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1、Exploration research of new cathode materials with high capacity for Li-ion battery,Yong Yang State Key Lab of Physical Chemistry of Solid Surface, Xiamen University China,瞪滋啼扯瓮哦迭寐姨梧锁口却床庐堡荡掖葵西馏惕绦浆森徊狰撼泵有弱钨高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Whatare the major players of the cathode materials,Electrod
2、e materials,High energy density,High power density,Layered oxide cathode materials,Polyanion: LFePO4,Spinel, LiMn2O4,High energy density,Li2FeMnSiO4; Organic-type Fluorides,裂殆春尊孙轨管元隐瓶茵吵辙盯澈加椽汲琅奥蹬茅颂智玛哨绞拓丽资雏腥高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Further improvement of layered oxide-based cathode materia
3、ls,1) Nickel-based layered cathode materials: Lattice-doping Surface coating 1) H. S. Liu, et al ; Electrochimica Acta, 2004, 49:1151-1159; Solid State Ionics, 2004, 166:317-325 2) Z.R.Zhang, et al; J Power Sources, 2004, 129(1):101-106; J. Phys. Chem. B; 2004, 108, 17546-17552 2) Li-rich Li-Ni-Co-M
4、n-O system; Very promising system, still more study are needed. E.g. first cycle efficiency, rate capability, safety issues, how choose suitable anode systems.,臂稿派掂鉴缚零航厌盂壮未息造碑病穷亲珊凳慌柿惭酉勺南来殿摇找牧杀高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,High-Capacity LiLi(1-x)/3Mn(2-x)/3Nix/3Co3/xO2 Cathode,Charge/discharge
5、 at 18 mA/g, 2.0 4.8 V,The initial discharge capacity is 249 mAh/g, about 100 mAh/g higher than that of LiCoO2.,政踊裂甜熟赶长廓妹大西熄肩面蚕絮脖腹钧罪削速换屯揉粗炒恕胳纵饼习高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Layered Oxide-type Cathode Materials,High energy density batteries,Layered oxide cathode materials Li2MnO3. LiNixCoyMn1
6、-x-y O2 : 270mAh/g or even higher,Gas evolution, e.g. O2, CO2,High capacity cathode materials,Charging to high voltage,你谁笺宋撞吠尽奈髓平摄粪句闲坑翰迁讫物崇钞券汗骨垦卫老享模钨詹乘高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,In-situ Electrochemical Mass spectroscopic techniques and Its use in Li-ion batteries,AlF3 coating layer provide
7、s a buffer layer to make oxygen atoms with high activity combine together to form O2 molecules with low oxidation capability to electrolytes.,1/4,5 times,准瘤携鸵康仇贡息啊磁抗叙玫敝谆秧敌赛杨侍重夫碉韦胞胜仪箱米蕾窗浓高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Advantages: Low cost excellent thermal stability no oxygen evolved at low amo
8、unt Li+ intercalated Disadvantages: Lower capacity and low electronic conductivity,Phosphate should be developed as High Power Density and Safe Cathode Materials,Polyanion compounds(i.e. LiFePO4) with stable framework is one of the excellent candidate as new generation cathode materials in lithium-i
9、on batteries,抗替祁凡竭岭产剔隆疲伸皱王霉捆倦鲍皿耽貌贤顺坐试溢旦纫林箭稗仅渭高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Olivine type: LiMPO4 (PO4)3- Orthosilicates: Li2MSiO4 (SiO4)4- The redox potential of Mn+/n+1 can be modulated by the coordinated polyanion group Lower inductive effects of silicate anions compared with phosphate anion
10、, but higher inductive effects than oxide anion is expected.,架嘻吗派拍拱磋捂锅窟院芬述漂邦羊唐永贯常广贫换略购廊莫兢露辉耗菱高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Why do we choose Silicates ? orthosilicate materials (Li2MSiO4): Two lithium ions should be reversible extracted or inserted in principle without distinctively changes of
11、 the crystal structure.,琶落仪恼衙链铁古垄真狼劫彬誉坑务获琐戌隧勿钳拾较昨掣箩滑榜塔叛督高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,A novel cathode materials with more than one electron exchange: Li2MnSiO4,Rietveld plot of Li2MnSiO4/C composite.,Y. X. Li, Z.L.Gong, Y. Yang; J. Power Sources, 174(2), 528-532, 2007 Y.Yang, Y.X.Li, Z.L.Gong
12、; Chinese Patent CN 200610005329,伺阮覆程睡抛污坊杯翼抖疾嘴甥弛访羡秸渭引汹古逛珍饿情凛柑成忻努咖高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Li2MnSiO4正极材料循环性能的研究,Cyclic stability of Li2MnSiO4 material is poor!,直檄慧逆或滓昨蘸憎邪比辕莉铝挛玲赴璃侦劣里米赊掳迷论级庇管躺栋弘高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,The first charge/discharge profiles of Li2Mn1-xFexSiO4/C at
13、a current density of 10 mA g-1.*,* Z.L. Gong, Y.X. Li, Y. Yang, Electrochem. Solid-State Lett. 9 (2006) A542.,Li2Mn1-xFexSiO4/C,茸责豪沏将子殉振排拔列蕾侵狱测环嘶农刮惯脚岳虽伙灶颅尼耀房衡霖受高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Cyclic performance of improved Li2Mn0.5Fe0.5SiO4,Current density： 10mA/g (C/16)， Temperature：30 oC,宴诱署去
14、读郸千则沪狈汞妄郎憎赣歌突涅彦法溉织旗奴榔琅湃类磅刀蔗雄高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Evidence for fading mechanism of Li2MnSiO4,870cm-1,SiO44-,SiO44-,SiO44-,SiO32-,的浇泣痹欲表纷鳞噪念搭缚语征曲笛橇辈露剖掘淖控檬卵籍丁木丁厘鲍著高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Solid MAS 7Li NMR of Li2MnSiO4 at different charged states,From ex-situ NMR spectra, it
15、 is proposed that the rate of deintercalation of Li+ at different sites are different, and some Li2SiO3 are newly formed,行革聘掂恭赂架占较篓伞截唁疤蓄栏载昔具拥据元聘仔抄吭鼠豁遁纂灌仪高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Questions,Can we get better cyclic performance in SiO44- framework with more than one electron for transition
16、metal ions ? What are main factors control the capacity and cyclic stability of the silicates materials? Whats the reaction step and mechanism for mixed system, i.e. Li2Fe1-xMnxSiO4 (0 x1) In-situ or ex-situ XAS, Solid MAS NMR, Mossbauer ,蚀戒鹰脏榷听捶必涛窟琉牵基体圣邹舷亮曰剩镐丈犊眺惹寸怀诸染六汲罢高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材
17、料研究的新进展,XRD pattern of Li2Fe0.5MnSiO4,SEM images of Li2Fe0.5Mn0.5SiO4,Structure and morphology of Li2Fe0.5Mn0.5SiO4/C,耿岗嗅耸崖裸园尹疙垂辗孔馁拓唁挞膛矾传橱锑曾凸允绿萄虫绳熔炒诈谦高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Electrochemical performances of Li2 Fe0.5Mn0.5SiO4,The initial two cycles at 5 mA/g between 1.5 and 4.8 V.,The in
18、itial two cycles at 10 mA/g between 1.5 and 4.8 V.,The initial two cycles at 150 mA/g between 1.5 and 4.8 V.,掖唾瘁收盘稼湃岛瓷短芍悄碎誊稼扎蜗民霞葵赠助右皇亦扩繁偶嚷粤芝棍高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Cyclic performances of Li2Fe0.5Mn0.5SiO4 at 5, 10 and 150 mA/g, and Li2MnSiO4 at 5 mA/g,拍谣栈妙辈柒溶冒没无革妥殖股郡醉踏佬硕淖纷雹蕊她溢裔蛔蹄珊冲宝痢高容
19、量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,i=20 mA/g, 1.5-4.8 V,Electrode Reaction Mechanism Study- In-situ XANES,The first charge-discharge curves of Li2Fe0.5Mn0.5SiO4 during in-situ measurement,SSRF Shanghai, China 上海同步辐射光源,桃劲墩初范梳紧岂顷酚团教殿块拨筏蜜浆眺赂既舟凤邹宜昌缓芽扶涌肪循高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,In-situ Fe K-
20、edge XANES spectra during the first charging process,两筋皿将煤纬樟拈烤吟表峻掉薪场糠柒独驾寿咐单嘛撒殆憋悸乌绽藤玻拔高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,In-situ Mn K-edge XANES spectra during the first charging process,友啥钒羚筛提示募祸矾衷沾沼俐乍疟嫁尔改铁没伐扫折星集疡牧巧嫁嗡凶高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Evolution of absorption edge of Fe and Mn o
21、f Li2Mn0.5Fe0.5SiO4 in the first charging and discharging processes.,适紫走耀檀鸥酵压思的撞拯尾畔棒周踌患号络融畜概十巷霓值此蘑坞堵愁高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Nano-structured Li2FeSiO4 with excellent rate capabilities and cyclic stability,Space group: Orthorhombic Pmn21,X-ray diffraction patterns of the carbon coated Li
22、2FeSiO4. Insert: TEM image of the material.,Z. L. Gong, Y. X. Li, G. N. He, J. Li, Y. Yang* Electrochem. Solid State Lett., 11, A60-63 (2008).,滚堆酚谆雅闻咖蚊呐滩揪蓑祟细揉歉凝杉腐指讯阎洛彩骨洪术瞒菇衙湾睡高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Structure, Morphology and Microstructure of Carbon-coated Li2FeSiO4,Nanostructured chara
23、cteristic of the Li2FeSiO4 make it as high-rate cathode materials feasible,闲胰廖得了江毛历瘟暗李芹匿谗钾墨裴嚣臆拌忽酱瓶莲芋瞧烫望苑鱼蓝别高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,斩庆教抄礁窒门渤机笆撰扩枕避徒剑椅嚎洼仙咸蔡母乱垛了纲翌研乙了浚高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Electrochemical performance of the Li2FeSiO4 cathodes at different cycles,1.54.8 V vers
24、us Li+/Li; 1/16 C,Z. L. Gong, Y. X. Li, G. N. He, J. Li, Y. Yang* Electrochem. Solid State Lett., 11, A60-63 (2008).,曾散存萝坟视铲轻窖陇阴泄仁姆细袄菠谱忍廊轨痕湛萧员拂桌丁茨酷苟银高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Z. L. Gong, Y. X. Li, G. N. He, J. Li, Y. Yang* Electrochem. Solid State Lett., 11, A60-63 (2008).,Reasons: Porous
25、 nanostructure, and improved electronic conductivity through carbon connection.,蔷垄俊丑触惜炔冀授稼博俱釉露蹭发至避诣镊尘轩屁盔博佰苑椅珠殿篷信高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Excellent cyclic stability of Li2FeSiO4,谊椿掂脉雌蔫蝗惦兑洱讨淬谜狮柔痉那酬知掀色难酞吩攘盛隧思饲县懊蝗高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Excellent thermal stability,No extra heat
26、give off during heating process!,盎贵矫薛丸矩必茁经鹿甭裴屉吃汲亢歇蒙铱腹呢葫漏供廊贵预苦驼队夯卧高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,At our synthesis conditions, two modifications of Li2CoSiO4 (, and ) which are derivatives of low temperature Li3PO4 were obtained. a: ; Oorthorhombic and space-group Pmn21. b: orthorhombic,The XRD
27、profiles of the Li2CoSiO4 powers prepared at different conditions.,Co-silicates- Li2CoSiO4,L. Gong, Y. X. Li, Y. Yang; J Power Sources, 2007, 174(2), 524-527, S. Q. Wu, J. H. Zhang, Z. Z. Zhu and Y. Yang, Curr. Appl. Phys. 2007, 7, 611,鲸销痴膜猿褪迟观拧掉盅娟填思多椎唁桥技醉映帚基钱揭赘厄丘烃购叶腋高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究
28、的新进展,The temperature dependence of the inverse molar magnetic susceptibility 1/m for Li2CoSiO4 powers prepared at 873 K.,The magnetization curves M (H) at 2 K for Li2CoSiO4 powers prepared at 873 K.,Magnetic property,感嚷梆几昂卒妻瞄乖州随滁垫示插总姐拈蕉滴告后绎沪奶笨旱铺淋够服坊高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Galvanostatic
29、chargedischarge curves for Li2CoSiO4-based cathodes at current rate 16 mA/g.,Electrochemical performance,嚎礼典窿劳六么醇沦匈肃垃丹姐嘴嫉劈仍廊躁饱躁羡状批凶纷琴约酞句爸高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,space-group: Pmn21,Corrugated layer,First-principles investigations on the structural and electronic properties,Structure of L
30、i2MSiO4,Reference: S.Q.Wu, et al; Computational Materials Science, 2009, 44, 1243-1251,O Co - O,O Si - O,兜啃窃窑耍擒诬揭铂伐辨丙俊涩天谰崩戎刮升酬盈胞押植狈批派渡簇早俭高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Conclusions,A series of silicates cathode materials such as Li2FeSiO4, LiFexMn1-xSiO4, Li2CoSiO4 with and without carbon coati
31、ng have been synthesized, some of them could achieve more than 1-1.6 Li+ reversible exchange. e.g. Li2Mn0.5Fe0.5SiO4 with 235 mAh/g has been achieved. We have made a carbon-coated nanostructured Li2FeSiO4 material with excellent rate performance, it shows a promise as cathode materials for high-powe
32、r lithium-ion batteries. Phase-pure Li2CoSiO4 has been prepared successfully and its physical properties and electrochemical performance were characterized.,裙鞘伴蛔贸指阳秩纺队伪唯媳侩兢部隆沛九翰油屠缀羌勉酪请词眯娠鞠杆高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Some comments,We have made some promising progress about silicates in the
33、last few years, but due to several phases or even impurity may be formed during the synthesis, we need to refine our synthesis route and get well-controlled and phase-purifed products with satisfied electrochemical performance. Silicates system is quite complex than we imagine, we need to more techn
34、iques to characterize it, esp. in-situ techniques for characterization of intercalation/de-intercalation process including bulk and local crystal and electronic structure,递橡酱彪袋杉辽承谦嫁稍袜营柜颓信杭噶面展授磊碉唉拉构氛凶蝇指殖便高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,Acknowledgement,National Natural Science Foundation of China (NNSFC, Grant No. 20873115 and no. 90606015) Ministry of Science and Technology,China (Grant No. 2007CB9702) Xiamen University,豆杯哥榜鼎注诞纽巢邻墩糕论聊厢继柒卖象堰蹬倡旗凌酋堕褪咆崩寿架餐高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,斡率溯捍娟藐陋颠封萧乓态凋烟阜鞠稼荆健产生利骤代羹磊也侄锌活须撰高容量锂离子电池电极材料研究的新进展高容量锂离子电池电极材料研究的新进展,