Reversible solid-liquid conversion enabled by self-capture effect for stable non-flow zinc-bromine batteries

Non-flow aqueous zinc-bromine batteries without auxiliary components(e.g.,pumps,pipes,storage tanks)and ion-selective membranes represent a cost-effective and promising technology for large-scale energy storage.Unfortunately,they generally suffer from serious diffusion and shuttle of polybromide(Br^(-),Br^(3-))due to the weak physical adsorption between soluble polybromide and host carbon materials,which results in low energy efficiency and poor cycling stability.Here,we develop a novel self-capture organic bromine material(1,10-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium bromine,NVBr4)to successfully realize reversible solid complexation of bromide components for stable non-flow zinc-bromine battery applications.The quaternary ammonium groups(NV^(4+)ions)can effectively capture the soluble polybromide species based on strong chemical interaction and realize reversible solid complexation confined within the porous electrodes,which transforms the conventional“liquid-liquid”conversion of soluble bromide components into“liquid-solid”model and effectively suppresses the shuttle effect.Thereby,the developed non-flow zinc-bromide battery provides an outstanding voltage platform at 1.7 V with a notable specific capacity of 325 mAh g^(-1)NVBr4(1 A g^(-1)),excellent rate capability(200 mAh g^(-1)NVBr4 at 20 A g^(-1)),outstanding energy density of 469.6 Wh kg^(-1)and super-stable cycle life(20,000 cycles with 100%Coulombic efficiency),which outperforms most of reported zinc-halogen batteries.Further mechanism analysis and DFT calculations demonstrate that the chemical interaction of quaternary ammonium groups and bromide species is the main reason for suppressing the shuttle effect.The developed strategy can be extended to other halogen batteries to obtain stable charge storage.

Electrode/Electrolyte Interfacial Chemistry Modulated by Chelating Effect for High-Performance Zinc Anode

Although Zn metal has been regarded as the most promising anode for aqueous batteries,its practical application is still restricted by side reactions and dendrite growth.Herein,an in-situ solid electrolyte interphase(SEI)film formed on the interface of electrode/electrolyte during the plating/stripping of zinc anodes by introducing trace amounts of multidentate ligand sodium diethyldithiocarbamate(DDTC)additive into 1 M ZnSO_(4).The synergistic effect of in-situ solid electrolyte interphase forming and chelate effect endows Zn^(2+)with uniform and rapid interface-diffusion kinetics against dendrite growth and surface side reactions.As a result,the Zn anode in 1 M ZnSO_(4)+DDTC electrolytes displays an ultra-high coulombic efficiency of 99.5%and cycling stability(more than 2000 h),especially at high current density(more than 600 cycles at 40 mA cm^(-2)).Moreover,the Zn//MnO_(2)full cells in the ZnSO_(4)+DDTC electrolyte exhibit outstanding cyclic stability(with 98.6%capacity retention after 2000 cycles at 10 C).This electrode/electrolyte interfacial chemistry modulated strategy provides new insight into enhancing zinc anode stability for high-performance aqueous zinc batteries.

High-performance magnesium/sodium hybrid ion battery based on sodium vanadate oxide for reversible storage of Na^(+)and Mg^(2+)

Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.

Synergistic enhancement of cathode/anode interfaces with high water-retentive organohydrogel enabling highly stable zinc ion batteries

Current aqueous battery electrolytes,including conve ntional hydrogel electrolytes,exhibit unsatisfactory water retention capabilities.The sustained water loss will lead to subsequent polarization and increased internal resistance,ultimately resulting in battery failure.Herein,a double network(DN) orga no hydrogel electrolyte based on dimethyl sulfoxide(DMSO)/H_(2)O binary solvent was proposed.Through directionally reconstructing hydrogen bonds and reducing active H_(2)O molecules,the water retention ability and cathode/anode interfaces were synergistic enhanced.As a result,the synthesized DN organohydrogel demonstrates exceptional water retention capabilities,retaining approximately 75% of its original weight even after the exposure to air for 20 days.The Zn MnO_(2) battery delivers an outstanding specific capacity of275 mA h g^(-1) at 1 C,impressive rate performance with 85 mA h g^(-1) at 30 C,and excellent cyclic stability(95% retention after 6000 cycles at 5 C).Zn‖Zn symmetric battery can cycle more than 5000 h at 1 mA cm^(-2) and 1 mA h cm^(-2) without short circuiting.This study will encourage the further development of functional organohydrogel electrolytes for advanced energy storage devices.

Secure Beamforming Design for SWIPT in Cooperative D2D Communications

In device-to-device(D2D) communications, device terminal relaying makes it possible for devices in a network to function as transmission relays for each other to enhance the spectral efficiency. In this paper we consider a cooperative D2D communication system with simultaneous wireless information and power transfer(SWIPT). The cooperative D2D communication scheme allows two nearby devices to communicate with each other in the licensed cellular bandwidth by assigning D2D transmitters as half-duplex(HD) relay to assists cellular downlink transmissions. In particular, we focus on secure information transmission for the cellular users when the idle D2D users are the potential eavesdroppers. We aim to design secure beamforming schemes to maximize the D2D users data rate while guaranteeing the secrecy rate requirements of the cellular users and the minimum required amounts of power transferred to the idle D2D users. To solve this non-convex problem, a semi-definite programming relaxation(SDR) approach is adopted to obtain the optimal solution. Furthermore, we propose two suboptimal secure beamforming schemes with low computational complexity for providing secure communication and efficient energy transfer. Simulation results demonstrate the superiority of our proposed scheme.

Diagnostic Value of Serum TSH,Ultrasound,and Enhanced CT in Papillary Thyroid Carcinoma with Lymph Node Metastasis

Objective:To explore the diagnostic value of serum TSH,ultrasound,and enhanced CT in papillary thyroid carcinoma with lymph node metastasis.Methods:168 patients who underwent thyroidectomy in Shaanxi Provincial People’s Hospital from January 2020 to December 2021 were selected as the research subjects.Based on the pathological nature(benign or malignant),they were divided into two groups,with 86 patients in the control group and 82 patients in the study group.Based on whether the pathology was accompanied with lymph node metastasis,the PTC group was divided into a lymph node metastasis group and a non-lymph node metastasis group,with 51 and 31 patients in the respective groups.Retrospective analysis was conducted to observe and analyze the pathological results of the thyroid nodules’thyroid ultrasound results,neck enhanced CT results,and thyroid function test serology results.Results:Compared with the PTC group,there were significant differences in TR classification,ultrasonic lymph nodes,and enhanced CT lymph nodes,but no significant differences in the course of disease,nodule distribution,and the number of nodules between the benign nodule group and PTC group;in the comparison of lymph node metastasis using ultrasound and enhanced CT,the number of patients with ultrasound lymph nodes without abnormal metastasis in the non-metastasis group was 28,while that of the metastasis group was 21;the number of patients with abnormal metastasis in the non-metastasis group was 3,while that of the metastasis group was 30.The number of patients with a single node without metastasis and metastasis was 14 and 8,respectively,whereas the number of patients with multiple nodes without metastasis and metastasis was 17 and 43,respectively.There were statistically significant differences in the number of ultrasound lymph nodes and nodules,but no statistically significant differences in TR classification,enhanced CT lymph nodes,nodules distribution,and disease course.Conclusion:Serum TSH can be used to identify the nature(benign and malignant)of thyroid nodules,and enhanced CT is better than ultrasound when evaluating complex lesions.It can be used as a supplement to ultrasound based on clinical context.

Diagnostic Value and Misdiagnosis Analysis of Conventional Ultrasonography Combined with Contrast-Enhanced Ultrasonography in Thyroid Nodules

Objective:To explore the diagnostic value of conventional ultrasonography combined with contrast-enhanced ultrasonography in thyroid nodules.Methods:From June 2021 to July 2022,163 patients with thyroid nodules enrolled in our hospital were selected as research subjects.After pathological diagnosis,24 cases were malignant thyroid nodules,and 139 cases were benign thyroid nodules.The diagnosis rate of malignant and benign thyroid nodules was observed and analyzed,with 95%CI.Results:Among them,the malignant and benign detection rates of routine ultrasound were 88.63%and 75.00%,respectively,and the malignant and benign detection rates of contrast-enhanced ultrasound were 81.82%and 81.25%,respectively.The malignant and benign detection rates of conventional ultrasound combined with contrast-enhanced ultrasound were 93.18%and 87.50%,respectively,and the 95%CI was greater than 0.7.Conclusion:Conventional ultrasound combined with contrast-enhanced ultrasound can help improve the diagnostic accuracy of benign and malignant thyroid nodules and reduce the misdiagnosis rate.

Application Value of Contrast-Enhanced Ultrasound in the Diagnosis of Breast Lesions

Objective:To explore the value and effect of contrast-enhanced ultrasound in the diagnosis of breast lesions.Methods:Seventy-two patients with breast lesions in Shaanxi Provincial People’s Hospital from June 2020 to December 2021 were selected as the research subjects.All 72 patients met the diagnostic criteria of breast lesions.Two patients with incomplete clinical data were excluded;hence,there were 70 patients remaining.The diagnostic results of the two examination methods and the diagnostic value of the joint examination for breast lesions were analyzed and compared.Results:The results of benign,malignant,missed,and misdiagnosed breast lesions by contrast-enhanced ultrasound were 31,32,6,and 1 cases,respectively,accounting for 44.29%,45.71%,8.57%,and 1.43%,respectively.The results of benign,malignant,missed,and misdiagnosed breast lesions by ultrasound automatic volume imaging were 21,24,17,and 8 cases,respectively,accounting for 30.00%,34.28%,24.29%,and 11.43%,respectively.There were statistical differences between the two groups for missed diagnosis and misdiagnosis,but there was no significant difference between the two groups for benign and malignant lesions.The accuracy,sensitivity,and specificity of contrast-enhanced ultrasound were 87.69%,83.62%,and 83.45%,respectively;the accuracy,sensitivity,and specificity of ultrasound automatic volume imaging were 71.39%,68.99%,and 74.69%,respectively;the accuracy,sensitivity,and specificity of contrast-enhanced ultrasound combined with ultrasound automatic volume imaging were 96.29%,92.68%,and 91.78%,respectively.Conclusion:Contrast-enhanced ultrasonography has a high clinical application value and a low inspection error rate in the diagnosis of breast lesions.It merits clinical advancement since it helps doctors diagnose and treat breast lesions more effectively.

Rocking-chair ammonium ion battery with high rate and long-cycle life

Aqueous rechargeable ammonium-ion batteries(AIBs)have drew considerable attention because of their capacity for high rates,low cost,and high safety.However,developing desired electrodes requiring stable structure in the aqueous fast ammoniation/de-ammoniation becomes urgent.Herein,an ammonium ion full battery using Cu_(3)[Fe(CN)_(6)]_(2)(CuHCF)acting to be a cathode and barium vanadate(BVO)acting to be an anode is described.Its excellent electrochemical behavior of Prussian blue analogs and the perfectly matched lattice structure of NH_(4)^(+)is expected.And the open structure of vanadium compounds satisfies the fast ammoniation/de-ammoniation of NH4+is also achieved.As a result of these synergistic effects,the BVO//CuHCF full cell retains 80.5 percent of its capacity following 1000 cycling.These achievements provide new ideas for developing low-cost and long-life AIBs.

Highly robust zinc metal anode directed by organic–inorganic synergistic interfaces for wearable aqueous zinc battery

Flexible aqueous zinc batteries(FAZBs)with high safety and environmental friendliness are promising smart power sources for smart wearable electronics.However,the bare zinc anode usually suffers from damnable dendrite growth and rampant side reaction on the surface,greatly impeding practical applications in FAZBs.Herein,a composite polymer interface layer is artificially self‐assembled on the surface of the zinc anode by graft‐modified fluorinated monomer(polyacrylic acid‐2‐(Trifluoromethyl)propenoic acid,PAA‐TFPA),on which an organic–inorganic hybrid(PAA‐Zn/ZnF2)solid electrolyte interface(SEI)with excellent ionic conductivity is formed by interacting with Zn2+.Both the pouch cell and fiber zinc anode exhibit excellent plating/stripping reversibility after protecting by this organic–inorganic SEI,which can be stably cycled more than 3000 h in symmetric Zn||Zn cells or 550 h in fiber Zn||Zn cells.Additionally,this interface layer preserves zinc anode with excellent mechanical durability under various mechanical deformation(stably working for another 1200 h after bending 100 h).The corresponding PAA‐Zn/ZnF2@Zn||MnO2 full cell displays an ultra‐long life span(79%capacity retention after 3000 cycles)and mechanical robustness(85%of the initial capacity for another 3000 cycles after bending 100 times).More importantly,the as‐assembled cells can easily power smart wearable devices to monitor the user's health condition.

Chemotherapy drugs induce pyroptosis through caspase-3-dependent cleavage of GSDME

Chemotherapy drugs can induce cancer cell death via a series of regulated cell death（RCD）pathways including apoptosis and regulated necrosis（Vanden Berghe et al.,2014）.Characterized by activation of the caspase family of cystine proteases,the occurrence of apoptosis leads to cell shrinkage and formation of apoptotic bodies.

Coverage of 13-Valent Pneumococcal Conjugate Vaccine Among Children 0–15 Months of Age—9 Provinces,China,2019–2021

Summary What is already known on this topic?Limited data exist regarding the coverage of the 13-valent pneumococcal conjugate vaccine(PCV13)in China.A lack of official statistics,coupled with an insufficient body of published literature,hinders the accurate depiction of the current situation.What is added by this report?This study investigated the utilization of PCV13 and estimated its coverage in nine provinces across eastern,central,and western China between 2019 and 2021.Despite an annual increase in PCV13 usage during this period,the overall coverage remained suboptimal.

ZIF-67 derived hollow Ni-Co-Se nano-polyhedrons for flexible hybrid supercapacitors with remarkable electrochemical performances

Nano-polyhedral NiSe2/CoSe2(Ni-Co-Se) with hollow architectures are synthesized by selenizing the precursors of Ni-Co bimetallic hydroxides that are directly derived from ZIF-67.The as-fabricated Ni-Co-Se electrodes exhibit high specific capacitance of 1668 F/g at 1 A/g accompanying with outstanding rate capability(about 82.8% retention of the initial capacity at 20 A/g).The corresponding Ni-Co-Se//AC all-solid-state hybrid supercapacitors are assembled by directly using the Ni-Co-Se on carbon fabric as the positive electrode,which deliver high energy density and power density(38.5 Wh/kg at 802.1 W/kg,32.0 Wh/kg at 8008.8 W/kg),excellent cyclic stability(82.3% retention after 5000 cycle) and robust mechanical flexibility(no obvious attenuation at bending to different angles).This work will provide a new and smart route for constructing transition metal selenides for supercapacitor devices.

Recent progress of diversiform humidity sensors based on versatile nanomaterials and their prospective applications

Humidity sensors are of significance in various fields,such as environmental and food quality monitoring,industrial processing,wearable and flexible electronics,and human health care.High-performance humidity sensors with high sensitivity,rapid response time,and good stability are of paramount importance in humidity sensing.In this paper,diversiform humidity sensors with different sensing mechanisms are summarized,including resistive,impedance,capacitive,quartz crystal microbalance(QCM),surface acoustic wave(SAW),field-effect transistor(FET),and optical fiber humidity sensors.Versatile nanomaterials such as graphene,transition-metal chalcogenide,MXenes,black phosphorus(BP),boron nitride(BN),polymers,and nanofibers were promising building-blocks for constructing humidity sensors.The latest progress in the wearable and flexible humidity sensors,and self-powered humidity sensors was summarized.The diversiform applications of the humidity sensors with great prospects were demonstrated in various fields in terms of human respiratory monitoring,skin dryness diagnosing,fingertip approaching,and non-contact switch.Moreover,the challenges and prospects of nanomaterials-based humidity sensors were discussed.

Booting the electrochemical properties of Fe-based anode by the formation multiphasic nanocomposite for lithium-ion batteries

Fe-based compounds with good environmental friendliness and high reversible capacity have attracted considerable attention as anode for lithium-ion batteries.But,similar to other transition metal oxides(TMOs),it is also affected by large volume changes and inferior kinetics during redox reactions,resulting in the destruction of the crystal structure and poor electrochemical performance.Here,Fe_(3)O_(4)/C nanospheres anchored on the two-dimensional graphene oxide as precursors are phosphated and sintered to build the multiphasic nanocomposite.XRD results confirmed the multiphasic nanocomposite composed of Fe2O3,Fe_(3)O_(4) and Fe_(3)PO_(7),which will facilitate the Li+diffusion.And the carbonaceous matrix will buffer the volume changes and enhance electron conduction.Consequently,the multiphasic Febased anode delivers a large specific capacity of 1086 mAh/g with a high initial Coulombic efficiency of 87%at 0.1 C.It also has excellent cycling stability and rate property,maintaining a capacity retention of~87%after 300 cycles and a high reversible capacity of 632 mAh/g at 10 C.The proposed multiphasic structure offers a new insight into improving the electrochemical properties of TMO-based anodes for advanced alkali-ion batteries.

耦合无枝晶锌负极和可逆脱嵌钙离子的磷酸钒钠正极实现先进钙锌混合离子电池

混合离子电池综合了单一离子电池的优点,为开发高性能二次电池提供了新的见解.本文合成了一种有无定形活性碳和还原氧化石墨烯包覆的NASICON型正极材料(NVP@AC@rGO)用于钙离子的可逆脱嵌,并组装了一种与锌金属负极和水系混合电解质耦合的Ca/Zn离子混合电池.这种完美的结合不仅充分发挥了钙离子在NASICON结构中优异的扩散动力学,而且巧妙利用钙离子的低还原电位,形成静电屏蔽效应,从而抑制了锌枝晶的形成.因此,该混合电池具有超高的比容量,出色的倍率性能以及循环稳定性.这种巧妙的组合平衡了单一多价离子电池的优缺点,为设计高性能的水性多价离子电池提供了一种新的可行途径.

Amorphous nickel borate nanosheets as cathode material with high capacity and better cycling performance for zinc ion battery

Zinc-ion batteries are under current research focus because of their uniqueness in low cost and high safety.However,the pursuing of high-performance cathode materials of aqueous Zinc ion batteries(AZBs)with low cost,high energy density and long cycle life has become the key problem to be solved.Herein we synthesized a series of amorphous nickel borate(AM-NiBO)nanosheets by varying corrosion time with in-situ electrochemical corrosion method.The AM-NiBO-T13 as electrode material possesses a high areal capacity of 0.65 m Ah/cm^(2) with the capacity retention of 95.1%after 2000 cycles.In addition,the assembled AM-NiBO-T13//Zn provides high energy density(0.77 m Wh/cm^(2) at 1.76 m W/cm^(2)).The high areal capacity and better cycling performance can be owing to the amorphous nanosheets structure and the stable coordination characteristics of boron and oxygen in borate materials.It shows that amorphous nickel borate nanosheets have great prospects in the field of energy storage.

Amorphous Ni-Co-S nanocages assembled with nanosheet arrays as cathode for high-performance zinc ion battery

The selection and development of cathode of alkaline zinc batteries(AZBs)is still hindered and often leads to poor rate capability and short cycle life.Here,amorphous hollow nickel-cobalt-based sulfides nanocages with nanosheet arrays(AM-NCS)are designed and constructed with ZIF-67 as the selftemplate to exchange with Ni^(2+) and S^(2-) by using a two-step ion exchange method.The synthesized AM-NCS possess the high specific capacity(160 m Ah/g at 2 A/g),and the assembled battery has excellent rate performance(146 m Ah/g reversible capacity at 5 A/g).The assembled device has excellent rate performance(155 m Ah/g at 2 A/g)and long cycling stability(7000 cycles,62.5%of initial capacity).The excellent electrochemical properties of the electrode materials are mainly attributed to the unique structure,in particular,polyhedron structure with hollow structure can improve the cyclic stability,and the amorphous structure can expose more reactive sites on the surfaces of nickel,cobalt and sulfur.This work provides a new strategy for the design and fabrication of high performance cathode materials for AZBs.

Metal-organic framework derived NiCoP hollow polyhedrons electrocatalyst for pH-universal hydrogen evolution reaction

Hollow nanostructures have attracted increasing research interest in hydrogen evolution reaction owing to their unique structural features.Herein,Ni-Co mixed metal phosphide hollow and porous polyhedrons was successfully composited(expressed as NiCoP).Benefiting from the synergistic effects of ZIF-67 by doping Ni elements and the well-defined hollow and porous structure,the as-synthesized NiCoP hollow and porous polyhedrons exhibit better electrochemical properties and mechanical stability for hydrogen evolution reaction over a pH-universal range,with a small Tafel slopes of 72,101,176 mV/dec,and a low overpotential of 82,102,261 mV at a current density of 10 mA/cm^(2) in 0.5 mol/L H_(2)SO_(4),1 mol/L KOH and1 mol/L phosphate buffer solution(PBS).This general strategy can also be applied to fabricate other hollow cobalt-based phosphides and MOFs-derived materials for HER.

Hollow polyhedron structure of amorphous Ni-Co-S/Co(OH)_(2) for high performance supercapacitors

In power storage technology,ion exchange is widely used to modify the electronic structures of electrode materials to stimulate their electrochemical properties.Here,we proposed a multistep ion exchange(cation exchange and anion exchange) strategy to synthesize amorphous Ni-Co-S and β-Co(OH)_(2) hybrid nanomaterials with a hollow polyhedron structures.The synergistic effects of different components and the remarkable superiorities of hollow structure endow Ni-Co-S/Co(OH)_(2) electrode with outstanding electrochemical performance,including ultra-high specific capacity(1440.0 C/g at 1 A/g),superior capacitance retention rate(79.1% retention at 20 A/g) and long operating lifespan(81.4% retention after5000 cycles).Moreover,the corresponding hybrid supercapacitor enjoys a high energy density of 58.4 Wh/kg at the power density of 0.8 kW/kg,and a decent cyclability that the capacitances are maintained at80.8% compared with the initial capacitance.This research presents a high-performance electrode material and provides a promising route for the construction of electrode materials for supercapacitors with both structural and component advantages.