【作者】 张鑫；

【导师】 王智；

【作者基本信息】 中北大学 ， 材料科学与工程， 2020， 硕士

【摘要】 苯并噁嗪树脂具有优良的综合性能,在众多领域得到广泛应用,但由于其固化温度高、脆性大,严重的制约了它的发展与应用。因此本文通过将过渡金属硝酸盐引入到苯并噁嗪的开环聚合过程中,在解决苯并噁嗪树脂固化温度高的同时,原位的将无机粒子与氧化氮引入到苯并噁嗪体系,为其作为碳材料前驱体从而制备碳材料的探索提供了基础。（1）运用同一周期、同一主族五种不同过渡金属硝酸盐（硝酸铝、硝酸镓、硝酸铟、硝酸铜和硝酸钴）作为苯并噁嗪树脂的催化剂研究其固化行为及固化机理。首先研究了不同体系的五种过渡金属硝酸盐在35 ^oC条件下对苯并噁嗪的催化作用。结果显示,过渡金属硝酸盐的加入确实催化了苯并噁嗪的固化过程,均使其固化温度降低了60 ^oC左右,且变化具有周期性。其次对不同体系进行了固化机理研究,发现,在35 ^oC时,金属离子攻击苯并噁嗪中噁嗪环,并与噁嗪环中O原子进行配位使其发生开环交联反应,开环形成C=N⁺中间体和⁺C-N中间体,结构中的⁺C-N中间体参与苯并噁嗪的交联反应,并与其它结构之间相互交联形成N,O-缩醛桥型结构、芳基胺曼尼希桥结构、酚类曼尼希桥结构这三种交联结构,随着反应时间的延长形成更多的N,O-缩醛桥型结构且逐渐向较为稳定芳基胺曼尼希桥结构转变,这种结构的转变提升了苯并噁嗪的热稳定性,并对其力学性能亦具有一定的促进作用。（2）由于苯并噁嗪自身的优异性能,是含氮碳材料的优良前体。使用过渡金属硝酸盐/苯并噁嗪复合材料体系作为碳材料的前体,并利用球磨法将过渡金属硝酸盐/苯并噁嗪复合材料包覆于磷酸铁锂前体表面,制备磷酸铁锂-过渡金属硝酸盐/苯并噁嗪碳材料（LFP-M-B）的前体,并使用该前体制备碳材料。发现相较@M-B碳材料来说,LFP@M-B碳材料所制备的电极材料的CV曲线显示出类似矩形的形状,且均具有小的、宽的氧化还原峰。它所制备的碳材料具有较优异的电容性能,比电容亦有很大的提升。（3）利用硝酸钴/苯并噁嗪复合材料体系作为苯并噁嗪碳材料的前体,用球磨法进行预处理,并利用KOH一步活化法对该复合材料进行常温活化处理,从而制备硝酸钴/苯并噁嗪碳材料（@Co-B/OH）,与@Co-B碳材料相比具有更高的结晶度、更大的层间间距及更多的化学反应位点,为电子传输和离子扩散过程提供了基础。当碳化温度为750 ^oC时,@Co-B碳材料与活化后@Co-B/OH碳材料相比,@Co-B/OH碳材料的比表面积得到了142.94 m²/g的提升。@Co-B/OH体现出更好的电容性能、比电容及功率/能量密度,@Co-B/OH碳材料当功率密度为25 W kg^-1时,其能量密度为0.95 Wh kg^-1。更多还原

【Abstract】 Benzoxazine resin has excellent comprehensive properties which makes it widely used in many fields.However,its high curing temperature and brittleness severely restrict its development and application.Therefore,the transition metal nitrate is introduced into the ring-opening polymerization process of benzoxazine resin.While solving the high curing temperature of benzoxazine resin,the in situ introduction of inorganic particles and nitrogen oxide into the benzoxazine system provided a basis for its exploration as a carbon material precursor to prepare carbon materials.The detail research content are in following aspects.（1）Five different metal nitrates（Aluminum Nitrate,Gallium Nitrate,Indium Nitrate,Copper Nitrate and Cobalt Nitrate）were used as catalysts for benzoxazine resins to study its curing behavior and curing mechanism.We found that the addition of metal nitrates indeed catalyzed the curing process of BA-a.All researched metal ion could reduce the curing temperature of BA-a by about 60 ^oC,and followed the change tendency of periodic changes.Secondly,at 35 ^oC,metal ions attack the oxazine ring in the benzoxazine and coordinate with the O atom in the oxazine ring to cause a ring-opening reaction to form a C=N⁺intermediate and a⁺C-N intermediate.The⁺C-N intermediate in the structure participates in the cross-linking reaction of benzoxazine,and cross-linked with other structures to form three cross-linked structures:N,O-acetal Bridge Structure,Arylamine Mannich Bridge Structure and Phenolic Mannich Bridge Structure.And at 35 ^oC,more N,O-acetal bridge structures were formed in the presence of the catalyst and gradually changed to a more stable Arylamine Mannich Bridge Structure.This structural change improves the thermal stability and the toughness of polybenzoxazine.（2）Due to its excellent properties,benzoxazine is an excellent precursor for nitrogen-containing carbon materials.Transition metal nitrate/benzoxazine composite system was used as the precursor of the carbon material,and a ball milling method was used to prepare a precursor of Lithium Iron Phosphate-metal nitrate/benzoxazine carbon material（LFP-M-B）by coating the transition metal nitrate/benzoxazine composite material on the surface of the lithium iron phosphate.It was found that the CV curve of the LFP@M-B showed a rectangular shape compared with the electrode material prepared by@M-B.The carbon material prepared by this method has a more excellent capacitance performance.Meanwhil and the specific capacitance are also greatly improved.（3）Using the Cobalt Nitrate/benzoxazine composite system as the precursor to make carbon material.The ball mill method was used for pretreatment,and then the composite materials were activated at room temperature by KOH one-step activation method to prepare cobalt nitrate/benzoxazine carbon material（@Co-B/OH）.Compared with@Co-B,it has higher crystallinity,larger interlayer spacing,and more chemical reaction sites,which provides a basis for electron transport and ion diffusion.When the carbonization temperature is 750 ^oC,the specific surface area of the activated@Co-B/OH is increased by 142.94 m²/g compared to that of@Co-B and@Co-B/OH.Better capacitance performance,specific capacitance and the improved power/energy density can be got in@Co-B/OH.@Co-B/OH has a enegry density of 0.95 Wh kg^-1 when the power density is 25 W kg^-1.更多还原