本文選題：鈉離子電池 + 負極材料��； 參考：《北京化工大學》2017年博士論文

【摘要】：由于具有原材料資源豐富、價格低廉、比容量較高等特點,鈉離子電池被認為是最適合大規(guī)模儲能的一種新型二次電池體系。與正極材料相比,鈉離子電池負極材料的研究相對滯后,開發(fā)具有高容量、長壽命和優(yōu)異倍率性能的負極材料是推動鈉離子電池獲得實際應用的關(guān)鍵。本論文從層間距調(diào)控、雜原子摻雜、構(gòu)建納米/多孔結(jié)構(gòu)和與金屬氧化物復合等思路出發(fā),制備了 5種新型的碳基負極材料(包括氮摻雜硬碳/石墨烯復合材料、氮摻雜多孔硬碳材料、花狀介孔碳材料、生物質(zhì)基氮摻雜介孔碳材料和Fe3O4量子點/石墨烯復合材料),研究了其電化學儲鈉性能,并對碳基負極材料的組成和結(jié)構(gòu)對其電化學性能的影響進行了探索。(1)在苯胺溶液中加入氧化石墨烯,經(jīng)過原位聚合、高溫熱解制備了三明治結(jié)構(gòu)氮摻雜碳/石墨烯(NCG)復合材料。由于具有大的層間距離(0.360 nm)和高的氮含量(7.54 at.%),NCG在30 mA g-1電流密度下的可逆儲鈉容量達到336 mAh g-1。位于三明治結(jié)構(gòu)中的高導電性石墨烯夾層保證了電子的快速傳遞,從而使NCG具有優(yōu)異的倍率性能,5 A g-1電流密度下比容量還保持有94 mAh g-1。NCG還表現(xiàn)出良好的循環(huán)穩(wěn)定性,在50 mAg-1的電流密度下循環(huán)200次后,容量保持率為89%。(2)在苯胺溶液中加入納米CaCO3模板,經(jīng)過原位聚合、高溫碳化并用稀鹽酸除去模板,制備出聚苯胺基氮摻雜介孔碳材料。氮吸附測試表明其具有多孔結(jié)構(gòu),XPS分析表明其氮含量高達7.78 at.%。聚苯胺基氮摻雜介孔碳材料在30 mA g-1電流密度下的首次可逆容量為338 mAh g-1,循環(huán)耐久性突出,500 mA g-1電流下循環(huán)800周后容量還可保持110.7 mAh g-1。(3)以檸檬酸鋅為碳源,在惰性氣氛下高溫熱解制備出具有高比表面和發(fā)達介孔結(jié)構(gòu)的花狀碳材料。檸檬酸鋅高溫熱解產(chǎn)生的納米氧化鋅同時充當了介孔模板,制備的碳材料BET比表面積和孔容分別達到1382 cm 2g-1和2.02 cm 3-1。獨特的花狀結(jié)構(gòu)、發(fā)達的介孔和大的層間距(0.42 nm),賦予該碳材料超高的可逆容量和優(yōu)異的倍率性能。在30 mAg-1電流密度下的首次可逆容量高達438.5 mAh g-1,當電流密度提高到10 A g-1,仍具有68.7 mAh g-1的放電比容量。(4)以蝦皮為原料,將其高溫熱解簡便制備出兼有高氮含量和發(fā)達介孔結(jié)構(gòu)的碳材料。蝦皮是由膠原蛋白和無機礦物質(zhì)組成的天然有機/無機納米復合材料,高溫熱解過程中,膠原蛋白作為富氮的碳源轉(zhuǎn)化為富氮炭,均勻分散在其中的納米無機礦物質(zhì)作為硬模板被洗去后留下豐富的介孔。隨熱解溫度升高,比表面和孔容呈增大的趨勢,氮含量減小。700 ℃制備的樣品兼有高的比表面(531 m2g-1)和高的氮含量(7.26 at %),表現(xiàn)出突出的電化學儲鈉性能。在30 mA g-1電流密度下的可逆鈉存儲容量高達434.6 mAh g-1,循環(huán)和倍率性能優(yōu)異。以天然納米復合材料為原料制備高性能鈉離子電池負極材料,方法簡單,成本低廉,變廢為寶,符合可持續(xù)發(fā)展的要求。(5)采用水熱法制備了 Fe3O4量子點與三維石墨烯(3D-0DFe3O4/石墨烯)的復合材料。Fe3O4量子點的平均尺寸為4.9 nm,鑲嵌在石墨烯的三維立體網(wǎng)絡結(jié)構(gòu)中。Fe3O4量子點具有高的電化學活性,充放電過程中體積變化較小,3D石墨烯一方面可抑制Fe3O4納米粒子的團聚及其在充電放電過程中的體積變化,另一方面可構(gòu)建電子傳導和離子遷移的快速通道。因此,3D-0DFe3O4/石墨烯復合材料表現(xiàn)出了超高的儲鈉容量(30 mA g-1電流密度下的可逆儲鈉容量高達525 mAh g-1),優(yōu)異的循環(huán)穩(wěn)定性(50 mA g-1電流下循環(huán)200周容量保持312 mAh g-1)和倍率性能(10 A g-1電流密度下比容量保持56 mAh g-1)。
[Abstract]:Because of the rich raw material resources, low price and higher specific capacity, sodium ion battery is considered to be the most suitable for large-scale energy storage of a new type of two battery system. Compared with the cathode material, the research of sodium ion battery negative electrode is relatively lagging, and the development of negative electrode with high capacity, long life and excellent performance ratio is a kind of negative material. In this paper, 5 new carbon based negative electrode materials (including nitrogen doped hard carbon / graphene composite, nitrogen doped porous hard carbon material, and flower like mesoporous carbon material) are prepared from interlayer spacing regulation, heteroatom doping, nano/ porous structure and metal oxide composite. Biomass based nitrogen doped mesoporous carbon materials and Fe3O4 quantum dots / graphene composite materials were used to study the electrochemical properties of its electrochemical properties. The effects of the composition and structure of carbon based anode materials on their electrochemical properties were explored. (1) the sandwich structure was prepared by in-situ polymerization and high temperature pyrolysis in the aniline solution. Nitrogen doped carbon / graphene (NCG) composites. Due to the large interlayer distance (0.360 nm) and high nitrogen content (7.54 at.%), the reversible sodium capacity of NCG at 30 mA g-1 current density reached 336 mAh g-1. high conductivity graphene interlayer in the sandwich structure ensuring the rapid transmission of electrons, thus making NCG with excellent multiplier. Performance, the specific capacity of 5 A g-1 current density remains 94 mAh g-1.NCG and has good cyclic stability. After 200 cycles of 50 mAg-1 current density, the capacity retention rate is 89%. (2) adding nano CaCO3 template in aniline solution, after in situ polymerization, high temperature carbonization and removal of template with dilute hydrochloric acid to prepare polyaniline based nitrogen doping. The nitrogen adsorption test shows that it has porous structure. XPS analysis shows that the nitrogen content is up to 7.78 at.%. polyaniline based mesoporous carbon materials at the 30 mA g-1 current density, the first reversible capacity is 338 mAh g-1, the cycle durability is prominent, the capacity of 500 mA g-1 current is 800 weeks after 800 weeks and 110.7 mAh g-1. (3) can be maintained. Zinc citrate is a carbon source. High specific surface and developed mesoporous carbon materials are prepared at high temperature under inert atmosphere. The nano Zinc Oxide produced by high temperature pyrolysis of zinc citrate simultaneously acts as a mesoporous template, and the prepared carbon material BET has a unique flower structure of 1382 cm 2g-1 and 2.02 cm 3-1., respectively. The developed mesoporous and large interlayer spacing (0.42 nm) gives the carbon material a high reversible capacity and excellent multiplier performance. The first reversible capacity at 30 mAg-1 current density is up to 438.5 mAh g-1, and when the current density increases to 10 A g-1, it still has a discharge specific volume of 68.7 mAh g-1. (4) the high temperature pyrolysis of the dried shrimps is prepared. It has high nitrogen content and developed mesoporous carbon. The shrimp skin is a natural organic / inorganic nanocomposite made up of collagen and inorganic minerals. During the high temperature pyrolysis process, collagen is converted to nitrogen rich carbon as a carbon rich source of nitrogen rich. With the increase of thermal decomposition temperature, the specific surface and pore volume are increasing. The reduction of nitrogen content at.700 C has both high specific surface (531 m2g-1) and high nitrogen content (7.26 at%), showing outstanding electrochemical sodium storage performance. The reversible sodium storage capacity at 30 mA g-1 current density is up to 434.6 mAh g-1, cycle and multiplying ratio. Excellent performance. The preparation of high performance sodium ion battery anode material with natural nano composite material is simple, low cost and waste into treasure, which meets the requirements of sustainable development. (5) the average size of.Fe3O4 quantum dots of Fe3O4 quantum dots and 3D-0DFe3O4/ graphene (graphene) is prepared by hydrothermal method, and the average size of the.Fe3O4 quantum dots is 4.9 nm, In the three-dimensional network structure embedded in graphene,.Fe3O4 quantum dots have high electrochemical activity, and the volume change is small during charge discharge. In one aspect, 3D graphene can inhibit the aggregation of Fe3O4 nanoparticles and their volume changes during charging and discharging. On the other hand, the rapid channel of electronic conduction and ion migration can be constructed. The 3D-0DFe3O4/ graphene composite exhibits super high sodium storage capacity (the reversible sodium capacity of 30 mA g-1 current density is up to 525 mAh g-1), excellent cyclic stability (50 mA g-1 current for 200 weeks capacity to maintain 312 mAh g-1) and multiplying performance (10 A g-1 current density under the capacity of 56 mAh).

【學位授予單位】：北京化工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TM912

【參考文獻】

相關(guān)期刊論文 前2條

1 Jian Liu;Hao Liu;Tianyu Yang;Guoxiu Wang;Moses O.Tade;;Mesoporous carbon with large pores as anode for Na-ion batteries[J];Chinese Science Bulletin;2014年18期

2 李慧;吳川;吳鋒;白瑩;;鈉離子電池:儲能電池的一種新選擇[J];化學學報;2014年01期

，

本文編號：1828099