堿性二次電池新型鐵負(fù)極材料的合成及性能的研究
發(fā)布時(shí)間：2019-07-10 15:45
【摘要】：在能源枯竭與環(huán)境污染問(wèn)題日益嚴(yán)重的今天,綠色二次電池作為一種新型高效的能源裝置獲得了與日俱增的關(guān)注。鐵鎳二次電池由于具有循環(huán)性能優(yōu)異、制造成本低、環(huán)境友好等優(yōu)點(diǎn),被認(rèn)為是未來(lái)較具競(jìng)爭(zhēng)力的化學(xué)電源。當(dāng)前,鐵鎳電池依舊存在充電效率低、極易鈍化、析氣嚴(yán)重、自放電、高倍率性能較差等缺點(diǎn)。因此,在一定程度上制約著其大規(guī)模商業(yè)化生產(chǎn)。針對(duì)上述鐵鎳電池存在的缺點(diǎn),本論文主要進(jìn)行了以下方面的研究:(1)新型FeS@RGO納米復(fù)合材料的合成與研究:通過(guò)一個(gè)簡(jiǎn)單的環(huán)境友好的直接共沉淀法將FeS納米粒子固定在還原氧化石墨烯納米片上,制備出FeS@RGO納米片復(fù)合材料,并將該新型材料首次用作堿性鐵鎳二次電池負(fù)極材料。形貌表征測(cè)試表明,FeS納米粒子均一的、緊密的固定在還原氧化石墨烯納米片的表面上。電性能測(cè)試表明,FeS/RGO電極在沒(méi)有任何導(dǎo)電添加劑以及具有較高的活性物質(zhì)負(fù)載量(約40 mg cm-2)的條件下,表現(xiàn)出了較好的高倍率充電/放電容量和優(yōu)異的循環(huán)穩(wěn)定性。在較高的充電/放電倍率5 C、10 C和20 C(6000 mA g-1)下,FeS@RGO電極的放電比容量分別為288 mAh g-1,258 mAh g-1和220 mAh g-1。值得一提的是,FeS@RGO電極在2 C充電/放電倍率下經(jīng)過(guò)300次循環(huán)后,容量保持率仍達(dá)到87.6%,表現(xiàn)出超好的循環(huán)性能。FeS@RGO材料的優(yōu)異的電化學(xué)性能主要來(lái)源于其具有較高的比表面積,較高的電導(dǎo)率和強(qiáng)健的薄片支撐結(jié)構(gòu)。由于具有快速的充放電能力,FeS@RGO納米復(fù)合材料非常適合作為高性能的堿性二次電池的負(fù)極材料。(2)新型Fe_3O_4@Ni_3S_2復(fù)合材料的合成與性能研究:通過(guò)簡(jiǎn)單的三步法成功地制備出Fe_3O_4@Ni_3S_2微球,并將其作為一種新型鐵鎳電池負(fù)極材料。在這種復(fù)合材料中,Ni_3S_2納米粒子緊密地包裹在Fe_3O_4微球的表面上。與純的Fe_3O_4和Fe_3O_4@NiO微球相比,合成出的Fe_3O_4@Ni_3S_2復(fù)合材料表現(xiàn)出更好的高倍率性能。在1200 mA g-1較高的放電倍率下Fe_3O_4@Ni_3S_2電極的放電比容量為481.2 mAh g-1,而純的Fe_3O_4電極的放電比容量?jī)H為83.7 mAh g-1。此外,相對(duì)于純的Fe_3O_4材料,Fe_3O_4@Ni_3S_2也表現(xiàn)出優(yōu)異的循環(huán)穩(wěn)定性。在120 mA g-1倍率下,Fe_3O_4@Ni_3S_2電極經(jīng)過(guò)100次循環(huán)后,容量保持率高達(dá)95.1%,然而純的Fe_3O_4電極的容量保持率僅為52.5%。可以得知,Ni_3S_2材料的包覆極大地改善了Fe_3O_4@Ni_3S_2電極的電化學(xué)性能。研究表明,Ni_3S_2涂層作為一個(gè)有益的添加劑,可以明顯阻止Fe(OH)2鈍化膜的形成,進(jìn)而增強(qiáng)電極的電子導(dǎo)電性,提高電極反應(yīng)的可逆性,同時(shí)一定程度上可以抑制鐵負(fù)極析氫反應(yīng)的發(fā)生。由于具有優(yōu)異的電化學(xué)性能,Fe_3O_4@Ni_3S_2復(fù)合材料將會(huì)是一種很有前途的堿性鐵鎳二次電池的負(fù)極材料。(3)花狀NiS的合成及其對(duì)鐵電極電性能的影響:首先運(yùn)用L-半胱氨酸輔助法合成花狀NiS,并將NiS當(dāng)作添加劑應(yīng)用到鐵鎳二次電池的負(fù)極材料中,研究NiS添加劑對(duì)鐵負(fù)極電化學(xué)性能的影響。與純的四氧化三鐵電極相比,添加NiS的鐵電極表現(xiàn)出較好的高倍率性能和循環(huán)穩(wěn)定性,尤其是添加10%的NiS性能最佳。添加10%的NiS電極在6000 mA g-1較高倍率下的放電容量能達(dá)到352.1mAh g-1。并且,在600 mA g-1的倍率下經(jīng)過(guò)100次循環(huán)后,其放電容量仍達(dá)到406.2 mAh g-1(對(duì)應(yīng)的循環(huán)保持率為80.3%)。初步研究表明,NiS可以用作高效的電極添加劑,提高鐵鎳電池的倍率和循環(huán)性能。
文內(nèi)圖片：
圖片說(shuō)明：(a)氧化石墨烯的拉曼光譜圖(b)氧化石墨烯的XRD圖
[Abstract]:As a new type of high-efficiency energy device, the green secondary battery has gained increasing attention in the day of energy exhaustion and environmental pollution. The iron-nickel secondary battery has the advantages of excellent cycle performance, low manufacturing cost, environmental protection and the like, and is considered to be a more competitive chemical power source in the future. At present, the iron-nickel cell still has the disadvantages of low charging efficiency, easy passivation, serious gassing, self-discharge, poor high-rate performance and the like. Therefore, the large-scale commercial production is restricted to a certain extent. In order to overcome the defects of the above-mentioned iron-nickel cell, the paper mainly studies the following aspects: (1) the synthesis and research of a new FeS@RGO-type nano-composite material: the FeS nano-particles are fixed on the reduction-oxidized graphene nano-sheet by a simple and environment-friendly direct-precipitation method; The FeS@RGO nano-sheet composite material is prepared, and the new material is used for the first time as the negative electrode material of the alkaline iron-nickel secondary battery. The results show that the FeS nano-particles are uniformly and tightly fixed on the surface of the reduction-oxidized graphene nanosheet. The electrical property test showed that the FeS/ RGO electrode exhibited good high rate charge/ discharge capacity and excellent cycle stability under the condition of no conductive additive and high active material loading (about 40 mg cm-2). At higher charge/ discharge rates of 5C, 10C and 20C (6000 mA g-1), the discharge specific capacity of the FeS@RGO electrode was 288 mAh g-1,258 mAh g-1 and 220 mAh g-1, respectively. It is worth mentioning that after 300 cycles of the FeS@RGO electrode at the charge/ discharge rate of 2C, the capacity retention rate still reaches 87.6%, and the excellent electrochemical performance of the super-good cyclic performance .FeS@RGO material mainly comes from the higher specific surface area, Higher conductivity and robust sheet support structures. The FeS@RGO nanocomposite is very suitable as a negative electrode material for a high-performance alkaline secondary battery due to the rapid charge-discharge capability. (2) The synthesis and performance of a new type of Fe_3O_4@Ni_3S_2 composite material: the Fe_3O_4@Ni_3S_2 microspheres were successfully prepared by a simple three-step method and used as a new type of iron-nickel battery cathode material. In this kind of composite material, the Ni _ 3S _ 2 nano-particles are closely packed on the surface of the Fe _ 3O _ 4 micro-sphere. Compared with pure Fe _ 3O _ 4 and Fe_3O_4@NiO microspheres, the synthesized Fe_3O_4@Ni_3S_2 composite has better high-rate performance. The discharge specific capacity of the Fe_3O_4@Ni_3S_2 electrode is 481.2 mAh g-1 at a discharge rate of 1200 mA g-1, and the discharge specific capacity of the pure Fe _ 3O _ 4 electrode is only 83.7 mAh g-1. In addition, the Fe_3O_4@Ni_3S_2 also exhibits excellent cycle stability with respect to the pure Fe _ 3O _ 4 material. The capacity retention rate of Fe _ 3O _ 4@Ni _ 3S _ 2 electrode was 95.1% after 100 cycles at 120 mA g-1. However, the capacity retention rate of pure Fe _ 3O _ 4 electrode was only 52.5%. It is known that the coating of the Ni _ 3S _ 2 material greatly improves the electrochemical performance of the Fe_3O_4@Ni_3S_2 electrode. The results show that the Ni _ 3S _ 2 coating as a beneficial additive can significantly prevent the formation of the Fe (OH)2 passivation film, thereby enhancing the electronic conductivity of the electrode and improving the reversibility of the electrode reaction, and at the same time, the occurrence of the hydrogen evolution reaction of the iron anode can be suppressed to a certain extent. Due to the excellent electrochemical performance, the Fe_3O_4@Ni_3S_2 composite material will be a promising cathode material for the alkaline iron-nickel secondary battery. (3) The synthesis of the flower-like NiS and its effect on the electrical property of the iron electrode: firstly, the flower-like NiS is synthesized by the L-cysteine-assisted method, and the NiS is used as an additive to the cathode material of the iron-nickel secondary battery, and the effect of the NiS additive on the electrochemical performance of the iron negative electrode is studied. Compared with the pure ferroferric oxide electrode, the Fe electrode added with the NiS shows good high-rate performance and cycle stability, in particular, the addition of 10% of the NiS performance is the best. The discharge capacity of 10% NiS electrode at a high rate of 6000 mA g-1 can reach 352.1 mAh g-1. After 100 cycles at 600 mA g-1, the discharge capacity still reached 406.2 mAh g-1 (the corresponding cycle retention rate was 80.3%). The preliminary study shows that NiS can be used as an efficient electrode additive to improve the rate and cycle performance of the iron-nickel cell.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM912
本文編號(hào)：2512701
文內(nèi)圖片：
圖片說(shuō)明：(a)氧化石墨烯的拉曼光譜圖(b)氧化石墨烯的XRD圖
[Abstract]:As a new type of high-efficiency energy device, the green secondary battery has gained increasing attention in the day of energy exhaustion and environmental pollution. The iron-nickel secondary battery has the advantages of excellent cycle performance, low manufacturing cost, environmental protection and the like, and is considered to be a more competitive chemical power source in the future. At present, the iron-nickel cell still has the disadvantages of low charging efficiency, easy passivation, serious gassing, self-discharge, poor high-rate performance and the like. Therefore, the large-scale commercial production is restricted to a certain extent. In order to overcome the defects of the above-mentioned iron-nickel cell, the paper mainly studies the following aspects: (1) the synthesis and research of a new FeS@RGO-type nano-composite material: the FeS nano-particles are fixed on the reduction-oxidized graphene nano-sheet by a simple and environment-friendly direct-precipitation method; The FeS@RGO nano-sheet composite material is prepared, and the new material is used for the first time as the negative electrode material of the alkaline iron-nickel secondary battery. The results show that the FeS nano-particles are uniformly and tightly fixed on the surface of the reduction-oxidized graphene nanosheet. The electrical property test showed that the FeS/ RGO electrode exhibited good high rate charge/ discharge capacity and excellent cycle stability under the condition of no conductive additive and high active material loading (about 40 mg cm-2). At higher charge/ discharge rates of 5C, 10C and 20C (6000 mA g-1), the discharge specific capacity of the FeS@RGO electrode was 288 mAh g-1,258 mAh g-1 and 220 mAh g-1, respectively. It is worth mentioning that after 300 cycles of the FeS@RGO electrode at the charge/ discharge rate of 2C, the capacity retention rate still reaches 87.6%, and the excellent electrochemical performance of the super-good cyclic performance .FeS@RGO material mainly comes from the higher specific surface area, Higher conductivity and robust sheet support structures. The FeS@RGO nanocomposite is very suitable as a negative electrode material for a high-performance alkaline secondary battery due to the rapid charge-discharge capability. (2) The synthesis and performance of a new type of Fe_3O_4@Ni_3S_2 composite material: the Fe_3O_4@Ni_3S_2 microspheres were successfully prepared by a simple three-step method and used as a new type of iron-nickel battery cathode material. In this kind of composite material, the Ni _ 3S _ 2 nano-particles are closely packed on the surface of the Fe _ 3O _ 4 micro-sphere. Compared with pure Fe _ 3O _ 4 and Fe_3O_4@NiO microspheres, the synthesized Fe_3O_4@Ni_3S_2 composite has better high-rate performance. The discharge specific capacity of the Fe_3O_4@Ni_3S_2 electrode is 481.2 mAh g-1 at a discharge rate of 1200 mA g-1, and the discharge specific capacity of the pure Fe _ 3O _ 4 electrode is only 83.7 mAh g-1. In addition, the Fe_3O_4@Ni_3S_2 also exhibits excellent cycle stability with respect to the pure Fe _ 3O _ 4 material. The capacity retention rate of Fe _ 3O _ 4@Ni _ 3S _ 2 electrode was 95.1% after 100 cycles at 120 mA g-1. However, the capacity retention rate of pure Fe _ 3O _ 4 electrode was only 52.5%. It is known that the coating of the Ni _ 3S _ 2 material greatly improves the electrochemical performance of the Fe_3O_4@Ni_3S_2 electrode. The results show that the Ni _ 3S _ 2 coating as a beneficial additive can significantly prevent the formation of the Fe (OH)2 passivation film, thereby enhancing the electronic conductivity of the electrode and improving the reversibility of the electrode reaction, and at the same time, the occurrence of the hydrogen evolution reaction of the iron anode can be suppressed to a certain extent. Due to the excellent electrochemical performance, the Fe_3O_4@Ni_3S_2 composite material will be a promising cathode material for the alkaline iron-nickel secondary battery. (3) The synthesis of the flower-like NiS and its effect on the electrical property of the iron electrode: firstly, the flower-like NiS is synthesized by the L-cysteine-assisted method, and the NiS is used as an additive to the cathode material of the iron-nickel secondary battery, and the effect of the NiS additive on the electrochemical performance of the iron negative electrode is studied. Compared with the pure ferroferric oxide electrode, the Fe electrode added with the NiS shows good high-rate performance and cycle stability, in particular, the addition of 10% of the NiS performance is the best. The discharge capacity of 10% NiS electrode at a high rate of 6000 mA g-1 can reach 352.1 mAh g-1. After 100 cycles at 600 mA g-1, the discharge capacity still reached 406.2 mAh g-1 (the corresponding cycle retention rate was 80.3%). The preliminary study shows that NiS can be used as an efficient electrode additive to improve the rate and cycle performance of the iron-nickel cell.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM912
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 徐宏賓;;綠色化學(xué)在新能源電池中的應(yīng)用[J];現(xiàn)代工業(yè)經(jīng)濟(jì)和信息化;2014年13期
2 郎雷鳴;徐正;;海膽狀硫化鎳空心球的制備及電化學(xué)性能研究[J];高等學(xué)�；瘜W(xué)學(xué)報(bào);2011年03期
3 林本蘭;沈曉冬;崔升;;納米四氧化三鐵磁性微粒的表面有機(jī)改性[J];無(wú)機(jī)鹽工業(yè);2006年03期
4 周潔,馬明,張宇,顧寧;不同尺寸Fe_3O_4磁性顆粒的制備和表征[J];東南大學(xué)學(xué)報(bào)(自然科學(xué)版);2005年04期
5 ;Influence of Four Factors on Discharge Capacity and Self-Discharge Rate of Iron Electrode[J];Journal of Materials Science & Technology;2003年06期
6 侯憲魯,南俊民;鐵電極材料在電池中的應(yīng)用[J];電池;2003年01期
7 林東風(fēng),蔡蓉,宋德瑛;鐵電極中鐵粉含量對(duì)其充電效率的影響[J];電源技術(shù);2002年04期
8 袁紅,蔡克霞;添加劑對(duì)球形Ni(OH)_2活性影響的研究[J];寧夏工程技術(shù);2002年02期
9 陳騰飛,黃伯云,賀萬(wàn)寧,王利君;球形氫氧化鎳同時(shí)摻雜Co、Zn的研究[J];湘潭礦業(yè)學(xué)院學(xué)報(bào);2001年03期
10 袁安保,張鑒清,曹楚南;鎳電極研究進(jìn)展[J];電源技術(shù);2001年01期
相關(guān)博士學(xué)位論文 前1條
1 袁永鋒;鋅鎳電池電極材料氧化鋅納米化與表面修飾的結(jié)構(gòu)及其電化學(xué)性能[D];浙江大學(xué);2007年
相關(guān)碩士學(xué)位論文 前4條
1 譚志勇;添加劑對(duì)鋅鎳二次電池鋅負(fù)極的性能影響[D];中南大學(xué);2012年
2 顧賽君;鋅鎳電池氧化鋅基負(fù)極材料的制備及電化學(xué)性能[D];浙江工業(yè)大學(xué);2012年
3 李青松;鐵鎳蓄電池鐵負(fù)極性能研究[D];河南師范大學(xué);2011年
4 姜敬輝;L-半胱氨酸輔助金屬硫化物微米材料的合成與表征[D];中南大學(xué);2010年
，本文編號(hào)：2512701
本文鏈接：http://sikaile.net/kejilunwen/dianlidianqilunwen/2512701.html
最近更新
教材專著
