發(fā)布時(shí)間：2018-06-18 07:15

  本文選題：鋰離子電池 + 負(fù)極材料�。� 參考：《湘潭大學(xué)》2014年博士論文

【摘要】：我國(guó)對(duì)鋰離子電池材料及其關(guān)鍵技術(shù)的發(fā)展尤為重視，將其列入到《2006~2020年的國(guó)家中長(zhǎng)期科技發(fā)展規(guī)劃綱要》中。與此同時(shí)，電動(dòng)汽車、混合動(dòng)力汽車等大型交通工具以及其它大型用電設(shè)備的高速發(fā)展也對(duì)鋰離子電池在容量方面提出了更高的要求。負(fù)極材料是影響鋰離子電池容量的關(guān)鍵材料之一。作為新型負(fù)極材料的杰出代表之一，錫基合金負(fù)極材料的理論質(zhì)量比容量(993mAh/g)是石墨負(fù)極的近三倍。但該材料在充放電過程中伴隨著巨大的體積變形(260%)，導(dǎo)致材料在充放電過程中粉化脫落，降低材料的電化學(xué)循環(huán)性能，該現(xiàn)象是阻礙錫基合金負(fù)極材料的市場(chǎng)化應(yīng)用的關(guān)鍵所在。提升錫基合金負(fù)極材料的循環(huán)性能的方法眾多，與碳材料復(fù)合是有效方式之一，其中與碳納米管復(fù)合的報(bào)道逐漸增多。一體化電極材料能減少傳統(tǒng)電極在集成過程中的冗余連接成分(導(dǎo)電劑與粘結(jié)劑)，從而提高空間與材料的利用率，因而該類型電極也被廣泛地應(yīng)用于錫基負(fù)極材料當(dāng)中。 本論文以錫基合金負(fù)極的商業(yè)化應(yīng)用為目標(biāo)，針對(duì)錫基合金負(fù)極存在的以上不足，借鑒集流體與活性材料一體化的思想，采用生產(chǎn)成本低廉，工藝簡(jiǎn)單的電沉積，結(jié)合熱處理的工藝方法，制備了不同結(jié)構(gòu)類型的電極，并對(duì)其微觀結(jié)構(gòu)與儲(chǔ)鋰性能進(jìn)行了研究。本論文獲得的創(chuàng)新性研究成果如下： (1)為了提高錫銅合金負(fù)極的循環(huán)性能，我們基于錫/銅交替的多層結(jié)構(gòu)，在低溫短時(shí)熱擴(kuò)散處理?xiàng)l件下形成了一體化Cu6Sn5合金負(fù)極。我們采用電鍍的方法，以銅帶基底成功制備了特定厚度比的錫/銅多層膜結(jié)構(gòu)材料。再對(duì)多層結(jié)構(gòu)材料進(jìn)行熱處理，從而得到一體化錫銅合金負(fù)極。并研究了熱處理溫度等參數(shù)對(duì)電極材料結(jié)構(gòu)與循環(huán)性能的影響。結(jié)果表明，由于不同溫度下原子活性不同，多層結(jié)構(gòu)材料熱處理形成的合金成分存在差異。多層結(jié)構(gòu)材料在200℃，熱處理30min時(shí)，其電化學(xué)循環(huán)性能最優(yōu)，且該電極材料比傳統(tǒng)方法制備的電極容量更高，循環(huán)更為穩(wěn)定，在經(jīng)過40次循環(huán)后，容量高出傳統(tǒng)錫銅合金負(fù)極26.9%。該電極性能優(yōu)越的原因在于電極活性材料主要為Cu6Sn5相，且材料晶粒細(xì)小，在熱處理前后變化不大。 (2)為了緩解錫基負(fù)極材料在充放電過程中材料粉化的問題，我們基于高強(qiáng)度，高導(dǎo)電的碳納米管，將其與錫金屬負(fù)極復(fù)合制備了Sn-CNTs一體化電極材料。我們采用復(fù)合電沉積的方式，制備了Sn-CNTs復(fù)合電極，并對(duì)制備復(fù)合電極的工藝參數(shù)以及CNTs直徑對(duì)電極循環(huán)性能的影響進(jìn)行了研究。結(jié)果表明，CNTs的含量隨電流密度不同而改變；采用直徑范圍為(10~20nm)的CNTs對(duì)電極的循環(huán)性能提升最為明顯。該電極循環(huán)性能最好的原因在于：電極內(nèi)CNTs含量最高，內(nèi)阻最小。 (3)為了增強(qiáng)集流體與活性材料之間的結(jié)合，進(jìn)一步減緩錫銅合金負(fù)極材料在充放電過程中材料粉化的問題，我們?cè)赟n-CNTs復(fù)合電極基礎(chǔ)上，基于Cu-CNTs復(fù)合鍍層，設(shè)計(jì)了Sn/Cu-CNTs雙層結(jié)構(gòu)電極，增強(qiáng)了活性材料(錫銅合金)與集流體(銅)之間的電連接，并最終熱處理得到Sn-Cu-CNTs一體化電極材料。我們采用電沉積的方式，首先在銅箔基底上制備Cu-CNTs復(fù)合鍍層，再電沉積了一定厚度的錫鍍層，最后熱處理得到Sn-Cu-CNTs一體化電極。我們首先研究了電流密度對(duì)復(fù)合鍍層表面形貌與碳納米管含量的影響，然后研究了熱處理溫度對(duì)電極電化學(xué)循環(huán)性能的影響。結(jié)果表明，Cu-CNTs復(fù)合鍍層形貌與碳含量均隨電流密度改變而改變，電極在200℃熱處理6h后循環(huán)性能最優(yōu)。該電極循環(huán)性能最優(yōu)的原因在于：電極活性材料晶粒細(xì)小，與集流體之間結(jié)合良好；CNTs與活性材料連接緊密，能起到骨架材料與導(dǎo)電連接的作用。 (4)為了提高了活性材料內(nèi)碳納米管的含量，達(dá)到改善錫基合金循環(huán)性能的目的，我們以Cu-CNTs連接層為基礎(chǔ)，將Sn-CNTs活性材料與Cu-CNTs連接層結(jié)合，設(shè)計(jì)了Sn-CNTs/Cu-CNTs復(fù)合電極。我們采用復(fù)合電沉積的方式，以銅箔為基底先電沉積Cu-CNTs復(fù)合鍍層，然后在電沉積Sn-CNTs復(fù)合鍍層制備了Sn-CNTs/Cu-CNTs復(fù)合電極材料，并對(duì)熱處理時(shí)間對(duì)電極循環(huán)性能的影響進(jìn)行了研究。結(jié)果表明，，經(jīng)過200℃，6h熱處理后，電極的循環(huán)性能最優(yōu)，在1C倍率下，充放電100次循環(huán)后容量仍可達(dá)到584.4mAh/g；且電極倍率性能良好，在20C倍率下充放電時(shí)，其容量仍可達(dá)到434.6mAh/g。電極循環(huán)性能最優(yōu)的原因在于：電極活性材料內(nèi)部分布有大量的CNTs，內(nèi)阻相對(duì)較小，離子傳導(dǎo)性好；電極內(nèi)部存在一定的孔隙結(jié)構(gòu)，能為錫銅合金在嵌脫鋰過程中的體積變化提供緩沖空間；電極相結(jié)構(gòu)以Cu6Sn5為主，且Sn與Cu3Sn的含量相對(duì)較少。 本文通過設(shè)計(jì)不同結(jié)構(gòu)類型的一體化錫基合金負(fù)極材料，采用廉價(jià)低成本的方法，極大地提升了錫銅合金負(fù)極材料的循環(huán)性能。由于本文采用的是一體化電極材料，減少了冗余的連接成分，因而能提升全電池的體積容量，為該材料的商業(yè)化應(yīng)用奠定了堅(jiān)實(shí)的基礎(chǔ)。
[Abstract]:China attaches great importance to the development of lithium ion battery materials and its key technologies, and puts it into the national medium and long term development plan of science and technology in <2006~2020. At the same time, the rapid development of large traffic tools, such as electric vehicles, hybrid electric vehicles and other large electric equipment, also puts forward the capacity of lithium ion batteries in terms of capacity. Higher requirements. Negative electrode material is one of the key materials affecting the capacity of lithium ion batteries. As one of the outstanding representative of the new anode material, the theoretical mass ratio (993mAh/g) of the tin based alloy negative electrode is nearly three times that of the graphite negative electrode. However, the material is accompanied by a huge volume deformation (260%) during the charge discharge process, which leads to the material. This phenomenon is the key to the market application of tin based alloy negative electrode during charge discharge, which is the key to the market application of tin based alloy negative electrode material. There are many ways to improve the cycle performance of tin based alloy negative electrode material, and the composite of carbon materials is one of the effective ways, and the report of composite with carbon nanotubes is increasing gradually. The integrated electrode material can reduce the redundant connection components (conductive agent and binder) of the traditional electrode in the integration process, thus improving the utilization of space and materials, so the type electrode is also widely used in tin based negative electrode materials.
In this paper, aiming at the commercialization of tin based alloy negative electrode, in view of the above shortcomings of tin based alloy negative electrode, using the idea of integration of fluid collection and active material, using low production cost, simple process electrodeposition and heat treatment process, the electrode of different structure types was prepared, and its microstructure and storage were also made. Lithium properties have been studied. The innovative research results obtained in this paper are as follows:
(1) in order to improve the cyclic performance of the tin copper alloy negative electrode, we formed an integrated Cu6Sn5 alloy negative electrode under the condition of low temperature and short-time heat diffusion treatment based on the multilayer structure of tin / copper alternately. The effects of heat treatment temperature and other parameters on the structure and cyclic properties of the electrode materials were investigated by heat treatment. The results showed that the alloy components formed by the heat treatment of multilayer structure materials were different because of the different atomic activity at different temperatures. The multilayer structure material was treated at 200 degrees C and heat treated for 30min. The optimal electrochemical performance, electrode capacity and the electrode material than the traditional preparation method of the higher cycle is more stable, after 40 cycles, the capacity is higher because of the advantages of traditional tin copper alloy anode electrode is 26.9%. the electrode active material is mainly Cu6Sn5 phase, and the material grains in heat treatment after a little change.
(2) in order to alleviate the material pulverization of tin based anode materials during charging and discharging, based on the high strength and high conductivity carbon nanotubes, we prepared the Sn-CNTs integrated electrode material with the tin metal anode. We prepared the Sn-CNTs composite electrode by composite electrodeposition, and the process parameters for the preparation of the composite electrode were made. The effect of the diameter of CNTs on the performance of the electrode cycle was studied. The results showed that the content of CNTs changed with the current density, and the cycle performance of the electrode with the diameter range of (10~20nm) was the most obvious. The best cycle performance of the electrode was that the CNTs content in the electrode was the highest and the internal resistance was the least.
(3) in order to enhance the combination of fluid collector and active material to further slow the material pulverization of Sn Cu alloy negative material during charge discharge process, based on the Sn-CNTs composite electrode, based on the Cu-CNTs composite coating, the Sn/Cu-CNTs double layer structure electrode was designed to enhance the active material (tin copper alloy) and the fluid collector (copper). Sn-Cu-CNTs integrated electrode materials were obtained by electric connection and final heat treatment. We first prepared Cu-CNTs composite coating on copper foil substrate by electrodeposition, and then electrodeposited a certain thickness of tin coating. Finally, the Sn-Cu-CNTs integrated electrode was obtained by heat treatment. The surface morphology of the composite coating was first studied. The influence of the content of carbon nanotubes was studied. The effect of heat treatment temperature on the electrochemical performance of electrode was studied. The results showed that the morphology and carbon content of the Cu-CNTs composite coating changed with the current density, and the performance of the electrode was the best after heat treatment at 200 c for 6h. The optimal cycle performance of the electrode was the electrode active material crystal. Fine particles are well integrated with the collector. CNTs is tightly linked with active materials, and can play a role in the connection between framework materials and conductive materials.
(4) in order to improve the content of carbon nanotubes in active materials and to improve the cycling performance of tin based alloys, we designed the Sn-CNTs/Cu-CNTs composite electrode by combining the Sn-CNTs active material with the Cu-CNTs connection layer on the basis of the Cu-CNTs connection layer. We used the composite electrodeposition to deposit the Cu-CNTs complex with copper foil as the base. Sn-CNTs/Cu-CNTs composite electrode was prepared by electrodeposition of Sn-CNTs composite coating, and the effect of heat treatment time on the performance of electrode cycle was studied. The results showed that after 6h heat treatment, the cycle performance of the electrode was the best, and the capacity of 100 cycles after charge discharge was 584.4mAh/g at 1C ratio. The performance of the electrode has a good performance. When charging and discharging at the 20C ratio, the capacity of the electrode can still reach the optimal cycle performance of the 434.6mAh/g. electrode. The internal distribution of the electrode has a large number of CNTs, the internal resistance is relatively small, the ionic conductivity is good, and the inner pore structure exists in the electrode, which can be the body of the tin and copper alloy in the process of lithium-ion removal. Product variation provides buffer space; the electrode structure is mainly Cu6Sn5, and the content of Sn and Cu3Sn is relatively small.
In this paper, the cyclic properties of tin copper alloy negative materials are greatly improved by the design of integrated tin based alloy negative materials with different structural types and low cost and low cost. Since this paper uses an integrated electrode material, it reduces the redundant connection components and thus improves the volume capacity of the whole battery as a Merchant of the material. The industrial application laid a solid foundation.
【學(xué)位授予單位】：湘潭大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM912

【共引文獻(xiàn)】

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