商用石墨陽(yáng)極的理論容量有限(372 mAh/g)和嵌鋰電位較低，已經(jīng)不能滿足新型鋰離子電池(LIBs)的需求 因此，開發(fā)和制備具有更高容量和安全性的新型負(fù)極材料(如Si、Ge、Sn、SnO2、Fe2O3、GeO2、MnO2和MoP等)取代石墨極為迫切[1] SnO2具有理論容量高(780 mAh/g)、低毒性和低成本的優(yōu)點(diǎn)，是一種很有前途的負(fù)極材料[2~4] 但是，在脫鋰/嵌鋰過(guò)程中SnO2較大的體積變化引起顆粒粉化和聚集，使純SnO2負(fù)極的倍率能力和循環(huán)性能降低[5,6] 盡管如此，設(shè)計(jì)和制備納米SnO2@C復(fù)合材料可提高其倍率性能和循環(huán)性能，因?yàn)樘坎牧峡商岣唠姌O的導(dǎo)電性，而納米級(jí)尺寸可縮短離子和電子的傳輸路徑，從而緩解SnO2在長(zhǎng)期循環(huán)過(guò)程中體積變化的影響[7~10] 常見的炭基材料，包括非晶無(wú)定形炭、炭納米管和石墨烯等 以炭材料為基體可制備出不同形貌的SnO2/C復(fù)合材料，如SnO2/C納米纖維[11]、SnO2/C納米孔炭微球[12]、SnO2/核殼結(jié)構(gòu)微球[13]、蜂巢納米片結(jié)構(gòu)的SnO2/石墨炭復(fù)合物[14]等 這些材料不僅儲(chǔ)鋰性能較高，在充放電過(guò)程中很少發(fā)生團(tuán)聚，而且首次充放電效率也較高，可逆放電容量均高于純納米氧化錫，具有良好的循環(huán)性能 目前存在的問(wèn)題有:(1)最常用的炭基材料碳納米管和石墨烯[15~18]，其理論儲(chǔ)鋰容量遠(yuǎn)低于錫氧化物，因此較高比例的炭影響復(fù)合材料的容量；若炭的比例過(guò)低則不能為錫氧化物提供穩(wěn)定的生長(zhǎng)網(wǎng)絡(luò)；(2)石墨烯基體的成本較高，石墨烯片強(qiáng)烈的π-π堆積效應(yīng)使其在循環(huán)過(guò)程中團(tuán)聚，影響復(fù)合材料的循環(huán)性能；(3)兩者較高的成本不利于大規(guī)模制備SnO2@C

糖類炭材料熱解后形成無(wú)定型的硬炭，其結(jié)構(gòu)優(yōu)勢(shì)使其理論容量為石墨材料的兩倍(782 mAh/g)[19] 圖1給出了近年來(lái)SnO2基鋰離子電池陽(yáng)極材料的循環(huán)次數(shù)和容量[20] 鑒于此，本文以兩種常見的糖類前驅(qū)物[C6H10O5]n葡萄糖(n=1)與淀粉(n>20)為碳源材料用簡(jiǎn)單的一步水熱法來(lái)制備SnO2@C復(fù)合材料，探討以硬炭為基體制備高容量、高倍率SnO2@C材料的可行性

圖1



圖1近年來(lái)SnO2基鋰離子電池陽(yáng)極材料的循環(huán)次數(shù)和容量報(bào)道[20]

Fig.1Capacities and cycle numbers of SnO2-based materials as anodes for LIBs reported in the recent literature[20]

1 實(shí)驗(yàn)方法1.1 試樣的制備

將1 g糖類前驅(qū)體和3.24 g SnCl4·5H2O溶解到80 mL去離子水中并將得到的溶液轉(zhuǎn)入100 mL水熱反應(yīng)釜，將溫度升高到180℃靜置12 h后隨爐冷卻 釜中的溶液變?yōu)樽厣?，?nèi)有黑褐色沉淀物 在真空抽濾器中用去離子水對(duì)沉淀物進(jìn)行充分洗滌和抽濾直至變成中性 在80℃干燥箱中將沉淀物烘干后再轉(zhuǎn)入真空管式爐，通入氬氣氣氛后在300℃下預(yù)分解2 h，然后在500℃燒結(jié)5 h，得到最終產(chǎn)品 將以葡萄糖為前驅(qū)體的試樣命名為TOC-G，以淀粉為前驅(qū)體的試樣命名為TOC-S

1.2 電極的制備

取質(zhì)量比為8:1:1的電極材料、Super P和海藻酸鈉 將粘結(jié)劑海藻酸鈉溶解在去離子水中，再加入混合好的電極材料與導(dǎo)電劑Super P，將其均勻涂布在Cu箔上 將其烘干后沖制成直徑為14 mm的電池正極片 以鋰片為對(duì)電極，在Ar保護(hù)氣氛的手套箱中裝配成2016型扣式電池 使用的隔膜為Celguard2400，電解液為1.3 mol/L LiPF6的EC/DMC(1:1)溶液

1.3 性能表征

用Bruke D8 ADVANCE X射線衍射儀進(jìn)行XRD分析；用Hitachi SU8220掃描電鏡和FEI Tecnai G2透射電鏡分析復(fù)合材料的形貌；用Micromeritics ASAP2020分析儀進(jìn)行N2吸脫附分析和孔徑分析；用Thermofisher Escalab 250Xi X射線光電子能譜儀測(cè)試XPS譜；在LAND-CT2001A電池測(cè)試系統(tǒng)上進(jìn)行恒電流充放電測(cè)試；使用CHI660C型電化學(xué)工作站進(jìn)行EIS與CV分析

2 結(jié)果與討論2.1 元素分析與孔徑分布

圖2給出了兩種試樣的XRD圖譜，可見所有衍射峰與金紅石型SnO2完全吻合(PDF #41-1445)，屬于空間群P42/mnm，a=b=0.4738 nm，c=0.3187 nm，晶胞體積0.716 nm3 兩個(gè)最強(qiáng)的主峰(26.4°與34.0°)對(duì)應(yīng)SnO2的(110)與(101)晶面，晶面間距分別為0.33 nm與0.26 nm 使用Jade軟件分析發(fā)現(xiàn)，兩主峰的峰強(qiáng)之比分別為91.8:100與71.6:100，其原因是葡萄糖熱解炭與淀粉熱解炭的結(jié)晶程度不同 碳的主要衍射峰位于26.6°，可見TOC-G的XRD圖譜上疊加了更強(qiáng)的碳衍射峰，即葡萄糖熱解硬炭比淀粉熱解硬炭的結(jié)晶度和有序度更高，導(dǎo)電性能更好

圖2



圖2TOC-G和TOC-S的XRD圖譜

Fig.2XRD patterns of TOC-G and TOC-S

圖3a給出了TOC-G與TOC-S的紅外光譜，用于分析分子中含有的化學(xué)鍵或官能團(tuán)信息 1162 cm-1處的尖銳峰對(duì)應(yīng)-C-OH基團(tuán)中的彈性拉伸，2957與3470 cm-1處的寬峰對(duì)應(yīng)-COOH與-OH基團(tuán)的振動(dòng)，這些官能團(tuán)在電沉積過(guò)程中為SnO2納米顆粒的附著提供缺陷位置[21] 含氧基團(tuán)將Sn4+氧化為SnO2晶核并在500℃結(jié)晶生長(zhǎng)為SnO2納米顆粒，但它與Li+發(fā)生不可逆結(jié)合而影響復(fù)合材料的首次充放電效率 1280和1630 cm-1處的峰為C-C與C=C的拉伸鍵，分別代表sp3雜化與sp2雜化 紅外光譜表明，淀粉熱解后形成的炭以sp3鍵合為主，也有部分炭原子以sp2方式互相鍵合；而葡萄糖糖熱解炭中sp2的比例非常少，表明葡萄糖熱解炭的有序程度相對(duì)更高，導(dǎo)電性更好 這在兩種試樣的HRTEM照片中也可看出

圖3



圖3試樣的紅外光譜(a)、N2吸脫附曲線和孔徑分布(b)

Fig.3FTIR patterns (a), N2 adsorption/desorption curve and pore distribution (b)

圖3b給出了TOC-G與TOC-S的N2吸脫附曲線和孔徑分布(>10 nm的孔很少，圖中沒(méi)有)，兩者的比表面積分別為280.3 m2/g和348.0 m2/g 兩者的吸脫附曲線均為典型的I型曲線(微孔型)，微孔較多的原因是微孔內(nèi)的強(qiáng)勢(shì)吸附使低壓端靠近Y軸 中壓端多為N2在介孔孔道內(nèi)的冷凝積聚 圖中可見中壓端的N2吸附量變化不大，說(shuō)明兩種材料中介孔比例都很少，以微孔為主，其中葡萄糖熱解炭幾乎沒(méi)有介孔 高壓端的上揚(yáng)程度可用來(lái)判斷粒徑的均勻程度，上揚(yáng)程度越高則粒徑越不均勻 從孔徑分布圖可以看出，TOC-G的孔類型為直徑0.8 nm左右的超微孔，而TOC-S則主要為直徑1~2 nm的微孔以及少量的介孔 微孔的數(shù)量影響電極材料的平臺(tái)容量，圖6中的充放電曲線也體現(xiàn)了這一點(diǎn)[22]

圖4



圖4TOC-G(a)和TOC-S(b)的TEM和HRTEM照片

Fig.4TEM and HRTEM images of TOC-G (a) and TOC-S (b)

圖5



圖5試樣的循環(huán)性能(a)和倍率性能(b)

Fig.5Cycle (a) and rate (b) performance of samples

圖6



圖6TOC-G 和TOC-S 的充放電曲線以及鋰離子在炭基體中的插層和吸附示意圖

Fig.6Charge/discharge curve of TOC-G (a) and TOC-S (b), sketch map of Li+ insertion and absorption in carbon matrix (c)

2.2 微觀結(jié)構(gòu)分析

圖4給出了復(fù)合材料的TEM與HRTEM圖譜 可以看出，兩種試樣均為團(tuán)絮狀結(jié)構(gòu)，SnO2顆粒與熱解炭之間沒(méi)有明確的界限 用DigitalMicrograph透射電鏡分析軟件分析HRTEM照片，發(fā)現(xiàn)主要存在0.26 nm與0.33 nm兩種晶面間距，XRD數(shù)據(jù)表明其對(duì)應(yīng)于SnO2的(101)與(110)晶面 這表明，HRTEM圖譜中球形的、直徑5 nm左右的顆粒為SnO2納米點(diǎn)，周圍包裹的無(wú)定型結(jié)構(gòu)即為炭基體

兩種試樣的差別在于TOC-G的SnO2納米點(diǎn)粒徑稍小 5點(diǎn)測(cè)量的平均值表明，TOC-G的平均粒徑為4.74 nm，TOC-S為5.62 nm 用作鋰離子電池負(fù)極材料，SnO2具有高容量、低成本的優(yōu)勢(shì)，但是它在循環(huán)過(guò)程中體積膨脹引起的粉化和破碎使其循環(huán)性能極差，達(dá)不到使用要求 本文使用的糖類前驅(qū)體熱解產(chǎn)生的炭基體起物理緩沖作用，而且粒徑極小的SnO2納米點(diǎn)具有更高的比表面積，可增加鋰/鈉離子進(jìn)入活性物質(zhì)的途徑，縮短鋰離子的傳輸路徑，這兩者協(xié)同作用能調(diào)節(jié)充放電過(guò)程中活性SnO2材料的體積膨脹，從而提高快速充放電能力與循環(huán)性能

2.3 電化學(xué)性能分析

以TOC-G和TOC-S為負(fù)極裝配的CR2016扣式電池其循環(huán)性能和倍率性能，如圖5a所示 可以看出，200次循環(huán)后(電流密度200 mA/g)TOC-G的放電比容量由1099.5 mAh/g降至732.9 mAh/g，TOC-S的放電比容量由948.6 mAh/g降至509 mAh/g，容量保持率分別為66.6%和53.8% 前文的分析表明，以葡萄糖為炭前驅(qū)體的TOC-G試樣其炭基體的有序化程度更高，SnO2納米點(diǎn)的粒徑更小，因此鋰離子在顆粒中的傳輸更快，SnO2的體積膨脹效應(yīng)更小，因此具有更好的循環(huán)性能 純SnO2前50次循環(huán)容量保持率低于50%，178次循環(huán)后容量衰減為零[22] Zhang等[24]制備的SnO2/石墨烯復(fù)合物循環(huán)100次后容量保持率約為60%，其他文獻(xiàn)的數(shù)據(jù)略低[25, 27] 試樣的倍率性能如圖5b所示，可見前10個(gè)循環(huán)衰減明顯，這是固態(tài)電解質(zhì)膜(SEI)的形成以及Li+與含氧基團(tuán)的不可逆反應(yīng)造成的 在隨后的循環(huán)中容量的保持率較好，電流密度達(dá)到2 A/g時(shí)容量大于400 mAh/g，且TOC-G的容量略高于TOC-S 在此電流密度下一次充放電時(shí)間約為10 min，即充放電倍率為12C，已經(jīng)遠(yuǎn)高于目前對(duì)商用鋰離子電池高倍率充放電的要求(5C)

本文負(fù)極材料電化學(xué)性能的提高得益于炭材料充當(dāng)了錨定和分離SnO2納米粒子的主體，均勻致密的碳基體緩沖了SnO2在鋰/脫鋰過(guò)程中的體積膨脹，促進(jìn)了電子的傳輸，穩(wěn)定了電極結(jié)構(gòu)；其次，SnO2顆粒納米化使鋰離子和電子轉(zhuǎn)移距離較短，Sn/Li2O界面間的互擴(kuò)散動(dòng)力學(xué)加強(qiáng)，從而提高了電化學(xué)反應(yīng)的可逆性，提高了循環(huán)性能

圖6a、b給出了兩種試樣不同循環(huán)次數(shù)的充放電曲線，其中加粗線為首次充放電曲線 由于SEI的形成和Li+與含氧基團(tuán)的不可逆反應(yīng)，兩者的首次庫(kù)倫效率(ICE)都較低，分別為66.5%與64.5% 首次庫(kù)倫效率與負(fù)極材料的燒結(jié)溫度相關(guān)，燒結(jié)溫度高于900℃后炭氧鍵斷裂使大量含氧基團(tuán)消失，使首次庫(kù)倫效率明顯提高[28] 但是溫度高于700℃時(shí)SnO2被炭還原為單質(zhì)[29, 30]，在充放電過(guò)程中體積的膨脹更為嚴(yán)重，因此本文選擇的熱解溫度為500℃ 文獻(xiàn)[30]表明，在充放電曲線的斜坡區(qū)域代表Sn的合金化反應(yīng)與鋰離子在碳層中的插層 插入/脫出電勢(shì)隨著Li+含量的增加而降低，因而形成斜坡；平臺(tái)區(qū)域代表Li+在微孔中的脫嵌過(guò)程，低電位平臺(tái)可以歸因于Li+吸附到隨機(jī)堆積的碳層之間的納米孔隙中 Li+被吸附到化學(xué)勢(shì)接近其本身的位置從而其電位接近0 V(圖6c) 隨著循環(huán)次數(shù)的增加平臺(tái)容量逐漸變少，尤其是TOC-S第200次循環(huán)時(shí)平臺(tái)容量幾乎為0 這也是TOC-S的循環(huán)性能不如TOC-G的原因 由孔徑分布曲線可見，TOC-S的微孔直徑大于TOC-G而能吸附更多的Li+ 可以推測(cè)，孔道深處吸附的Li+會(huì)形成團(tuán)簇，且因傳輸距離更遠(yuǎn)而逐漸失去電化學(xué)活性，造成容量的損失

圖7給出了兩種試樣的循環(huán)伏安曲線，掃描速率為0.03 mV/s，曲線上不同峰位所代表的電化學(xué)反應(yīng)如圖上的標(biāo)識(shí) 在首次CV曲線上，0.6~0.8 V之間的兩個(gè)明顯的陽(yáng)極峰對(duì)應(yīng)SEI膜的形成和部分不可逆反應(yīng)(標(biāo)識(shí)①)；0 V附近的陽(yáng)極峰代表Sn與Li+的可逆反應(yīng)(Sn+xLi++xe-→LixSn(0≤x≤4.4))和Li+在炭層中的插入(xLi++C+xe-→LixC)(標(biāo)識(shí)②) 在SnO2的放電過(guò)程中鋰先與氧結(jié)合形成無(wú)定形的Li2O而金屬錫被還原出來(lái)分散在無(wú)定型的Li2O網(wǎng)格中，無(wú)定型的網(wǎng)格起緩沖介質(zhì)的作用；隨后鋰與錫發(fā)生合金化反應(yīng)，生成LixSn；標(biāo)識(shí)③、④、⑤則代表SnO2電極的充電電化學(xué)反應(yīng):③對(duì)應(yīng)完全可逆反應(yīng)LixSn→Sn+xLi++xe-，④、⑤對(duì)應(yīng)Sn+2Li2O→SnO2+4Li++4e-，但這個(gè)反應(yīng)的可逆性尚有爭(zhēng)議[32, 34] 有研究表明，對(duì)于微米級(jí)SnO2此反應(yīng)是不可逆的，因此理論容量約為780 mAh/g；而納米級(jí)SnO2則是可逆或部分可逆的，理論容量最高可達(dá)1494 mAh/g 本文中的循環(huán)伏安曲線出現(xiàn)明顯的寬峰，說(shuō)明材料在此反應(yīng)上確實(shí)是可逆的，且TOC-G的可逆性更好 標(biāo)識(shí)⑥代表Li+在碳層中的脫出過(guò)程，也是完全可逆的

圖7



圖7TOC-G試樣(a)和TOC-S試樣(b)的循環(huán)伏安曲線(前三次循環(huán)和第100次循環(huán))

Fig.7Cyclic voltammetry curves (the first three cycles and the 100th cycle) (a) TOC-G, (b) TOC-S

3 結(jié)論

以糖類有機(jī)物葡萄糖和淀粉為炭前驅(qū)體，用一種簡(jiǎn)單方法可合成SnO2@C復(fù)合物TOC-G和TOC-S 復(fù)合物的微觀結(jié)構(gòu)是，SnO2納米點(diǎn)嵌在團(tuán)絮狀的炭基體上形成了穩(wěn)定的復(fù)合結(jié)構(gòu) 兩種復(fù)合物的表面均有豐富的微孔，其中TOC-G上的微孔直徑小于0.8 nm，TOC-S上的微孔以1~2 nm為主 微孔較大時(shí)，鋰離子容易在微孔中發(fā)生不可逆沉積從而影響循環(huán)性能 TOC-G的循環(huán)性能略優(yōu)于TOC-S，200次循環(huán)后的容量保持率為66.6%，倍率性能也較好，在2 A/g的大電流密度下其容量約為435 mAh/g

參考文獻(xiàn)

View Option 原文順序文獻(xiàn)年度倒序文中引用次數(shù)倒序被引期刊影響因子

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用直流電弧等離子體法制備金屬鉬納米粉體再使其與赤磷發(fā)生固相反應(yīng),用兩步法制備出磷化鉬納米粒子 使用X射線衍射(XRD)和透射電鏡(TEM)等手段表征磷化鉬納米粒子的結(jié)構(gòu)并進(jìn)行了電化學(xué)性能測(cè)試 結(jié)果表明,MoP納米粒子呈球狀,粒徑為20~50 nm；在電流密度為100 mA/g的條件下MoP納米粒子負(fù)極材料的首次放電比容量達(dá)到746 mAh/g,50次循環(huán)后放電比容量為241.9 mAh/g；電流密度為2000 mA/g時(shí)放電比容量為99.90 mAh/g,電流密度恢復(fù)到100 mA/g其放電比容量仍然保持247.60 mAh/g 用作鋰離子電池的負(fù)極材料,MoP納米粒子具有優(yōu)異的穩(wěn)定性和可逆性

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用直流電弧等離子體法制備金屬鉬納米粉體再使其與赤磷發(fā)生固相反應(yīng),用兩步法制備出磷化鉬納米粒子 使用X射線衍射(XRD)和透射電鏡(TEM)等手段表征磷化鉬納米粒子的結(jié)構(gòu)并進(jìn)行了電化學(xué)性能測(cè)試 結(jié)果表明,MoP納米粒子呈球狀,粒徑為20~50 nm；在電流密度為100 mA/g的條件下MoP納米粒子負(fù)極材料的首次放電比容量達(dá)到746 mAh/g,50次循環(huán)后放電比容量為241.9 mAh/g；電流密度為2000 mA/g時(shí)放電比容量為99.90 mAh/g,電流密度恢復(fù)到100 mA/g其放電比容量仍然保持247.60 mAh/g 用作鋰離子電池的負(fù)極材料,MoP納米粒子具有優(yōu)異的穩(wěn)定性和可逆性

[2]

Idota Y, Kubota T, Matsufuji A, et al.

Tin-based amorphous oxide: a high-capacity lithium-ion-storage material

[J]. Science, 1997, 276: 1395

[3]

Wang C, Zhou Y, Ge M Y, et al.

Large-scale synthesis of SnO2 nanosheets with high lithium storage capacity

[J]. J. Am. Chem. Soc., 2010, 132: 46

PMID " />

We report the creation of a nanoscale electrochemical device inside a transmission electron microscope--consisting of a single tin dioxide (SnO(2)) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO(2)) cathode--and the in situ observation of the lithiation of the SnO(2) nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a

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Wang W C, Li P H, Fu Y B, et al.

The preparation of double-void-space SnO2/carbon composite as high-capacity anode materials for lithium-ion batteries

[J]. J. Power Sources, 2013, 238: 464

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Zhao Y, Wei C, Sun S N, Wang L P, et al.

Reserving interior void space for volume change accommodation: An example of cable-like MWNTs@SnO2@C composite for superior lithium and sodium storage

[J]. Adv. Sci., 2015, 2: 1500097

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Ju H S, Hong Y J, Cho J S, et al.

Strategy for yolk-shell structured metal oxide-carbon composite powders and their electrochemical properties for lithium-ion batteries

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Zhang X Q, Huang X X, Geng X, et al.

Flexible anodes with carbonized cotton covered by graphene/SnO2 for advanced lithium-ion batteries

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Lu J, Peng Q, Li Y D.

Synthesis of iron oxide-tin oxide-carbon composite nanobelts and their applications in lithium-ion batteries

[J].Chin. Sci. Bull., 2013, 58: 3213

(

陸君, 彭卿, 李亞棟.

氧化鐵-氧化錫-碳復(fù)合納米帶的合成及其在鋰電池中的應(yīng)用

[J]. 科學(xué)通報(bào), 2013, 58: 3213)

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Yang Z X, Du G D, Guo Z P, et al.

Easy preparation of SnO2@carbon composite nanofibers with improved lithium ion storage properties

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Lin Y S, Duh J G, Hung M H.

Shell-by-shell synthesis and applications of carbon-coated SnO2 hollow nanospheres in lithium-ion battery

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Cover feature: core-shell structure of SnO2@c/PEDOT: PSS microspheres with dual protection layers for enhanced lithium storage performance (ChemElectroChem 8/2019)

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Wang H K, Wang J K, Cao D X, et al.

Honeycomb-like carbon nanoflakes as a host for SnO2 nanoparticles allowing enhanced lithium storage performance

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Li S, Yang Z X, Guo T L, et al.

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[J].Chin. J. Vac. Sci. Technnol., 2013, 33: 1260

(

李松, 楊尊先, 郭太良等.

一步水熱法合成CNTs/SnO2@C一維殼核結(jié)構(gòu)復(fù)合納米材料及其鋰存儲(chǔ)特性研究

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Synthesis and electrochemical performance of SnO2/Graphene anode material for lithium ion batteries

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(

虞禎君, 王艷莉, 鄧洪貴等.

SnO2/石墨烯鋰離子電池負(fù)極材料的制備及其電化學(xué)行為研究

[J]. 無(wú)機(jī)材料學(xué)報(bào), 2013, 28: 515)

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[本文引用: 3]

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Carbon-confined SnO2-electrodeposited porous carbon nanofiber composite as high-capacity sodium-ion battery anode material

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PMID " />

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PMID

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MoP納米粒子鋰離子電池負(fù)極材料的制備及其電化學(xué)性能

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