膨胀石墨/多壁碳纳米管基共晶盐复合相变材料的制备及热特性北大核心CSCD

单一水合盐作为相变蓄热材料使用时常常由于过冷、相分离、易泄漏以及其相变温度而受到限制,因此迫切需要制备出一种储热密度高、相变温度适宜、热导率大的复合相变材料。本工作采用熔融共混法在NH_(4)Al(SO_(4))_(2)·12H_(2)O(AASD)中掺入不同质量分数的MgSO_(4)·7H_(2)O(MSH),成功制备了AASD-MSH共晶盐相变材料,其质量比为55∶45,相变温度为76.4℃,相变潜热为189.4 J/g。共晶盐的X射线衍射图谱和傅里叶红外光谱表明其为物理混合。引入质量分数1%成核剂CaCl_(2)·2H_(2)O及1%增稠剂可溶性淀粉降低共晶盐过冷度,过冷度从34.9℃降低至28.0℃。引入改性膨胀石墨(MEG)与多壁碳纳米管(MWCNTs)制备复合相变材料,改善共晶盐易泄漏及热导率低等问题,当MWCNTs质量分数为0.5%时,复合相变材料的热导率高达8.185 W/(m·K),为共晶盐的19.98倍,其中共晶盐占比为75.6%,相变温度为74.3℃,相变焓值为133.5 J/g,过冷度进一步降低至22.2℃。热重实验表明与MEG-MWCNTs的复合增加了共晶盐的热稳定性,且经过100次冷热循环后复合相变材料的相变焓值基本不变,具有良好的循环稳定性。本工作制备得到的AASD-MSH/MEG-MWCNTs复合相变材料是一种相变温度适合、相变焓值较高、热导率较大的相变材料,且具有良好的热循环稳定性,应用潜力极大。     

十水硫酸钠相变储能材料研究进展

十水硫酸钠(sodium sulfate decahydrate,SSD)具有适宜的相变温度(2.4℃)、较高的相变潜热值(大于200 J/g)、价格低廉、来源广和安全无毒等优点,是一种广受关注的无机水合盐相变材料.然而,在应用过程中存在过冷度大、相分离严重及泄漏等问题.本文综述了近年来解决上述问题的研究进展、共晶盐相变材料的制备及相关应用,并对后续的研究方向做了如下展望:在降低过冷度方面,采用硼砂、制备共晶盐或添加外场扰动的方式来改善过冷;在抑制相分离方面,采用高导热的多孔材料吸附相变材料,利用真空浸渍法制备定型相变材料的方法来改善或消除相分离现象;在共晶盐材料方面,可以绘制二元相图,寻找新型共晶相变材料进行研究,尤其是目前结合较少的有机相变材料;在应用方面,注重结合十水硫酸钠相变储能装置和系统进行研究并拓宽其应用范围.     

石墨泡沫/共晶盐复合相变材料制备

选择KNO3/NaNO3二元体系按照质量比4∶6制备共晶盐,对共晶盐进行了熔点及熔化潜热的测量;将石墨泡沫这一新型材料作为强化基体,共晶盐作为相变材料（PCM）,采用熔融浸渗法制备了适用于太阳能热发电系统储能装置的石墨泡沫/共晶盐复合相变材料。采用扫描电镜对复合相变材料表面的微观结构进行了表征,并对其熔点、潜热、等效导热系数等热物性参数进行了测试。结果表明：共晶盐与石墨泡沫复合效果比较理想;复合前后共晶盐的熔点和潜热几乎没有发生变化;复合相变材料的等效导热系数得到了显著提升,石墨泡沫对相变材料起到了导热强化作用,满足高温蓄热的要求。     

N掺杂多孔碳海绵定形芒硝基复合相变材料的制备及其热性能北大核心CSCD

芒硝相变储能材料作为一种潜热值高、来源广泛的无机水合盐,因存在相分层、过冷度等问题,限制了其在储能领域的广泛应用。本工作以N掺杂多孔碳为载体,将芒硝相变储能材料与N掺杂多孔碳复合,解决芒硝相变储能材料在实际应用中存在的问题。基于水热反应在聚氨酯泡沫上负载N原子,随后通过高温碳化得到N掺杂的多孔碳海绵(NPCS-M),并将其作为Na_(2)SO_(4)·10H_(2)O/Na_(2)HPO_(4)·12H_(2)O共晶盐的载体,最终制备出N掺杂多孔碳海绵封装的芒硝基复合相变材料(NPCM)。结果表明:N掺杂多孔碳海绵为蜂窝状结构,N含量为4.3%,比表面积为42.52 m^(2)/g,该材料对共晶盐的吸附量达到了自重的120倍。同时研究了该材料在5~60℃温度范围内循环1000次、3000次和5000次后的固液相变性能,经5000次循环后,该复合相变材料的潜热仍在130 J/g以上,且有降低共晶盐多次循环后过冷度的作用。该N掺杂多孔碳海绵复合相变材料在储能领域具有广阔的应用前景。     

MWCNTs-水合盐复合相变材料的蓄热性能研究

研究CH₃COONa·3H₂O(SAT)/Na₂HPO₄·12H₂O(DSP)共晶盐的相变过程，分析亲水碳纳米管(HCNTs)对共晶盐热性能的优化效果。结果表明：SAT/DSP质量比为9∶1时共晶盐循环稳定性最好，且过冷度仅为2.5℃；随着HCNTs掺量提高，复合材料的热导率呈线性增长趋势，最高达到1.29 W/(m·K)，较未加HCNTs时提升了182.89%，蓄热密度呈线性下降趋势，最多降低了5.59%。最后对各组HCNTs/SAT/DSP复合相变材料(CPCM)进行200次固-液循环，结果表明各组材料的循环稳定性良好，具备实际应用价值。     

十二水硫酸铝钾相变蓄热材料研究进展北大核心CSCD

十二水硫酸铝钾[KAl(SO_(4))_(2)·12H_(2)O]具有相变潜热高、价格低廉和安全无毒等优点,是一种来源丰富的中低温无机水合盐相变蓄热材料,可以广泛应用在谷电蓄热、建筑供暖、产品节能、太阳能热利用以及电池热管理等领域。过冷度大与导热系数低等诸多水合盐的共性问题,严重影响了其蓄放热性能。十二水硫酸铝钾的相变温度偏高,将其制备成共晶或非共晶复合相变材料可以降低相变温度,由此扩大应用范围。本文通过对近年来十二水硫酸铝钾相变蓄热材料相关文献的梳理,综述了减小过冷度、提高导热系数以及复合调温的策略,着重阐述了成核剂、导热增强剂以及调温剂对十二水硫酸铝钾热物性能的影响,并介绍了十二水硫酸铝钾及其复合相变材料的主要应用研究情况。最后,对未来相关工作的研究方向进行了展望,包括新型添加剂及其对基材作用机理的探索、大量的熔化-凝固循环后结晶水损失的抑制和热可靠性的保障,以及相关应用领域的进一步拓展,为促进十二水硫酸铝钾相变蓄热材料的发展和实际应用提供借鉴。     

月桂酸-十四醇二元复合相变材料的相变特性

为了获得适合在建筑领域应用的相变材料和相变温度,以月桂酸(LA)和十四醇(TD)为原料,采用熔融共混法制备一系列二元酸-醇相变材料。采用步冷曲线法测定不同组分二元相变材料的结晶温度,通过绘制的相图确定二元体系低共晶点,LA-TD二元体系在23.1℃达到共晶点;采用红外光谱(FTIR)表征复合相变材料的结构,表明复合相变材料中LA与TD通过分子间作用力结合在一起;采用DSC差示扫描量热法测量LA-TD混合物的相变温度及相变潜热,低共晶物的相变起始温度为24.46℃,相变潜热达到150.45 J/g,经300次0~60℃冷热循环后热稳定性良好。     

癸酸-石蜡二元低共熔复合相变材料的制备及性能研究

为充分利用冬季太阳辐射热,将传统建筑材料与相变材料结合形成新型绿色建筑材料,可充分发挥其储能控温特性,并缩短热量被吸收进室内的时间,降低冬季采暖能耗,实现建筑节能。利用熔融共混法制备了质量配比为0.81∶0.19、共晶温度为27.4℃的癸酸-石蜡(CA-PC)低共熔复合相变材料。通过傅里叶红外光谱仪(FT-IR)对该二元低共熔物的化学结构进行分析,发现CA与PC是通过物理作用结合的,无新物质产生;并且通过500次加速冷热循环实验,证实了CA-PC复合相变材料具有良好的热循环稳定性。此外,由差示扫描量热仪(DSC)分析得到CA-PC的相变温度为27.0℃,相变潜热为153.7 J/g,这一结果与步冷曲线所得的共晶温度相吻合,进一步表明了该复合相变材料在用于制备新型建筑储能材料领域极具发展潜力。     

癸酸-棕榈酸二元复合相变材料的相变特性研究

通过熔融共混法制备一系列二元脂肪酸复合相变材料,并利用步冷曲线法确定癸酸-棕榈酸(CA-PA)二元复合相变材料的最佳质量配比为86∶14,其共晶温度为22.1℃。采用傅里叶红外光谱仪(FT-IR)、冷热加速循环实验和瞬态平面热源法(TPS)等研究CA-PA复合相变材料的结构与性能,发现CA-PA的FT-IR曲线上同时存在CA和PA的特征吸收峰,表明CA与PA是通过分子力作用在一起的。然后对CA-PA进行400次5~80℃冷热加速循环后,发现其相变温度变化不大于0.5℃,可见CA-PA热稳定性良好,且导热系数为0.151 W/(m·K)。同时,根据差示扫描量热仪(DSC)分析得到CA-PA的相变温度和相变潜热分别为21.78℃和154.7 J/g,这与通过步冷曲线得到的共晶温度十分符合,因此该CA-PA复合相变材料适用于建筑节能和热回收领域。     

碱催化制备乙酰胺/SiO2复合相变储能材料

以氨水为催化剂,乙酰胺作相变材料,采用溶胶-凝胶法制备出有机-无机复合相变蓄热材料。通过改变醇盐-醇-水体系配比及相变材料的加入量来控制蓄热能力和相变温度。采用差示扫描量热仪(DSC)和扫描电镜(SEM)进行表征。结果表明:含相变材料35.8%的复合材料的相变温度为32.0℃,相变潜热高达176.4kJ/kg,经过1500次循环后其相变温度和潜热变化不大。氨水和相变材料对复合材料性能的影响显著:随着氨浓度的增加,复合材料粒径增大;相变材料增多,复合材料储热能力提高,材料致密度增加。     

Thermal decomposition of hydroxylammonium nitrate at kilobar pressures

The Raman spectrum of an 11 molar hydroxylammonium nitrate (HAN) solution at ambient and unconfined conditions has been recorded and analyzed. Experiments at elevated pressures have been conducted using a diamond anvil cell. Pressure and temperature of the cell were varied over the range of 2–7 kbar and 22–120°C. At pressures near 6 kbar and temperatures near 90°C a significant and irreversible change in the HAN spectra was observed. This change is interpreted as the result of thermal decomposition occurring within the sample. The disappearance of features related to HAN nitrogenoxygen bonds was observed. Evidence of nitrous oxide formation was found. Some of the nitrous oxide appears to be present in the solid state. A transient appearance of nitrogen dioxide in an early reaction stage is indicated by our results.     

Thermodynamic performance of absorption-compression hybrid refrigeration cycles based on lithium nitrate+1-butyl-3-methylimidazolium nitrate/water working fluid

In this paper, LiNO₃ (lithium nitrate)-[BMIM]NO₃ (1-butyl-3-methylimidazolium nitrate)/H₂O is presented for absorption-compression hybrid refrigeration. The thermophysical properties and corrosion of this ternary system were measured. The performance of this hybrid system using LiNO₃-[BMIM]NO₃/H₂O was studied and compared with those based on LiBr (lithium bromide)/H₂O, LiNO₃/H₂O, and LiNO₃-[MMIM][DMP] (1,3-dimethylimidazolium dimethylphosphate)/H₂O. Results showed that the hybrid refrigeration cycles can work at much lower generator and evaporator temperatures in comparison with the pure absorption cycle. Generator temperatures of both hybrid cycles based on this working fluid were lower than those using the other working fluids. At different refrigeration temperatures, the generator temperatures of both hybrid cycles using this presented working fluid were reduced about 7 and 10 K, respectively, in comparison with those based on LiBr/H₂O. Compared with other working fluids, both single- and double-effect hybrid systems using this new working fluid achieved a larger coefficient of performance around 0.88 and 1.6, respectively. Additionally, the exergetic efficiency for both hybrid cycles is also about 10% larger than that using LiBr/H₂O. And this working fluid shows an excellent thermal stability below 598.32 K and acceptable high-temperature anti-corrosion to metallic materials. Moreover, the hybrid cycle using LiNO₃-[BMIM]NO₃/H₂O of 80 kW has a shorter payback period of 5.51 years when utilizing solar energy as the driven heat source. Therefore, LiNO₃-[BMIM]NO₃/H₂O shows great advantages in the absorption-compression hybrid cycles.     

Investigation of nitrate salts for solar latent heat storage

Solar thermal applications require some means of thermal energy storage. Amongst several storage concepts, latent heat storage is quite suitable because of its high storage density and almost constant temperature during charging and discharging. The temperature range between 200 and 300°C is considered to be important for solar total energy systems. In this temperature range, sodium nitrate and its mixed salts with other nitrates including eutectic and off-eutectic salts are candidates.

The present paper deals with heat transfer in a latent heat storage unit utilizing these salts. A method of rough estimation of the thermal conductivity of the storage materials is described, and the temperature history of the storage material experimentally obtained is compared with numerical solutions and found to be in reasonably good agreement.

It is seen that the temperature of the heat transfer surface quickly drops soon after the appearance of a solid phase due to low thermal conductivity of these salts. Ways to avoid this temperature drop are discussed.     

Thermal properties of a low-melting-point nitrate molten salt system

利用硝酸盐熔盐熔点低、比热容高、热分解温度高的特性,制备一种新型硝酸盐熔盐[在Ca（NO₃）₂：KNO₃为0.47：0.53的熔盐体系中添加0.1%~15%的新型添加剂],并对该熔盐的热力学特性及使用成本进行了测试分析。结果表明,新型熔盐的熔点为120.1℃,熔化潜热为76.37 J/g,分解温度为588℃,平均比热容为1.598 J/（g·K）,相比较于传统的Solar salt和Hitec熔盐热力学性能具有较大提升。采用测量范围内比热容的积分平均值来代替整个温度范围内熔盐的比热容,通过计算得出该体系熔盐的显热蓄热成本为108元/（kW·h）。此外,对新型熔盐的热扩散系数以及导热系数进行的测试分析,进一步证明了该熔盐在太阳能光热发电中作为蓄热传热介质具有巨大的潜在应用价值。     

同步脱氮脱硫技术的研究进展

废水同步脱氮脱硫技术因其具有成本低、时间短、二次污染少等优势而成为研究热点;基于废水同步脱氮脱硫的技术,废水脱氮与沼气脱硫同步进行也成为可能;综述了同步脱氮脱硫技术的化学基础、微生物基础,以及其工艺条件等方面的最新研究进展。     

High-performance direct ethanol fuel cell using nitrate reduction reaction

In this study, we propose a high-performance direct ethanol fuel cell (DEFC) using nitrate reduction reaction with a carbon felt electrode (DEFC-HNO₃) instead of oxygen reduction reaction (ORR) on a Pt catalyst (DEFC-O₂). The activation energy for the nitrate reduction reaction on the carbon electrode is found to be relatively low at ～14.2 kJ mol^?1, compared to the ORR. By using the nitrate reduction reaction at the cathode and oxidation of ethanol as a fuel at the anode, the DEFC shows a significantly high open circuit voltage of 0.85 V and two-fold maximal power density of 68 mW cm^?2 at 80 °C, compared to the DEFC-O₂, due to the significantly fast reaction rate of the nitrate reduction reaction.     

Chemical reaction and ignition in mixtures of magnesium and sodium nitrate

The isothermal kinetics and self-heating in binary mixtures of magnesium and sodium nitrate have been studied as a function of temperature and reactant composition. The effects of reduced pressures (down to 10⁻¹ torr) and of replacing the air over the reactants by argon have been examined. Comparative studies of mixtures of sodium nitrate with magnesium oxide, aluminium oxide, and aluminium were also made. From these measurements it is concluded that magnesium is oxidized in the melt by oxygen atoms produced by the decomposition of sodium nitrate and that it is the exothermicity of this reaction which leads to ignition.     

纳米颗粒对二元硝酸盐表面张力和密度的影响

为准确计算纳米熔盐的传热储热能力,利用高温熔融法将SiO2纳米颗粒分散至二元硝酸盐(60％NaNO3-40％KNO3)中,制备了5种不同含量SiO2纳米颗粒的纳米熔盐复合材料.基于阿基米德法测量液体密度和拉筒法测量液体表面张力的原理改进实验装置,搭建高温熔盐密度、表面张力实验台.实验对制备的5种纳米熔盐的表面张力和密度进行实验测量,并对实验数据进行拟合,得到5种纳米熔盐密度和表面张力随温度的变化关系,拟合得到纳米熔盐密度和表面张力与温度之间的实验关联式.结果表明,基盐及5种纳米熔盐的密度均随温度的升高而下降,且加入SiO2纳米颗粒后,熔融盐的密度变化不明显.基盐及5种纳米熔盐的表面张力也随温度的升高而下降,且加入SiO2纳米颗粒后,熔融盐的表面张力值均有所增加.提出纳米熔盐形成机理,并对纳米熔盐密度和表面张力改变的原因进行解释.     

Hydrogen-based membrane biofilm reactors for nitrate removal from water and wastewater

H₂-based membrane biofilm reactor (MBfR), a kind of autotrophic denitrification system, is a novel and special membrane bioreactor using hydrogen as inorganic electron donor to reduce nitrate and nitrite in water and wastewater. In this paper, the state of the art of recent research on denitrification through H₂-based MBfRs is reviewed, including theoretical fundamentals, key influencing factors, possible problems and applications. Hydrogen/nitrate counter-diffusion has been described as Dual substrates limitations. The denitrifying bacteria in H₂-based MBfR were summarized. The key factors affecting the performance of H₂-based MBfR were listed in terms of substrate concentrations, membrane materials, reactor types, biofilm management and operation conditions. The pH value, salinity, dissolved oxygen, HRT (hydraulic retention time) and carbon source have been identified as main operational conditions affecting H₂-MBfR performance. Furthermore, membrane fouling in H₂-based MBfRs was emphasized. H₂-MBfR was proved excellent in denitrification based on its high performance for groundwater, IX brine and aquaculture wastewater treatment. Several aspects may be considered in future works were proposed.