An intrinsically self-healing and anti-freezing molecular chains induced polyacrylamide-based hydrogel electrolytes for zinc manganese dioxide batteries

The anti-freezing strategy of hydrogels and their self-healing structure are often contradictory,it is vital to break through the molecular structure to design and construct hydrogels with intrinsic anti-freezing/self-healing for meeting the rapid development of flexible and wearable devices in diverse service conditions.Herein,we design a new hydrogel electrolyte(AF/SH-Hydrogel)with intrinsic anti-freezing/self-healing capabilities by introducing ethylene glycol molecules,dynamic chemical bonding(disulfide bond),and supramolecular interaction(multi-hydrogen bond)into the polyacrylamide molecular chain.Thanks to the exceptional freeze resistance(84%capacity retention at-20℃)and intrinsic self-healing capabilities(95%capacity retention after 5 cutting/self-healing cycles),the obtained AF/SH-Hydrogel makes the zinc||manganese dioxide cell an economically feasible battery for the state-of-the-art applications.The Zn||AF/SH-Hydrogel||MnO_(2)device offers a near-theoretical specific capacity of 285 m A h g^(-1)at 0.1 A g^(-1)(Coulombic efficiency≈100%),as well as good self-healing capability and mechanical flexibility in an ice bath.This work provides insight that can be utilized to develop multifunctional hydrogel electrolytes for application in next generation of self-healable and freeze-resistance smart aqueous energy storage devices.

Hydrophilic polyanionic hydrogel electrolyte for anti-freezing and bending resistant zinc-ion hybrid supercapacitors

Zinc-ion hybrid supercapacitors(ZHSCs)have been widely considered as promising candidates for flexible electrochemical energy storage devices.The key challenge is to develop hydrogel electrolytes with high hydrophilicity,anti-freezing,bending resistance,and stable interface with electrodes.This study reported a hydrogel electrolyte system that can meet the above functions,in which the zincophilic and negatively charged SO3−,migratable Na+,abundant hydrophilic functional groups,gum xanthan,and porous architecture could effectively promote the electrochemical performance of ZHSCs.ZHSCs with such hydrogel electrolytes not only exhibited good low-temperature performance but also showed excellent bending resistance ability.A high specific capacitance could be kept after a long air-working lifespan over 10,000 cycles under a wide operation voltage of 1.85 V at−10℃.Furthermore,flexible ZHSCs could maintain the capacitance retention of 93.18%even after continuous 500 bends at an angle of 180°.The designed hydrogel electrolytes could be also used for other electrochemical energy storage devices with anti-freezing and bending resistance by changing electrolyte salt.

Wide temperature range-and damage-tolerant microsupercapacitors from salt-tolerant, anti-freezing and self-healing organohydrogel via dynamic bonds modulation

The advance of microelectronics requires the micropower of microsupercapacitors(MSCs) to possess wide temperature-and damage-tolerance beyond high areal energy density.The properties of electrolyte are crucial for MSCs to meet the above requirements.Here,an organohydrogel electrolyte,featured with high salt tolerance,ultralow freezing point,and strong self-healing ability,is experimentally realized via modulating its inner dynamic bonds.Spectroscopic and theoretical analysis reveal that dimethyl sulfoxide has the ability to reconstruct Li^(+)solvation structure,and interact with free water and polyvinyl alcohol chains via forming hydrogen bonds.The organohydrogel electrolyte is employed to build MSCs,which show a boosted energy density,promising wide temperature range-and damage-tolerant ability.These attractive features make the designed organohydrogel electrolyte have great potential to advance MSCs.

Research Progress on Plant Anti-Freeze Proteins

Plant antifreeze proteins(AFPs)are special proteins that can protect plant cells from ice crystal damage in low-temperature environments,and they play a crucial role in the process of plants adapting to cold environ-ments.Proteins with these characteristics have been found infish living in cold regions,as well as many plants and insects.Although research on plant AFPs started relatively late,their application prospects are broad,leading to the attention of many researchers to the isolation,cloning,and genetic improvement of plant AFP genes.Studies have found that the distribution of AFPs in different species seems to be the result of independent evolu-tionary events.Unlike the AFPs found infish and insects,plant AFPs have multiple hydrophilic ice-binding domains,and their recrystallization inhibition activity is about 10–100 times that offish and insect AFPs.Although different plant AFPs have the characteristics of low TH and high RI,their DNA and amino acid sequences are completely different,with small homology.With in-depth research and analysis of the character-istics and mechanisms of plant AFPs,not only has our understanding of plant antifreeze mechanisms been enriched,but it can also be used to improve crop varieties and enhance their freezing tolerance,yield,and quality through genetic engineering.In addition,the study of plant AFPs also contributes to our understanding of freezing resistance mechanisms in other organisms and provides new research directions for thefield of biotech-nology.Therefore,based on the analysis of relevant literature,this article will delve into the concepts,character-istics,research methods,and mechanisms of plant AFPs,summarize the latest research progress and application prospects of AFPs in plant,and provide prospects for the future development of AFP gene research.

Effect of Anti-freezing Admixtures on Alkali-silica Reaction in Mortars

The influence of anti-freezing admixture on the alkali aggregate reaction in mortar was analyzed with accelerated methods. It is confirmed that the addition of sodium salt ingredients of anti-freezing admixture accelerates the alkali silica reaction to some extent, whereas calcium salt ingredient of anti-freezing admixture reduces the expansion of alkali silica reaction caused by high alkali cement. It is found that the addition of the fly ash considerably suppresses the expansion of alkali silica reaction induced by the anti-freezing admixtures.

Mechanical reliable,NIR light-induced rapid self-healing hydrogel electrolyte towards flexible zinc-ion hybrid supercapacitors with low-temperature adaptability and long service life

Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to drastic reduction in ionic conductivity and mechanical properties that deteriorates the performance of flexible ZICs.Besides,the mechanical fracture during arbitrary deformations significantly prunes out the lifespan of the flexible device.Herein,a Zn^(2+)and Li^(+)co-doped,polypyrrole-dopamine decorated Sb_(2)S_(3)incorporated,and polyvinyl alcohol/poly(N-(2-hydroxyethyl)acrylamide)double-network hydrogel electrolyte is constructed with favorable mechanical reliability,anti-freezing,and self-healing ability.In addition,it delivers ultra-high ionic conductivity of 8.6 and 3.7 S m^(-1)at 20 and−30°C,respectively,and displays excellent mechanical properties to withstand tensile stress of 1.85 MPa with tensile elongation of 760%,together with fracture energy of 5.14 MJ m^(-3).Notably,the fractured hydrogel electrolyte can recover itself after only 90 s of infrared illumination,while regaining 83%of its tensile strain and almost 100%of its ionic conductivity during−30–60°C.Moreover,ZICs coupled with this hydrogel electrolyte not only show a wide voltage window(up to 2 V),but also provide high energy density of 230 Wh kg^(-1)at power density of 500 W kg^(-1)with a capacity retention of 86.7%after 20,000 cycles under 20°C.Furthermore,the ZICs are able to retain excellent capacity even under various mechanical deformation at−30°C.This contribution will open up new insights into design of advanced wearable flexible electronics with environmental adaptability and long-life span.

Coupling of Adhesion and Anti‑Freezing Properties in Hydrogel Electrolytes for Low‑Temperature Aqueous‑Based Hybrid Capacitors

Solid-state zinc-ion capacitors are emerging as promising candidates for large-scale energy storage owing to improved safety,mechanical and thermal stability and easy-to-direct stacking.Hydrogel electrolytes are appealing solid-state electrolytes because of eco-friendliness,high conductivity and intrinsic flexibility.However,the electrolyte/electrode interfacial contact and anti-freezing properties of current hydrogel electrolytes are still challenging for practical applications of zinc-ion capacitors.Here,we report a class of hydrogel electrolytes that couple high interfacial adhesion and anti-freezing performance.The synergy of tough hydrogel matrix and chemical anchorage enables a well-adhered interface between hydrogel electrolyte and electrode.Meanwhile,the cooperative solvation of ZnCl2 and LiCl hybrid salts renders the hydrogel electrolyte high ionic conductivity and mechanical elasticity simultaneously at low temperatures.More significantly,the Zn||carbon nanotubes hybrid capacitor based on this hydrogel electrolyte exhibits low-temperature capacitive performance,delivering high-energy density of 39 Wh kg^(-1)at-60°C with capacity retention of 98.7%over 10,000 cycles.With the benefits of the well-adhered electrolyte/electrode interface and the anti-freezing hydrogel electrolyte,the Zn/Li hybrid capacitor is able to accommodate dynamic deformations and function well under 1000 tension cycles even at-60°C.This work provides a powerful strategy for enabling stable operation of low-temperature zinc-ion capacitors.

Bioinspired anti-freezing 3D-printable conductive hydrogel microfibers for highly-sensitive and wide-range detection of ultralow and high strains

Soft strain sensors that can transduce stretch stimuli into electrical readouts are promising as sustainable wearable electronics.However,most strain sensors cannot achieve highly-sensitive and wide-range detection of ultralow and high strains.Inspired by bamboo structures,anti-freezing microfibers made of conductive poly(vinyl alcohol)hydrogel with poly(3,4-ethylenedioxythiphene)-poly(styrenesulfonate)are developed via continuous microfluidic spinning.The microfibers provide unique bamboo-like structures with enhanced local stress to improve both their length change and resistance change upon stretching for efficient signal conversion.The microfibers allow highlysensitive(detection limit:0.05%strain)and wide-range(0%-400%strain)detection of ultralow and high strains,as well as features of good stretchability(485%strain)and anti-freezing property(freezing temperature:-41.1°C),fast response(200 ms),and good repeatability.The experimental results,together with theoretical foundation analysis and finite element analysis,prove their enhanced length and resistance changes upon stretching for efficient signal conversion.By integrating microfluidic spinning with 3D-printing technique,the textiles of the microfibers can be flexibly constructed.The microfibers and their 3D-printed textiles enable highperformance monitoring of human motions including finger bending and throat vibrating during phonation.This work provides an efficient and general strategy for developing advanced conductive hydrogel microfibers as highperformance wearable strain sensors.

An aqueous magnesium-ion hybrid supercapacitor operated at-50℃

The recent advances in aqueous magnesium-ion hybrid supercapacitor(MHSC)have attracted great attention as it brings together the benefits of high energy density,high power density,and synchronously addresses cost and safety issues.However,the freeze of aqueous electrolytes discourages aqueous MHSC from operating at low-temperature conditions.Here,a low-concentration aqueous solution of 4 mol L^(-1) Mg(ClO_(4))_(2) is devised for its low freezing point(-67℃)and ultra-high ionic conductivity(3.37 mS cm^(-1) at-50℃).Both physical characterizations and computational simulations revealed that the Mg(ClO_(4))_(2) can effectively disrupt the original hydrogen bond network among water molecules via transmuting the electrolyte structure,thus yielding a low freezing point.Thus,the Mg(ClO_(4))_(2) electrolytes endue aqueous MHSC with a wider temperature operation range(-50℃–25℃)and a higher energy density of 103.9 Wh kg^(-1) at 3.68 kW kg^(-1) over commonly used magnesium salts(i.e.,MgSO_(4) and Mg(NO_(3))_(2))electrolytes.Furthermore,a quasi-solid-state MHSC based on polyacrylamide-based hydrogel electrolyte holds superior low-temperature performance,excellentflexibility,and high safety.This work pioneers a convenient,cheap,and eco-friendly tactic to procure low-temperature aqueous magnesium-ion energy storage device.

Why would sea-level rise for global warming and polar ice-melt?

Two major causes of global sea level rise such as thermal expansion of the oceans and the loss of landbased ice for increased melting have been claimed by some researchers and recognized by the IPCC.However, other climate threat investigators revealed that atmosphere-ocean modeling is an imperfect representation, paleo-data consist of proxy climate information with ambiguities, and modern observations are limited in scope and accuracy. It is revealed that global warming and polar ice-melt although a reality would not contribute to any sea level rise. Floating-ice of the polar region on melting would reoccupy same displaced volume by floating ice-sheets. Land-ice cover in the polar region on melting can reduce load from the crust to activate elastic rebound that would raise land for its isostatic equilibrium.Such characteristics would not contribute to sea level rise. Equatorial bulge, polar flattening, elevation difference of the spheroidal surface between equator and pole with lower in the pole, strong gravity attraction of the polar region and week gravity attraction of the equatorial region, all these phenomena would play dominant role in preventing sea level rise. Palaeo-sea level rise and fall in macro-scale(10-100 m or so) were related to marine transgression and regression in addition to other geologic events like converging and diverging plate tectonics, orogenic uplift of the collision margin, basin subsidence of the extensional crust, volcanic activities in the oceanic region, prograding delta buildup, ocean floor height change and sub-marine mass avalanche. This study also reveals that geophysical shape, gravity attraction and the centrifugal force of spinning and rotation of the earth would continue acting against sea level rise.

Rapid self-healing,self-adhesive,anti-freezing,moisturizing,antibacterial and multi-stimuli-responsive PVA/starch/tea polyphenol-based composite conductive organohydrogel as flexible strain sensor

The complexity of application environment stimulates the development of wearable devices based on functional hydrogels.Among all the promising performances,self-healing and self-adhesion properties are ideal for hydrogel sensors,which can guarantee good accuracy,comfort and long service life.However,it is still a challenge to achieve simultaneous self-healing and self-adhesion in different environments(in the air,underwater and at low temperatures).Herein,a feasible new strategy was successfully carried out to prepare a starch-based composite conductive organohydrogel based on the reversible borate ester bonds formed by complexing starch/polyvinyl alcohol(PVA)/tea polyphenol(TP)with borax,and multiple hydrogen-bond interactions among PVA,starch,TP and ethylene glycol(EG).Silver nanoparticles(Ag-NPs),reduced and stabilized by TP,and MWCNTs(multi-walled carbon nanotubes)were introduced into the cross-linking networks to endow the resulting PBSTCE organohydrogel with considerable antibacterial property and conductivity,respectively.The organohydrogel possessed rapid self-healing(HE(self-healing efficiency)=96.07%in 90 s,both in the air and underwater,also at-20℃),considerable self-adhesion(both in the air and underwater,also at-20℃),remarkable stretchability(814%of elongation),anti-freezing(-20℃)and moisture-retention abilities,antibacterial activity,sensitive pH/sugar-responsiveness,and plasticity.The strain sensor formed by the PBSTCE organohydrogel can not only effectively record large-scale human motions(e.g.finger/wrist/elbow bending,walking,etc.),but also accurately capture subtle motion changes(e.g.breathing,chewing,swallowing,speaking,smiling and frowning).Moreover,the self-healed organohydrogel sensor also exhibited almost invariable mechanical,electrical and sensing behaviors.This work demonstrates a feasible strategy to construct multifunctional starch-based organohy-drogels,and promotes their efficient,stable and eco-friendly application as flexible wearable devices.

化冰盐对灾后长沙城市森林植物的危害

2008年1月中旬至2月初,50年以来罕见的严重冰冻灾害,对长沙城市森林植物损害巨大[1]。抗冰救灾期间,为保交通,对市区范围"6纵15横"共21条主干道进行撒盐融冰,据有关部门统计,至2月4日,累计抛撒工业用盐近7000t,日均撒盐量达600t[2-3]。大量使用工业盐或氯盐类融雪剂化冰,对桥梁、公路及植物等产生的次生灾害国内外己有深刻的教训。为此,我们对长沙市主干道绿化带进行了跟踪调查,发现目前大面积花灌木死亡或生长不良的主要原因除遭受严重冻害之外,渗入绿化带土壤中的盐分已使土壤出现不同程度的盐碱化,对适宜酸性土生长的本土植物构成了不可低估的生态灾害。本文旨在为长沙城市森林灾后重建工作提出解决途径。

An anti-freezing and anti-drying multifunctional gel electrolyte for flexible aqueous zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs)have attracted immense attention for flexible energy storage devices due to their high safety and low cost.However,conventional flexible aqueous ZIBs will undergo severe capacity loss at subzero temperature due to the inevitably freeze of electrolytes.In addition,under large bending or stretching strains,the encapsulation of devices would be damaged,which causes the evaporation of water in electrolytes and results in device failure.Herein,an anti-freezing and anti-drying gel electrolyte based on polyacrylamide(PAM)and glycerol(Gly)is developed.The strong hydrogen-bonding interactions between PAM or Gly and water molecules not only avoid the crystallization of the gel electrolyte at low temperatures,but also constrain the free water and restrict its evaporation.Therefore,such gel electrolyte displays a high ionic conductivity of 9.65×10^(−5)S cm^(−1)at−40℃.Furthermore,it can restrict the dehydration process when the electrolyte is exposed to ambient environment.The flexible ZIBs based on such gel electrolyte exhibit excellent electrochemical performance at−40℃and the devices without encapsulation retain 98%of their initial capacity in ambient condition after 30 days.This work provides a route to design anti-freezing and anti-drying gel electrolytes for aqueous energy storage devices.

Applicability of Air Bubbler Lines for Ice Control in Harbours

Ice formation in the harbours in arctic region such as in Finland is a problem in winter times. The air bubblers are often used for controlling the growth of ice near the harbour pier walls. This paper gives an in-depth description of the harbour ice problem and the applicability of the bubblers. A numerical method of flow and heat-transfer is used to predict the effectiveness of the air bubblers in controlling the ice accumulation in the harbours. Empirical models of formatting and melting the ice are presented and used in the numerical solutions. It shows that the numerical method can realistically predict the ice-melting effect of the air bubblers.

Decomposition behaviors of methane hydrate in porous media below the ice melting point by depressurization

The decomposition behaviors of methane hydrate below the ice melting point in porous media with different particle size and different pore size were studied.The silica gels with the particle size of 105–150μm,150–200μm and 300–450μm,and the mean pore diameters of 12.95 nm,17.96 nm and 33.20 nm were used in the experiments.Methane recovery and temperature change curves were determined for each experiment.The hydrate decomposition process in the experiments can be divided into the depressurization period and the isobaric period.The temperature in the system decreases quickly in the depressurization process with the hydrate decomposition and reaches the lowest point in the isobaric period.The hydrate decomposition in porous media below ice-melting point is very fast and no self-perseveration effect is observed.The hydrate decomposition is influenced both by the driving force and the initial hydrate saturation.In the experiments with the high hydrate saturation,the hydrate decomposition will stop when the pressure reaches the equilibrium dissociation pressure.The stable pressure in the experiment with high hydrate saturation exceeds the equilibrium dissociation pressure of bulk hydrate and increases with the decrease of the pore size.

Wellhead anti-frost technology using deep mine geothermal energy

The auxiliary shaft is an important location for coal mine heating in the winter, where the main purpose of heating is to prevent icing of the shaft. Wellhead heating requires characteristics of openness, no-noise and big heat loads. The original coal-fired boiler heating mode causes significant waste of energy and environmental pollution due to the low efficiency of the heat exchange. Therefore, to solve these prob- lems, we will use deep mine geothermal energy to heat the wellhead by making full use of its negative pressure field and design a low-temperature water and fan-free heating system. Through numerical cal- culations we will simulate temperature fields, pressure fields and velocity fields under different air sup- ply temperatures, as well as different air supply outlet locations and varying number of radiators in the wellhead room of a new auxiliary shaft to find the proper layout and number of radiators that meet well- head anti-frost requirements from our simulation results, in order to provide guidelines for a practical engineering design. Tests on the Zhangshuanglou auxiliary shaft wellhead shows good, look promising and appear to resolve successfully the problem of high energy consumption and high pollution of well- head heating by a coal-fired boiler.

Microscopic Pore Structure of Asphalt Mixture Incorporating with MFL

In order to analyze the microstructure of salt anti-freezing asphalt concrete, i e, MFL（Mafilon） modified asphalt concrete, MIP（mercury intrusion porosity） method was used to obtain the data including porosity and pore size distribution in micro scale. Results show that the porosity grows up with the increase of immersion duration and the salt content. During the immersion, the amount of large pores（60-200 μm） grow up gradually and porosity also grows up correspondingly. Even with different immersion duration, most pores＇ size distribute is beyond 7000 nm.

Laterally Sandwich-typed Hydrogel Columns with Liner Poly(N-isopropylacrylamide) Layer:Preparation, Swelling/deswelling Kinetics and Drug Delivery Characteristics

A novel thermo-responsive hydrogel column, featured with both ends of linear poly（N- isopropylacrylarnide） （PNIPAM） chains being grafted onto cross-linked PNIPAM chains, was reported. The laterally sandwich-typed hydrogel columns were fabricated by radical polymerization in a three-step process using a method of ice-melting synthesis. The initiating path, morphology and thermoresponsive characteristics of the prepared hydrogel columns were experimentally studied. The results show that the hydrogel column obtained by the initiator inside part has more quick swelling and deswelling rates responsing to temperature cycling than other hydrogels owing to linear PNIPAM chains to form supermacroporous structure. The proposed hydrogel structure provide a new mode of the phase transition behavior for thermo-sensitive ＂smart＂ or ＂intelligent＂ monodisperse micro-actuators, which is highly attractive for targeting drug delivery systems, chemical separations, and sensors and so on.

An Investigation of Freezing of Supercooled Water on Anti-Freeze Protein Modified Surfaces

This work investigates how functionalization of aluminium surfaces with natural type III Anti-Freeze Protein （AFP） affects the mechanism of heterogeneous ice nucleation. First the bulk ice nucleation properties of distilled water and aqueous solution of AFP were evaluated by differential scanning calorimetry. Then the modified surface was characterized by Secondary Ions Mass Spectroscopy （SIMS）, Fourier Transform InfraRed （FTIR） spectroscopy and contact angle measurement. Freezing experiments were then conducted in which water droplets underwent a slow controlled cooling. This study shows that compared to uncoated aluminium, the anti-freeze proteins functionalized surfaces exhibit a higher and narrower range of freezing temperature. It was found that these proteins that keep living organisms from freezing in cold environment act in the opposite way once immobilized on surfaces by promoting ice nucleation. Some suggestions regarding the mechanism of action of the observed phenomena were proposed based on the Classical Nucleation Theory （CNT）.

Transient Chemical Activation of Covalent Bonds for Healing of Kinetically Stable and Multifunctional Organohydrogels

It remains a great challenge to balance the kinetic stability and intrinsic healing ability of polymer materials.Here,we present an efficient strategy of using a synthetic reaction cycle to regulate the intrinsic healing ability of thermodynamically stable and kinetically inert multifunctional organohydrogels.By combining a double decomposition reaction with spontaneous energy dissipation,we can construct the simplest synthetic reaction cycle that can induce a transient out-of-equilibrium state for achieving the healing of organohydrogels with kinetically locked acylhydrazone bonds.In addition to balancing kinetic stability and healing ability,the synthetic reaction cycle also enables the polymer materials to have high tolerance to organic solvents,high ionic strength,high and low temperatures,and other harsh conditions.Therefore,the kinetically stable and healable organohydrogels remain mechanically flexible and electrically conductive even down to−40°C and are readily recyclable.The integration of chemical networks into healable polymers may provide novel,versatile materials for building next-generation electronic devices.