硬炭微球的制备及其储锂性能研究

以二乙烯基苯(DVB)为交联剂、偶氮二异丁腈(AIBN)为引发剂、聚乙烯吡咯烷酮(PVP)为模版剂,通过自组装,制备聚苯乙烯微球。经过氧化和高温炭化转换成硬炭微球。考察了硬炭微球作为锂离子负极材料的电化学性能。结果表明硬炭微球的首次放电比容量为505 mA·h/g,40次循环后保持在304 mA·h/g。     

Aromatic carbon coated tin composites as anode materials for lithium ion batteries

Aromatic carbon coated tin composites (A/Sn) have been prepared by thermal decomposition of the stannous 1,8-naphthalenedicarboxylate precursors, which is a reformative preparation method. Sugar carbon coated tin composites (S/Sn) also are prepared as a contrast with the A/Sn composites. The morphology and composition of the products were characterized by Scanning Electricity Microscopy (SEM) and X-Ray Diffraction (XRD). Their electrochemical performance as anode materials for lithium ion batteries were investigated; the results indicated that these materials exhibited good performance, and the cycle stability of A/Sn composites is especially superior to the S/Sn composites due to its special carbon resource.     

锡基复合氧化物负极材料的研究

采用共沉淀法制备了SnFeO2.5和SnPbO2两种锡基复合氧化物粉末.XRD分析表明,这两种锡基复合氧化物在26°～28°处都有波峰,属无定形结构;SEM的形貌观察发现SnFeO2.5颗粒分层紧密堆积、团聚在一起,SnPbO2颗粒为棱柱状、表面光滑.将其分别作为Li+电池负极材料的活性物质,利用恒电流电池测试仪研究它们的电化学性能,发现这两种锡基复合氧化物都有较高的电化学容量.     

稻壳制备锂离子电池负极材料的研究

研究了升温速率、热解温度、碱浓度对稻壳制备锂离子电池负极材料的结构和电化学性能的影响.利用差热-热重(DT-TGA)分析、元素分析、X射线衍射(XRD)等测试手段对不同条件处理后的炭材料进行表征,通过电化学分析其充、放电性能.结果表明:该材料属于无定形炭材料,首次充电容量为678.0 mA·h/ g,首次放电容量为239.0 mA·h/ g,十次循环以后容量基本稳定,可逆容量保持在206.1 mA·h/ g左右.     

Dead lithium phase investigation of Sn-Zn alloy as anode materials for lithium ion battery

In this work, based on First-principle plane wave pseudo-potential method, we have carried out an in-depth study on the possible dead lithium phase of Sn-Zn alloy as anode materials for lithium ion batteries. Through investigation, we found that the phases Li_xSn₄Zn₄(x = 2, 4, 6, 8) contributed to reversible capacity, while the phases Li_xSn₄Zn_8−(x−4)(x = 4.74, 7.72) led to capacity loss due to high formation energy, namely, they were the dead lithium phases during the charge/discharge process. And we come up with a new idea that stable lithium alloy phase with high lithiation formation energy (dead lithium phase) can also result in high loss of active lithium ion, besides the traditional expression that the formation of solid electrolyte interface film leads to high capacity loss. Supported by the National Natural Science Foundation of China (Grant No. 50771046), Natural Science Foundation of Guangdong Province (Grant No. 05200534), Key Projects of Guangdong Province and Guangzhou City (Grant Nos. 2006A10704003 and 2006Z3-D2031) and China Postdoctoral Science Foundation (Project No. 20080440764)     

重新堆积和钴离子掺杂的MoS2负极材料的合成与性能研究

以原料MoS2为前驱体,经正丁基锂剥离和水热处理,制备出重新堆积的MoS2和钴离子掺杂的MoS2.利用XRD、TEM、SEM和EDS等分析手段对样品的形貌和化学组成进行表征.结果表明:重新堆积的MoS2和钴离子掺杂的MoS2的晶型均为2H-MoS2,但结晶度都比原料的差.重新堆积的样品的组成仍为MoS2,Co2+掺杂的...     

Embedding Co3O4 nanoparticles into graphene nanoscrolls as anode for lithium ion batteries with superior capacity and outstanding cycling stability

Co_3O_4 is a promising high-performance anode for lithium ion batteries(LIBs), but suffers from unsatisfied cyclability originating duo to low electrical conductivity and large volume expansion during charge and discharge process. Herein, we successfully constructed the Co_3O_4 nanoparticles embedded into graphene nanoscrolls(GNSs) as advanced anode for high-performance LIBs with large capacity and exceptional cyclability. The onedimensional(1 D) Co_3O_4/GNSs were synthesized via liquid nitrogen cold quenching of large-size graphene oxide nanosheets and sodium citrate(SC) modified Co_3O_4 nanoparticles, followed by freeze drying and annealing at400 °C for 2 h in nitrogen atmosphere. Benefiting from the interconnected porous network constructed by 1 D Co_3O_4/GNSs for fast electron transfer and rapid ion diffusion, and wrinkled graphene shell for significantly alleviating the huge volume expansion of Co_3O_4 during lithiation and delithiation. The resultant Co_3O_4/GNSs exhibited ultrahigh reversible capacity of 1200 mAh g~(-1) at 0.1 C, outperforming most reported Co_3O_4 anodes.Moreover, they showed high rate capability of 600 m Ah g-1 at 5 C, and outstanding cycling stability with a high capacity retention of 90% after 500 cycles. Therefore, this developed strategy could be extended as an universal and scalable approach for intergrating various metal oxide materials into GNSs for energy storage and conversion applications.     

Double carbon decorated lithium titanate as anode material with high rate performance for lithium-ion batteries

Spinel lithium titanate(Li_4Ti_5O_(12)) has the advantages of structural stability, however it suffers the disadvantages of low lithium-ion diffusion coefficient as well as low conductivity. In order to solve issues,we reported a simple method to prepare carbon-coated Li_4Ti_5O_(12)/CNTs(C@Li_4Ti_5O_(12)/CNTs) using stearic acid as surfactant and carbon source to prepare carbon coated nanosized particles. The obtained Li_4Ti_5O_(12) particles of 100 nm in size are coated with the carbon layers pyrolyzed from stearic acid and dispersed in CNTs matrix homogeneously. These results show that the synthesized C@Li_4Ti_5O_(12)/CNTs material used as anode materials for lithium ion batteries, presenting a better high-rate performance(147 m Ahg~(-1)at20 C). The key factors affecting the high-rate properties of the C@Li_4Ti_5O_(12)/CNTs composite may be related to the synergistic effects of the CNTs matrix and the carbon- coating layers with conductivity enhancement. Additionally, the amorphous carbon coating is an effective route to ameliorate the rate capability of Li_4Ti_5O_(12)/CNTs.     

退役三元NCM锂离子电池正极材料资源化回收研究进展

三元镍钴锰酸锂(NCM)电池是一种重要的锂离子电池,具有广阔发展前景和应用价值.本文概括了三元锂离子电池相比传统电池具有的优点,分析了三元电池的组成部分,重点综述了三元正极材料不同回收方法与反应机理,并对NCM三元锂离子电池应用前景作出展望,结合技术创新研发项目的新型工艺路线,有效解决了现有回收方法存在的正极活性物质与铝箔分离困难,以及容易产生二次废液的问题.     

炭气凝胶微球的制备及在锂离子电池负极材料中的应用

以间苯二酚和甲醛为原料,在催化剂和表面活性剂的作用下经溶胶-凝胶、超临界干燥、炭化等过程合成一种新型的炭气凝胶微球。采 用扫描电镜(SEM)、X-射线衍射(XRD)、低温氮吸附（BET）和充放电测试等表征了炭气凝胶微球微观形貌、结构和电化学性能。结果表明:炭气 凝胶微球具有纳米网络结构（孔径集中分布在3.5nm左右）,微球直径≤40μm,比表面积为555m²/g。电化学性能表现出很大的首次不可逆容量 损失,这主要与材料大的比表面积有关。但在首次循环后,具有良好的循环性能,循环20次后可逆充电容量为281mAh/g,循环效率达到100％ 。     

Influence of structure and atom sites on Sn-based anode materials for lithium ion batteries: a first-principle study

To understand the influence of structure and atom sites on the electrochemical properties of Sn-based anode materials,the lithium intercalation–deintercalation mechanisms into SnNi2Cu and SnNiCu2phases were studied using the first-principle plane wave pseudo-potential method.Calculation results showed that both SnNi2Cu and SnNiCu2were unsuitable anode materials for lithium ion batteries.The Sn-based anode structure related to the number of interstitial sites,theoretical specific capacity,and volume expansion ratio.Different atom sites led to different forces at interstitial sites,resulting in variations in formation energy,density of states,and hybrid orbital types.In order to validate the calculated model,the SnNi2Cu alloy anode material was synthesized through a chemical reduction-codeposition approach.Experimental results proved that the theoretical design was reasonable.Consequently,when selecting Snbased alloy anodes,attention should be paid to maximizing the number of interstitial sites and distributing atoms reasonably to minimize forces at these sites and facilitate the intercalation and deintercalation of lithium ion.     

锂离子电池用Si-Fe复合电极材料的制备及其性能

以Fe粉与Si粉为混合粉原料,研究经机械球磨、退火热处理后混合粉的形貌、结构与恒电流充放电性能,同时对比研究Si-Fe合金粉的性能.研究结果表明:混合粉原料经过高能机械球磨,生成了Si-Fe合金相,而Si-Fe合金的生成改善了Si作为锂离子电池负极材料的循环性能;与工业级Si-Fe合金负极材料相比,合金化程度影响了合金材料的电化学性能,合金化程度越高,合金材料电化学性能越好;而退火热处理也可以在一定程度上改善合金材料的脱嵌锂性能.     

锂离子电池核型G@Cu0.85Sn0.15@C负极材料的改性

针对锡负极材料充放电过程中的体积效应,本文综合采用组分改性与结构改性的研究方法,合成Sn-Cu合金负极材料,研究Cu的掺入对Sn电化学稳定性的影响,同时基于优化改性的Sn-Cu合金开展核壳结构设计,研究最佳核壳结构构造工艺。结果表明,掺入Cu能在一定程度上改善Sn的循环稳定性,Sn-Cu样品的容量在60周循环后趋于稳定,库伦效率较高;核壳结构处理能大幅提升Sn-Cu合金负极材料的循环稳定性,采用球形改性天然石墨(d50=15μm)作为内核的样品首次放电比容量接近800mAh/g,充电比容量最大值超过了500mAh/g,100周容量保持率大于85%,最佳的核壳结构构造工艺是使用片状石墨作为内核,内核粒径为d50=15μm,外壳厚度为柠檬酸裂解碳占复合材料质量比的20%。核壳结构能将Sn-Cu合金的体积效应控制在“囚笼”式结构内,利于材料容量的发挥及循环稳定性的提升。核壳结构的可控制备对实现锡基合金负极材料的产业化具有重要的作用。     

Synthesis of amorphous SeP2/C composite by plasma assisted ball milling for high-performance anode materials of lithium and sodium-ion batteries

To promote substantially the performances of red phosphorous(P) anode for lithium and sodium-ion batteries, a simple plasma assisted milling(P-milling) method was used to in-situ synthesize SeP₂/C composite. The results showed that the amorphous SeP₂/C composite exhibits the excellent lithium and sodium storage performances duo to the small nano-granules size and complete combination of selenium(Se) and phosphorous(P) to generate Se–P alloy phase. It was observed that insid...     

锂离子电池锑基负极材料的研究进展

综述了锂离子电池锑基负极材料——金属锑簿膜、锑基合金、锑基复合氧化物的研究进展,重点介绍了锑基合金材料的不同制备方法,并阐述了锑基负极材料的研究进展与开发前景。     

A designed core-shell structural composite of lithium terephthalate coating on Li4Ti5O12 as anode for lithium ion batteries

A core-shell structural composite was synthesized with lithium terephthalate（Li₂C₈H₄O₄） coated on spinel Li₄Ti₅O₁₂（LTO）. The composite displays a capacity of about 200 mA h g^-1 and a good rate capability with two charge/discharge platforms at 1.55 and 0.8 V. The excellent cycling performance of the composite is attributed to the successful combination of high cycling stability of LTO and high specific capacity of Li₂C₈H₄O₄. In addition, an interesting phenomena is observed for the first time for this composite which is that lithium ions transfer between LTO and Li₂C₈H₄O₄ at a fast speed. This is investigated in details via the asymmetric charge/discharge measurement and cyclic voltammogram（CV）.The LTO/Li₂C₈H₄O₄ composite may have potential applications to be used as an anode material for the electric vehicle batteries, which is shallowly charged/discharged at ordinary times using the charge/discharge platform of LTO and fully charged/discharged at emergency to release the extra high capacity from Li₂C₈H₄O₄.     

具有分级结构的Co_3O_4绣球花状微米球的构筑及其锂离子电池负极性能研究

采用溶剂热法合成了绣球花状Co_3O_4纳米材料,并利用扫描电子显微镜和X射线衍射仪进行了微观形貌和结构的表征,结果显示样品的形貌为4~6μm绣球花状分级结构微米球,结晶良好,无杂相生成。该绣球花状Co_3O_4纳米材料用做锂离子电池负极材料时表现出很高的可逆比容量和良好的循环性能。在300 m A/g电流密度下,首次放电比容量达1 508 m A·h/g,经过20次循环可逆比容量为1 300 m A·h/g。其良好的电化学性能归功于绣球花状Co_3O_4材料的独特形貌,其多级结构能够缩短锂离子的传输路径,并且拥有足够大的孔隙,来适应和缓解电极材料在循环过程的体积效应。     

高性能锂离子电池负极材料一氧化锰/石墨烯复合材料的合成

通过冻干-煅烧合成了一氧化锰/石墨烯(MnO/rGO)复合材料,并将其用作锂离子电池负极材料.在500 mA·g-1的电流密度下,MnO/rGO复合材料表现出高达830 mAh·g-1的可逆容量,且在充放电循环160圈后,其可逆容量依然高达805 mAh·g-1.倍率测试结果显示,循环225圈后,在2.0 A·g-1的电流密度下,其可逆容量高达412 mAh·g-1.复合材料中的石墨烯在提高材料导电性的同时有效地缓解了一氧化锰充放电过程中的体积膨胀.通过对比容量-电压的微分分析,发现复合材料超出一氧化锰理论容量的部分是由形成了更高价态的锰引起的.MnO/rGO复合材料比纯一氧化锰(p-MnO)更容易出现高价态的锰,可能是因为rGO上残留的氧为电极反应提供了额外所需的氧源.该一氧化锰/石墨烯复合材料因其简单绿色的合成过程及优异的电化学性质,有望在未来的锂电负极中得到广泛的实际应用.     

中间相沥青基介孔炭的表征及其用作锂离子电池负极材料的电化学性能

以中间相沥青为碳源、CaCO_3为模板,制备中间相沥青基介孔炭(MPMC)。采用XRD、SEM、TEM等手段表征所制介孔炭的结构和形貌,并将其用作锂离子电池的负极材料,测试电化学性能。结果表明,所制MPMC具有丰富的介孔结构和较大的比表面积及孔体积,随着CaCO_3质量分数的增加,MPMC的比表面积和孔体积先增加后减小,当CaCO_3的质量分数为70%时,所制MPMC的比表面积和孔体积最大;MPMC用作锂离子电池负极材料具有良好的电化学性能,能有效提高锂离子电池的可逆比容量,具有良好的循环稳定性和倍率性能。