnO2 electrode in 0.5 mol/L aqueous Na2SO4 electrolyte:(a)CV curves of the electrode at the scan rate from 5 mV/s to 200 m V/s;(b)GCD curves of the electrode at the current densities from 0.5 A/g to 10.0 A/g;(c)cycling performance of the electrode material;(d)Nyquist curve after the first cycle.

The fabrication process of the LPMS is shown in Fig.1.A typical LPMS was fabricated in the following steps.Firstly,polyethylene terephthalate(PET)was chosen as the flexible substrate;then a thin layer of nickel was magnetron-sputtered at ambient temperature with 1μm in thickness.Then the electrode slurry was bladed onto the substrate and dried in vacuum oven at 120°C for 12 h.The thickness of the electrode was13μm in this work and can be tunable.Afterwards,the laser beam(wavelength:355 nm,model:Han’s Laser EP-15-DW)was used to ablate redundant parts of the CNTs/δ-Mn O2 film and nickel layer to form an interdigital-electrode-structure LPMS array.In this work,the area of a single LPMS unit was controlled to be 60 mm 2.The width of the interdigital fingers and the interspace between them were 300μm and 250μm,respectively,and these con figurations can be conveniently modified.

在压水试验之后，将配制好的水泥浆通过高压泵和注浆管注入桩端土层中。初注时压力较小，浆液由稀到稠。注意注浆压力、注浆量和压力软管变化，并注意注浆节奏。同时，用百分表监测桩的上抬量。注浆完毕或较长时间停泵时，须对高压注浆泵、浆液拌和机及地面管路系统等认真清洗，以防水泥浆结块，堵塞管路和泵体。完成注浆后须立即将注浆管顶端用堵头封闭，以免回浆而降低注浆效果。

Considering the laser scribing technique is a power tool for meticulous fabrications,here it is used to fabricate thick electrodes.The symmetric LPMS can be fabricated by laser beam ablating the CNTs/δ-Mn O2 electrode and the thin nickel layer(current collector)to form interdigital electrode arrays.Moreover,the theoretical energy density of the micro-supercapacitors is in direct proportion to the square of the working potential as can be seen from equation S4(Supporting information).Hence,to develop a high performance micro-supercapacitor,the narrow working voltage window needs to be overcome by using non-aqueous electrolytes.In addition,better thermal stability of the nonaqueous electrolyte can render the LPMS resistant to the high temperature working process.Here we chose room temperature ionic liquid,[C2MIm]BF4,as the electrolyte so as to operate at a stable working voltage window of 2.0 V.

Then the CNTs/δ-Mn O2 powder(1.28 g)was mixed with 0.16 g PVDF binder,0.16 g super P conductive agent and NMP solvent(8 m L)in a planetary rotator mixer(Hasai 300,China)for preparing the electrode slurry.

Fig.3.Electrochemical characterizations of the LPMS in Na2SO4 electrolyte:(a)CV curves at the scan rate from 10 m V/s to 100 m V/s;(b)GCD curves of the material at various current densities;(c)Ca values versus scanning rate calculated by GCD study;(d)Cycling performance of the LPMS.

To characterize the electrochemical performance of the LPMS,Fig.3 illustrates the CV,GCD and cycling performance of a fully packed cell unit,which show s superior capacitive characteristic and rate performance.The CV characterization of the LPMS was performed under various scan rates ranging from 10 m V/s to 100 m V/s,as shown in Fig.3a.Calculated from equation S1(Supporting information),Ca of the LPMS can reach to 16.0 m F/cm 2,which was based on the total area of the device.

The GCD test was also perform ed to further characterize the electrochemical performance of the LPMS device.As is shown in Fig.3b,the IR drop calculated from the GCD curve was only 0.12 V at a current density of 0.2 A/g,by virtue of the small Ohmic contact resistance of the electrode materials.Specific capacitance of Ca values versus scanning rate calculated by CV study is shown in Fig.3c,w here it reveals that with the increase of the scan rate,the device cannot make full use of pseudocapacitance in the electrode material,the Ca value decreased accordingly.Additionally,as is shown in Fig.3d,the LPMS was subjected to 5,000 cycles of fulldepth charge/discharge at the scan rate of 100 m V/s,and a capacitance retention of 81.7%was obtained.The capacitance decay tendency during the continuing cycling test could be attributed to the following factor[32,33]:The volume expansion of active materials can be induced by intercalation and transportation of electrolyte ion into the bulk material during the redox reaction.

Fig.2a illustrates the typical CV performance of the electrode with various scan rates ranging from 5 m V/s to 200 m V/s.It shows that the CV curves were relatively rectangular in shape at low scan rate,and exhibited a near mirror-image current response on voltage reversal.When the scan rate got faster,there were no significant differences in the shape of the curves,indicating a fast charge/discharge capability and effective diffusion of electrolyte in the electrode material.As is presented in Fig.2b,the GCD curves of the CNTs/δ-Mn O2 electrode at various current densities of 0.5,1.0,2.0,5.0 and 10.0 A/g suggest excellent reversibility of charge storage and small voltage drop(0.05 V),which could be attributed to the high electrical conductivity of the CNTs/δ-Mn O2 composite electrode,further demonstrating the excellent capacitive behaviour of the composite electrode.The calculated Cm of the CNTs/δ-Mn O2 electrode as a function of current density,calculated from the GCD tests based on equation S1(Supporting information),exhibited a maximum value of 257 F/g at the current density of 0.5 A/g.

Owing to the relatively thick film of the electrode material by slurry dispensing technique,the areal capacitance of our LPMS is even better than those of the state-of-the-art thin film based ones(Table S1 in Supporting information).

Fig.4.Photographic images of laser scribed electrodes with various design.(a)Several LPMSs.(b)Artistic designed LPMS with a vivid pattern of“auspicious cloud”can stick on a necklace.(c)Different electrodes patterned of “shamrocks”and “crow n”.(d)Magnified image of the necklace in Fig.4b.

The detailed characterization and electrochemical measurements were provided in the Supporting information.

For future applications in portable micro-electronics,apart from unique functionality,the shape diversity and artistic property of devices are highly preferred.In this regard,the laser-scribing technique is probably the most flexible and versatile method to achieve high-performance micro-devices with artistic design.Particularly in this work,as shown in Fig.4b,LPMS with a vivid pattern of“auspicious cloud”is small enough to stick on a necklace.To verify such a concept,various designs of electrodes are presented in Fig.4c.These electrodes,showing wondrously visual and artistic property,can be further encapsulated into microsupercapacitors in a planar layout or a sandwich structure.

Here w e developed a CNTs/δ-Mn O2 composite-based microsupercapacitor.The CNTs/δ-Mn O2 electrode was synthesized using efficient and easy-fabrication methods including solution-phase assembly and slurry dispensing technique.The conventional slurry printing technique,can not only render a face-to-face assembly of electrode material,but also fabricate a thick electrode with the significance of optimizing the performance of micro-devices.The result of electrochemical tests con firm ed superior specific capacitance and long cycle life of the electrode,which could be attributed to several factors,including 3D network for the transportation of ions and electrons,good conductivity of the electrode material and superior electrochemical properties along the in-plane direction.Owing to the meticulous laser-scribing technique,the electrode can be patterned with a high resolution and made into a planar micro-supercapacitor.Last but not the least,desirably aesthetic property and shape diversity are crucial factors for the future micro-devices;the laser-scribing technique is arguably a flexible and versatile method to achieve these factors.Our work may open up opportunities for facile and delicate fabrication of energy devices with shape diversity and meaning of art.We believe that it may open a new era of the energy storage devices in future to meet the specific demand of the wearable/portable electronics.

错因：一是对题意把握不准而错选B项,该情况是忽视了离子组合的共存必须符合强酸性或强碱性环境任一情况的要求;二是忽

Acknowledgments

This work is financially supported by the National Key Basic Research Program of China(No.2014CB932400), the National Nature Science Foundation of China( Nos.51607102,51578310),China Postdoctoral Science Foundation (No.2016M601017),Guangdong Province Science and Technology Department(Nos.2014B090915002,2014A010105002,2015A030306010),and Natural Science Foundation of Guangdong Province (No.2017A030313279).

随着道路交通运输行业的快速发展，运输业务繁忙，加之各类因素的影响，比如天气等，使得各类安全事故发生。当事故发生后，若相关及时响应应急处置预案，做好及时救援工作，对减少事故损失，有着重要的意义。若想快速获取安全事故的相关信息，及时开展救援以及处置工作，必须要结合实际构建安全事故报告以及应急处置工作机制。道路运输主管部门要切实履职，做好各项工作部署，保证安全事故处理工作得以有效开展。通过明确安全事故报告时间节点以及内容等，优化安全事故报告程序，完善事故应急处置，进而保证安全事故得以有效控制。

Appendix A.Supplementary data

Supplementary data associated with this article can be found,in the online version,at https://doi.org/10.1016/j.cclet.2018.01.024.

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